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Sample records for formation reactions progress

  1. The Progression of Sequential Reactions

    Directory of Open Access Journals (Sweden)

    Jack McGeachy

    2010-01-01

    Full Text Available Sequential reactions consist of linked reactions in which the product of the first reaction becomes the substrate of a second reaction. Sequential reactions occur in industrially important processes, such as the chlorination of methane. A generalized series of three sequential reactions was analyzed in order to determine the times at which each chemical species reaches its maximum. To determine the concentration of each species as a function of time, the differential rate laws for each species were solved. The solution of each gave the concentration curve of the chemical species. The concentration curves of species A1 and A2 possessed discreet maxima, which were determined through slope-analysis. The concentration curve of the final product, A3, did not possess a discreet maximum, but rather approached a finite limit.

  2. Nuclear reaction studies: Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Thaler, R.M.

    1986-11-19

    A principal focus of recent research has been the three-body problem. A great deal of effort has been devoted to the creation of a computer program to calculate physical observables in the three body problem below 1 GeV. Successful results have been obtained for the triton. Additional work concerns scattering of K/sup +/ mesons from nuclei, antinucleon physics, relativistic nuclear physics and inclusive reactions. (DWL)

  3. Learning Progressions that Support Formative Assessment Practices

    Science.gov (United States)

    Alonzo, Alicia C.

    2011-01-01

    Black, Wilson, and Yao (this issue) lay out a comprehensive vision for the way that learning progressions (or other "road maps") might be used to inform and coordinate formative and summative purposes of assessment. As Black, Wilson, and others have been arguing for over a decade, the effective use of formative assessment has great potential to…

  4. Galaxy Formation and Evolution Recent Progress

    CERN Document Server

    Ellis, Richard S

    2001-01-01

    In this series of lectures I review recent observational progress in constraining models of galaxy formation and evolution highlighting the importance advances in addressing questions of the assembly history and origin of the Hubble sequence in the context of modern pictures of structure formation.

  5. Progress in microscopic direct reaction modeling of nucleon induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dupuis, M.; Bauge, E.; Hilaire, S.; Lechaftois, F.; Peru, S.; Pillet, N.; Robin, C. [CEA, DAM, DIF, Arpajon (France)

    2015-12-15

    A microscopic nuclear reaction model is applied to neutron elastic and direct inelastic scatterings, and pre-equilibrium reaction. The JLM folding model is used with nuclear structure information calculated within the quasi-particle random phase approximation implemented with the Gogny D1S interaction. The folding model for direct inelastic scattering is extended to include rearrangement corrections stemming from both isoscalar and isovector density variations occurring during a transition. The quality of the predicted (n,n), (n,n{sup '}), (n,xn) and (n,n{sup '}γ) cross sections, as well as the generality of the present microscopic approach, shows that it is a powerful tool that can help improving nuclear reactions data quality. Short- and long-term perspectives are drawn to extend the present approach to more systems, to include missing reactions mechanisms, and to consistently treat both structure and reaction problems. (orig.)

  6. The spectrum of progressive derecho formation environments

    Science.gov (United States)

    Guastini, Corey T.

    Progressive derechos are severe mesoscale convective systems that often form east of the Rocky Mountains during the warm season (May--August) and cause, by definition, straight-line wind damage along paths upwards of 400 km long. This study develops a subjective, seven-category classification scheme that spans the spectrum of progressive derecho formation environments from those dominated by robust upper-level ridges to those characterized by vigorous upper-level troughs. A climatology of 256 progressive derecho events is created for 1996--2013 and is categorized according to the developed classification scheme. Derecho initiation-relative composites are constructed for each of the seven groups using 0.5° Climate Forecast System Reanalysis data to document the environmental characteristics unique to each group as well as those shared among them. Finally, two in-depth case studies and five cursory case studies provide examples of the seven categories and reveal important nuances in mesoscale dynamic and thermodynamic structure inherent to all derecho cases. Results of the climatology show progressive derecho activity increases from 1 May through 1 July before decreasing again through the end of August and follows a northward trend in latitude from 1 May through 1 August before shifting slightly southward through the end of the warm season. Upslope flow in the vicinity of the Rocky Mountains initiates 28 percent of progressive derechos, upper-level troughs initiate 20 percent, 47 percent form in benign synoptic environments, and 5 percent are unclassifiable. Composite results show all progressive derecho initiation environments are marked by a long axis of instability caused by the overlap of high atmospheric moisture content and steep midlevel lapse rates, but the relative positions and strengths of upper-level troughs and ridges are crucial in determining how the instability axis develops and what its orientation in space will be. Case studies reveal instability

  7. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    None

    2003-02-21

    The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  8. Recent Experimental Progress on Surrogate Reactions

    Science.gov (United States)

    Beausang, Cornelius

    2014-09-01

    Reactions on unstable nuclei are important in a wide variety of nuclear physics scenarios. Cross sections for neutron (or light charged particle) induced reactions on target nuclei spanning the chart of the nuclei are important for nuclear astrophysics (r-process, s-process rp- and p-processes etc.), for nuclear energy generation and for national security applications. Many such reactions occur on short-lived unstable nuclei. Even with the present generation of radioactive beam facilities, many such reactions are difficult, if not impossible, to measure directly. For these reactions, often the surrogate reaction technique provides the only option to provide some experimental guidance for the calculations. The experimental and theoretical techniques required are described in some detail in the recent review article by Escher et al.. Originally introduced in the 1970's the last decade has seen a resurgence of interest in the surrogate technique. Various ratio techniques, external, internal and hybrid, have been developed to minimize the effect of target contamination. In the actinide region, a large number of surrogate (n,f) cross sections have been measured. In general, these show agreement to within 5--10%, with directly measured (n,f) data where these data exist (benchmarking), for equivalent neutron energies ranging from ~100 keV up to tens of MeV. For (n, γ) reactions, measurements have been attempted for select nuclei in various mass regions (A ~ 90, 150 and 235) and for these the agreement with directly measured data is less good. The various experimental techniques employed will be described as well as the current state of the experimental data. Some future directions will be described. Reactions on unstable nuclei are important in a wide variety of nuclear physics scenarios. Cross sections for neutron (or light charged particle) induced reactions on target nuclei spanning the chart of the nuclei are important for nuclear astrophysics (r-process, s

  9. Progress in all-order breakup reaction theories

    Indian Academy of Sciences (India)

    R Chatterjee

    2010-07-01

    Progress in breakup reaction theories, like the distorted wave Born approximation, the continuum discretized coupled channels method and the dynamical eikonal approximation, is brought into focus. The need to calculate exclusive reaction observables and the utility of benchmark tests as arbitrators of theoretical models are discussed.

  10. An Overview of the Biology of Reaction Wood Formation

    Institute of Scientific and Technical Information of China (English)

    Sheng Du; Fukuju Yamamoto

    2007-01-01

    Reaction wood possesses altered properties and performs the function of regulating a tree's form, but it is a serious defect in wood utility. Trees usually develop reaction wood in response to a gravistimulus. Reaction wood in gymnosperms is referred to as compression wood and develops on the lower side of leaning stems or branches.In arboreal, dicotyledonous angiosperms, however, it is called tension wood and is formed on the upper side of the leaning. Exploring the biology of reaction wood formation is of great value for the understanding of the wood differentiation mechanisms, cambial activity, gravitropism, and the systematics and evolution of plants. After giving an outline of the variety of wood and properties of reaction wood, this review lays emphasis on various stimuli for reaction wood induction and the extensive studies carried out so far on the roles of plant hormones in reaction wood formation. Inconsistent results have been reported for the effects of plant hormones. Both auxin and ethylene regulate the formation of compression wood in gymnosperms. However, the role of ethylene may be indirect as exogenous ethylene cannot induce compression wood formation. Tension wood formation is mainly regulated by auxin and gibberellin. Interactions among hormones and other substances may play important parts in the regulation of reaction wood formation.

  11. Thiazole formation through a modified Gewald reaction

    Directory of Open Access Journals (Sweden)

    Carl J. Mallia

    2015-05-01

    Full Text Available The synthesis of thiazoles and thiophenes starting from nitriles, via a modified Gewald reaction has been studied for a number of different substrates. 1,4-Dithiane-2,5-diol was used as the aldehyde precursor to give either 2-substituted thiazoles or 2-substituted aminothiophenes depending on the substitution of the α-carbon to the cyano group.

  12. Vesicular Contact Reaction May Progress into Erythema Multiforme.

    Science.gov (United States)

    Czarnecka-Operacz, Magdalena; Jenerowicz, Dorota; Szulczyńska-Gabor, Joanna; Teresiak-Mikołajczak, Ewa; Szyfter-Harris, Joanna; Bowszyc-Dmochowska, Monika

    2016-12-01

    Dear Editor, Erythema multiforme is considered an acute skin condition, characterized by a self-limiting and sometimes recurrent course. It is regarded as a type IV hypersensitivity reaction associated with certain infections, medications, and other various triggers. Allergic contact dermatitis is in turn a delayed type of induced allergy as a result of cutaneous contact with a specific allergen to which the patient develops specific sensitivity. This type of cutaneous reaction is associated with inflammation manifesting with erythema, edema, and vesicles. A 27-year old female patient presented with a 3-day history of erythematous and vesicular lesions which developed 24 hours after cesarean section. Initially the lesions were localized in the area of surgery (mainly the abdomen and upper thighs) and on the next day progressed to the buttocks and lumbar area. The patient was referred to the Outpatient Clinic and was treated with antihistamines, but her dermatological state deteriorated rapidly. At the day of admission to the Department of Dermatology, numerous erythematous and vesicular lesions were present on the skin of the abdomen, thighs, and back (Figure 1, a), but the skin of the neck, chest, and extremities was also covered with erythematous and edematous patches. On the second day of hospitalization, we observed the evolution of lesions localized within the chest and extremities into an erythema multiforme-like targetoid eruption (Figure 1, b). Initially the patient was treated with intravenous injections of dexamethasone and ceftriaxone and orally with second-generation antihistamines (in four-fold doses), followed by intravenous metyloprednisolone pulse-therapy (total dose of 3 g). As the new vesicobullous lesions started to appear on the face and arms, we introduced cyclosporine A orally 400 mg daily. We could then observe gradual remission, but on the seventh day of hospitalization the patient developed a massive labial herpes simplex infection and had

  13. Formation of Superheavy Nuclei in Massive Fusion Reactions

    Institute of Scientific and Technical Information of China (English)

    FENG Zhao-qing; JIN Gen-ming; LI Jun-qing; Scheid Werner

    2009-01-01

    Within the concept of the dinuclear system(DNS),by incorporating the coupling of the relative motion to the nucleon transfer process,a dynamical model is proposed for describing the formation of superheavy residue nucleus in massive fusion reactions,in which the capture of two heavy colliding nuclei,the formation of compound nucleus and the de-excitation process are calculated using empirical coupled channel model,solving master equation numerically and statistical theory,respectively.By using the DNS model,the evaporation-residue excitation functions in the ~(48)Ca induced fusion reactions and in the cold fusion reactions are investigated systematically and compared with available experimental data.Optimal evaporation channels and combinations as well as the corresponding excitation energies are proposed.The possible factors that influencing the isotopic dependence of the production cross sections are analyzed.The formation of the superheavy nuclei based on the isotopes U with different projectiles are also investigated.

  14. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    Energy Technology Data Exchange (ETDEWEB)

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  15. Formation of superheavy nuclei in cold fusion reactions

    CERN Document Server

    Feng, Zhao-Qing; Li, Jun-Qing; Scheid, Werner

    2007-01-01

    Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus and the de-excitation process are calculated by using an empirical coupled channel model, solving a master equation numerically and applying statistical theory, respectively. Evaporation residue excitation functions in cold fusion reactions are investigated systematically and compared with available experimental data. Maximal production cross sections of superheavy nuclei in cold fusion reactions with stable neutron-rich projectiles are obtained. Isotopic trends in the production of the superheavy elements Z=110, 112, 114, 116, 118 and 120 are analyzed systematically. Optimal combinations and the corresponding excitation energies are proposed.

  16. Progress in spondylarthritis. Mechanisms of new bone formation in spondyloarthritis.

    Science.gov (United States)

    Lories, Rik J U; Luyten, Frank P; de Vlam, Kurt

    2009-01-01

    Targeted therapies that neutralize tumour necrosis factor are often able to control the signs and symptoms of spondyloarthritis. However, recent animal model data and clinical observations indicate that control of inflammation may not be sufficient to impede disease progression toward ankylosis in these patients. Bone morphogenetic proteins and WNTs (wingless-type like) are likely to play an important role in ankylosis and could be therapeutic targets. The relationship between inflammation and new bone formation is still unclear. This review summarizes progress made in our understanding of ankylosis and offers an alternative view of the relationship between inflammation and ankylosis.

  17. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

    Energy Technology Data Exchange (ETDEWEB)

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; Crowley, Michael F.

    2016-06-15

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the ..alpha..-O cleavage reaction is lower than that of the ..beta..-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

  18. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    Directory of Open Access Journals (Sweden)

    S. M. Murphy

    2007-01-01

    Full Text Available Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+ nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively and photooxidation (23% and 8% respectively. The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  19. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    Directory of Open Access Journals (Sweden)

    S. M. Murphy

    2007-01-01

    Full Text Available Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+ nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively and photooxidation (23% and 8% respectively. The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  20. THE PROGRESSION OF STAR FORMATION IN THE ROSETTE MOLECULAR CLOUD

    Energy Technology Data Exchange (ETDEWEB)

    Ybarra, Jason E.; Lada, Elizabeth A. [Department of Astronomy, University of Florida, Gainesville, FL 32605 (United States); Roman-Zuniga, Carlos G. [Instituto de Astronomia, Universidad Nacional Autonoma de Mexico, Unidad Academica de Ensenada, Apdo. Postal 22860, Ensenada, B. C. (Mexico); Balog, Zoltan [Max-Planck-Institut fuer Astronomie, Heidelberg (Germany); Wang Junfeng [Department of Physics and Astronomy and Center for Interdisciplinary Exploration and Research in Astrophysics (CIERA), Northwestern University, 2131 Tech Dr, Evanston, IL 60208 (United States); Feigelson, Eric D., E-mail: jybarra@astro.ufl.edu [Pennsylvania State University, University Park, PA 16802 (United States)

    2013-06-01

    Using Spitzer Space Telescope and Chandra X-Ray Observatory data, we identify young stellar objects (YSOs) in the Rosette Molecular Cloud (RMC). By being able to select cluster members and classify them into YSO types, we are able to track the progression of star formation locally within the cluster environments and globally within the cloud. We employ the nearest neighbor method analysis to explore the density structure of the clusters and YSO ratio mapping to study age progressions in the cloud. We find a relationship between the YSO ratios and extinction that suggests star formation occurs preferentially in the densest parts of the cloud and that the column density of gas rapidly decreases as the region evolves. This suggests rapid removal of gas may account for the low star formation efficiencies observed in molecular clouds. We find that the overall age spread across the RMC is small. Our analysis suggests that star formation started throughout the complex around the same time. Age gradients in the cloud appear to be localized and any effect the H II region has on the star formation history is secondary to that of the primordial collapse of the cloud.

  1. EXFOR systems manual: Nuclear reaction data exchange format

    Energy Technology Data Exchange (ETDEWEB)

    McLane, V. [ed.

    1996-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. In addition to storing the data and its bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine).

  2. Holographic Grating Formation in Cationic Photopolymers with Dark Reaction

    Institute of Scientific and Technical Information of China (English)

    WEI Hao-Yun; CAO Liang-Cai; GU Claire; XU Zhen-Feng; HE Ming-Zhao; HE Qing-Sheng; HE Shu-Rong; JIN Guo-Fan

    2006-01-01

    @@ We propose a new formula to describe the dynamics of holographic grating formation under low intensity pulse exposures in cationic photopolymers, in which the dark reaction contributes dominantly to the grating strength.The formula is based on the living polymerization mechanism and the diffusion-free approximation. The analytical solution indicates that the grating formation time depends on the termination rate constant, while the final grating strength depends linearly on the total exposure energy. These theoretical predictions are verified experimentally using the Aprilis HMC-400μm photopolymer. The results can provide guidelines for the control and optimization of the holographic recording conditions in practical applications.

  3. Strangeness production and hypernucleus formation in antiproton induced reactions

    CERN Document Server

    Feng, Zhao-Qing

    2015-01-01

    Formation mechanism of fragments with strangeness in collisions of antiprotons on nuclei has been investigated within the Lanzhou quantum molecular dynamics (LQMD) transport approach combined with a statistical model (GEMINI) for describing the decays of excited fragments. Production of strange particles in the antiproton induced nuclear reactions is modeled within the LQMD model, in which all possible reaction channels such as elastic scattering, annihilation, charge exchange and inelastic scattering in antibaryon-baryon, baryon-baryon and meson-baryon collisions have been included. A coalescence approach is developed for constructing hyperfragments in phase space after de-excitation of nucleonic fragments. The combined approach could describe the production of fragments in low-energy antiproton induced reactions. Hyperfragments are formed within the narrower rapidities and lower kinetic energies. It has advantage to produce heavier hyperfragments and hypernuclides with strangeness s=-2 (double-$\\Lambda$ fra...

  4. Formation of Complex Molecules via radiative association reactions

    Science.gov (United States)

    Acharyya, Kinsuk; Herbst, Eric

    2016-07-01

    The detection of increasing numbers of complex organic molecules in the various phases of star formation plays a key role since they follow the same chemical rules of carbon-based chemistry that are observed in our planet Earth. Many of these molecules are believed to be formed on the surfaces of grains, and can then be released to the gas phase when these grains are heated. This is evident when we observe a rich chemistry in hot core regions. However, recently complex organic molecules have also been observed in cold clouds. Therefore, it is necessary to re-examine various pathways for the formation of these molecules in the gas phase. In this presentation, I will discuss role of radiative association reactions in the formation of complex molecules in the gas phase and at low temperature. We will compare abundance of assorted molecules with and without new radiative association reactions and will show that the abundance of a few complex molecules such as HCOOCH3, CH3OCH3 etc. can go up due to introduction of these reactions, which can help to explain their observed abundances.

  5. Catalysis of Dialanine Formation by Glycine in the Salt-Induced Peptide Formation Reaction.

    Science.gov (United States)

    Suwannachot, Yuttana; Rode, Bernd M.

    1998-02-01

    Mutual catalysis of amino acids in the salt-induced peptide formation (SIPF) reaction is demonstrated for the case of glycine/alanine. The presence of glycine enhances dialanine formation by a factor up to 50 and enables dialanine formation at much lower alanine concentrations. The actual amounts of glycine play an important role for this catalytic effect, the optimal glycine concentration is 1/8 of the alanine concentration. The mechanism appears to be based on the formation of the intermediate Gly-Ala-Ala tripeptide, connected to one coordination site of copper(II) ion, and subsequent hydrolysis to dialanine and glycine.

  6. Role of ADAMs in cancer formation and progression.

    LENUS (Irish Health Repository)

    Duffy, Michael J

    2012-02-01

    The ADAMs (a disintegrin and metalloproteinase) comprise a family of multidomain transmembrane and secreted proteins. One of their best-established roles is the release of biologically important ligands, such as tumor necrosis factor-alpha, epidermal growth factor, transforming growth factor-alpha, and amphiregulin. Because these ligands have been implicated in the formation and progression of tumors, it might be expected that the specific ADAMs involved in their release would also be involved in malignancy. Consistent with this hypothesis, emerging data from model systems suggest that ADAMs, such as ADAM-9, ADAM-12, ADAM-15, and ADAM-17, are causally involved in tumor formation\\/progression. In human cancer, specific ADAMs are up-regulated, with levels generally correlating with parameters of tumor progression and poor outcome. In preclinical models, selective ADAM inhibitors against ADAM-10 and ADAM-17 have been shown to synergize with existing therapies in decreasing tumor growth. The ADAMs are thus a new family of potential targets for the treatment of cancer, especially malignancies that are dependent on human epidermal growth factor receptor ligands or tumor necrosis factor-alpha.

  7. Effects of a Single Water Molecule on the Reaction Barrier of Interstellar CO2 Formation Reaction.

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-08-25

    The mechanism by which CO2 is formed in the interstellar space remains a mystery. The most likely reaction is collision between CO and OH; however, previous theoretical works have shown that the activation barrier for CO2 formation is high enough to prevent the reaction at the low thermal conditions of space (∼10 K). The effects of single water molecule on the reaction barrier of CO2 formation from reaction between CO and OH have been investigated here by means of ab initio calculation. The barrier height along the lowest-energy pathway in the reaction between CO and OH in the absence of the H2O molecule was calculated to be 2.3 kcal/mol when CCSD(T) energy corrections are combined with the MP2 basis set limit. In the case of the hydrated (H2O-CO-OH) system, the inclusion of a single H2O molecule into the system significantly decreased the barrier height to 0.2 kcal/mol. This suggests that CO2 can be formed when CO and OH react in the presence of H2O, even under thermal conditions as low as 10 K.

  8. Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

    Science.gov (United States)

    Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

    Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

  9. The Effect of Trabeculectomy on Cataract Formation or Progression

    Directory of Open Access Journals (Sweden)

    Zhale Rajavi

    2009-04-01

    Full Text Available PURPOSE: To determine the effect of trabeculectomy on cataract formation or progression in patients with chronic glaucoma. METHODS: This controlled clinical trial was performed on patients over 50 years of age with glaucoma who were referred to Imam Hossein Hospital, Tehran, Iran, from 2006 to 2007. Trabeculectomy was indicated only in one eye while the fellow eye had well-controlled intraocular pressure with medication(s. The fellow eyes served as controls. Lens opacity was evaluated using three criteria: visual acuity (VA, and Lens Opacification Classification System III (LOCS III photographs and scores. RESULTS: Overall 82 eyes of 41 patients including 53.7% male and 46.3% female subjects with mean age of 62.5±9.3 (range 50-75 years were evaluated. Cataract progression in operated eyes was statistically significant according to VA (P=0.02, LOCS III photo-graphs (P=0.05 and LOCS III scores (P=0.01. However, compared to fellow control eyes, cataract progression was significant according to VA (P=0.023 and LOCS III scores (P=0.057 but not based on LOCS III photographs. Mean VA reduction was 2 Snellen lines in operated eyes; there were 3 cases of cataract formation or

  10. Formation of molecular oxygen in ultracold O + OH reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kendrick, Brian Kent [Los Alamos National Laboratory; Quemener, Goulven [UNLV; Balakrishman, Naduvalath [UNLV

    2008-01-01

    We discuss the formation of molecular oxygen in ultracold collisions between hydroxyl radicals and atomic oxygen. A time-independent quantum formalism based on hyperspherical coordinates is employed for the calculations. Elastic, inelastic and reactive cross sections as well as the vibrational and rotational populations of the product O{sub 2} molecules are reported. A J-shifting approximation is used to compute the rate coefficients. At temperatures T = 10--100 mK for which the OH molecules have been cooled and trapped experimentally, the elastic and reactive rate coefficients are of comparable magnitude, while at colder temperatures, T < 1 mK, the formation of molecular oxygen becomes the dominant pathway. The validity of a classical capture model to describe cold collisions of OH and O is also discussed. While very good agreement is found between classical and quantum results at T = 0.3 K, at higher temperatures, the quantum calculations predict a higher rate coefficient than the classical model, in agreement with experimental data for the O + OH reaction. The zero-temperature limiting value of the rate coefficient is predicted to be about 6 x 10{sup -12} cm{sup 3} s{sup 01}, a value comparable to that of barrierless alkali metal atom-dimer systems and about a factor of five larger than that of the tunneling dominated F + H{sub 2} reaction.

  11. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    Directory of Open Access Journals (Sweden)

    Stockwell Timothy B

    2007-04-01

    Full Text Available Abstract Background Multiple Displacement Amplification (MDA is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications.

  12. Aerosol formation yields from the reaction of catechol with ozone

    Science.gov (United States)

    Coeur-Tourneur, Cécile; Tomas, Alexandre; Guilloteau, Angélique; Henry, Françoise; Ledoux, Frédéric; Visez, Nicolas; Riffault, Véronique; Wenger, John C.; Bedjanian, Yuri

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm -3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas-particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.

  13. Progress and Application of Plastein Reaction in Food Proteins

    Institute of Scientific and Technical Information of China (English)

    ZHOU Zunlai; FENG Zhibiao

    2006-01-01

    Plastein reaction is considered a reversal of the usual protein hydrolysis by proteinase, which was applied to prepare a higher-molecular, protein-like substance. It can improve biological value and functional properties of food proteins, meliorate flavor of protein hydrolysates and, especially, provide a way to synthesize new sources of proteins. Although the mechanism(s) of the plastein reaction is not clarified, it will have great values in food industry with the development of technologies in enzymology and microbiology.

  14. Adaptive progressive download based on the MPEG-4 file format

    Institute of Scientific and Technical Information of China (English)

    F(A)RBER Nikolaus; D(O)HLA Stefan; ISSING Jochen

    2006-01-01

    In this paper we describe how progressive download and adaptive streaming can be combined into a simple and efficient streaming framework. Based on the MPEG-4 file format (MP4) we use HTTP for transport and argue that these two components are sufficient for specifying an open streaming architecture. The client selects appropriatechunks from the MP4 file to be transferred based on (1) the header information (i.e. the "moov" box) in the first part of the file and (2) his observation of network throughput. The framework is completely client driven which allows for better server scalability and reduces signalling overhead. We discuss architecture and implementation issues such as complexity, interoperability and scalability and compare to 3GPP PSS Rel-6 adaptive streaming when appropriate. Measurements from a simple MP4/HTTP streaming client are presented showing that appropriate chunks are selected such that increased reliability is achieved.

  15. Time scales for molecule formation by ion-molecule reactions

    Science.gov (United States)

    Langer, W. D.; Glassgold, A. E.

    1976-01-01

    Analytical solutions are obtained for nonlinear differential equations governing the time-dependence of molecular abundances in interstellar clouds. Three gas-phase reaction schemes are considered separately for the regions where each dominates. The particular case of CO, and closely related members of the Oh and CH families of molecules, is studied for given values of temperature, density, and the radiation field. Nonlinear effects and couplings with particular ions are found to be important. The time scales for CO formation range from 100,000 to a few million years, depending on the chemistry and regime. The time required for essentially complete conversion of C(+) to CO in the region where the H3(+) chemistry dominates is several million years. Because this time is longer than or comparable to dynamical time scales for dense interstellar clouds, steady-state abundances may not be observed in such clouds.

  16. Reactions and Coulex at TRIUMF, progress and prospects of SHARC

    Science.gov (United States)

    Diget, Christian Aa.; Sarazin, Fred

    2008-10-01

    The Silicon Highly-segmented Array for Reactions and Coulex (SHARC) is a multi-purpose array for charged-particle detection. The array is designed to have high spatial resolution, a large solid angle coverage, and particle identification of the measured reaction products. This combination offers unique capabilities when integrated with the TIGRESS gamma-ray detectors and the post-accelerated beams at the ISAC-II facility at TRIUMF, Canada. Two major research programs will gain significantly from the utilization of SHARC: Reaction studies with particular emphasis on transfer reactions used to indirectly probe nuclear reaction rates important for explosive stellar scenarios as well as nuclear structure studies in which Coulomb excitation will play an important role. The project is funded by the UK-STFC and is lead from the University of York with collaborators from the UK Universities of Birmingham, Liverpool, Manchester, and Surrey, and Daresbury Laboratory; Colorado School of Mines and Louisiana State University of the USA; and from Canada: TRIUMF as well as McMaster, Saint Mary's, and Simon Fraser Universities.

  17. Progress in Nanoscale Studies of Hydrogen Reactions in Construction Materials

    Science.gov (United States)

    Schweitzer, J. S.; Livingston, R. A.; Cheung, J.; Rolfs, C.; Becker, H.-W.; Kubsky, S.; Spillane, T.; Zickefoose, J.; Castellote, M.; Bengtsson, N.; Galan, I.; de Viedma, P. G.; Brendle, S.; Bumrongjaroen, W.; Muller, I.

    Nuclear resonance reaction analysis (NRRA) has been applied to measure the nanoscale distribution of hydrogen with depth in the hydration of cementitious phases. This has provided a better understanding of the mechanisms and kinetics of cement hydration during the induction period that is critical to improved concrete technology. NRRA was also applied to measure the hydrogen depth profiles in other materials used in concrete construction such as fly ash and steel. By varying the incident beam energy one measures a profile with a depth resolution of a few nanometers. Time-resolved measurements are achieved by stopping the chemical reactions at specific times. Effects of temperature, sulfate concentration, accelerators and retarders, and superplasticizers have been investigated. Hydration of fly ashes has been studied with synthetic glass specimens whose chemical compositions are modeled on those of actual fly ashes. A combinatorial chemistry approach was used where glasses of different compositions are hydrated in various solutions for a fixed time. The resulting hydrogen depth profiles show significant differences in hydrated phases, rates of depth penetration and amount of surface etching. Hydrogen embrittlement of steel was studied on slow strain rate specimens under different corrosion potentials.

  18. Progression of radical reactions on microscopic scale in food emulsions

    DEFF Research Database (Denmark)

    Raudsepp, Piret

    Understanding the progression of lipid oxidation in oil-in-water emulsions from the aspect of the food quality and safety, consumer satisfaction and cleaner food label is of importance, because most of the food emulsions are oil-in-water emulsions. There is an increasing tendency in the food...... industry to incorporate unsaturated oils into food products, but that results in shortened shelf-life. Therefore, studying the factors and consequences of the oxidative instability provides beneficial insight into prolonging the antioxidative stage and inhibiting undergoing oxidation processes to improve...... the food quality and increase the shelflife of the food products. In the present work, lipid oxidation in oil-in-water emulsions was studied via conventional analytical and via novel state-of-the-art techniques. For the first time, the effect of mixing emulsions made of saturated medium-chain triglyceride...

  19. Progression of radical reactions on microscopic scale in food emulsions

    DEFF Research Database (Denmark)

    Raudsepp, Piret

    Understanding the progression of lipid oxidation in oil-in-water emulsions from the aspect of the food quality and safety, consumer satisfaction and cleaner food label is of importance, because most of the food emulsions are oil-in-water emulsions. There is an increasing tendency in the food...... the food quality and increase the shelflife of the food products. In the present work, lipid oxidation in oil-in-water emulsions was studied via conventional analytical and via novel state-of-the-art techniques. For the first time, the effect of mixing emulsions made of saturated medium-chain triglyceride...... industry to incorporate unsaturated oils into food products, but that results in shortened shelf-life. Therefore, studying the factors and consequences of the oxidative instability provides beneficial insight into prolonging the antioxidative stage and inhibiting undergoing oxidation processes to improve...

  20. Theoretical studies in nuclear reactions and nuclear structure. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1992-05-01

    Research in the Maryland Nuclear Theory Group focusses on problems in four basic areas of current relevance. Hadrons in nuclear matter; the structure of hadrons; relativistic nuclear physics and heavy ion dynamics and related processes. The section on hadrons in nuclear matter groups together research items which are aimed at exploring ways in which the properties of nucleons and the mesons which play a role in the nuclear force are modified in the nuclear medium. A very interesting result has been the finding that QCD sum rules supply a new insight into the decrease of the nucleon`s mass in the nuclear medium. The quark condensate, which characterizes spontaneous chiral symmetry breaking of the late QCD vacuum, decreases in nuclear matter and this is responsible for the decrease of the nucleon`s mass. The section on the structure of hadrons contains progress reports on our research aimed at understanding the structure of the nucleon. Widely different approaches are being studied, e.g., lattice gauge calculations, QCD sum rules, quark-meson models with confinement and other hedgehog models. A major goal of this type of research is to develop appropriate links between nuclear physics and QCD. The section on relativistic nuclear physics represents our continuing interest in developing an appropriate relativistic framework for nuclear dynamics. A Lorentz-invariant description of the nuclear force suggests a similar decrease of the nucleon`s mass in the nuclear medium as has been found from QCD sum rules. Work in progress extends previous successes in elastic scattering to inelastic scattering of protons by nuclei. The section on heavy ion dynamics and related processes reports on research into the e{sup +}e{sup {minus}} problem and heavy ion dynamics.

  1. Ionic liquid effects on Mizoroki-Heck reactions: more than just carbene complex formation.

    Science.gov (United States)

    Gyton, Matthew R; Cole, Marcus L; Harper, Jason B

    2011-08-28

    Reaction profiles for a Mizoroki-Heck reaction in either an ionic liquid or a molecular solvent with different palladium sources demonstrate that the rate enhancements observed in ionic liquids cannot be solely attributed to Pd-carbene complex formation.

  2. Thermokinetics of the Formation Reaction of Zinc Histidine Complex

    Institute of Scientific and Technical Information of China (English)

    GAO,Sheng-Li(高胜利); CHEN,San-Ping(陈三平); HU,Rong-Zu(胡荣祖); SHI,Qi-Zhen(史启祯)

    2002-01-01

    The enthalpy change of reaction of zinc chloride with L-α-histidine in the temperature range of 25-50 ℃ has been determined by a microcalorimeter. On the basis of experimental and calculated results, three thermodynamics parameters (the activation enthalpy, the activation entropy, the activation free energy), the rate constant and three kinetic parameters (the activation energy, the pre-exponential constant and the reaction order) of the reaction, and the standard enthalpy of formarion of Zn(His)2+ (aq.) are obtained. The results showed that the title reaction easily took place at the studied temperature.

  3. Protein-Templated Formation of an Inhibitor of the Blood Coagulation Factor Xa through a Background-Free Amidation Reaction.

    Science.gov (United States)

    Jaegle, Mike; Steinmetzer, Torsten; Rademann, Jörg

    2017-03-20

    Protein-templated reactions enable the target-guided formation of protein ligands from reactive fragments, ideally with no background reaction. Herein, we investigate the templated formation of amides. A nucleophilic fragment that binds to the coagulation factor Xa was incubated with the protein and thirteen differentially activated dipeptides. The protein induced a non-catalytic templated reaction for the phenyl and trifluoroethyl esters; the latter was shown to be a completely background-free reaction. Starting from two fragments with millimolar affinity, a 29 nm superadditive inhibitor of factor Xa was obtained. The fragment ligation reaction was detected with high sensitivity by an enzyme activity assay and by mass spectrometry. The reaction progress and autoinhibition of the templated reaction by the formed ligation product were determined, and the structure of the protein-inhibitor complex was elucidated.

  4. Nested arithmetic progressions of oscillatory phases in Olsen's enzyme reaction model.

    Science.gov (United States)

    Gallas, Marcia R; Gallas, Jason A C

    2015-06-01

    We report some regular organizations of stability phases discovered among self-sustained oscillations of a biochemical oscillator. The signature of such organizations is a nested arithmetic progression in the number of spikes of consecutive windows of periodic oscillations. In one of them, there is a main progression of windows whose consecutive number of spikes differs by one unit. Such windows are separated by a secondary progression of smaller windows whose number of spikes differs by two units. Another more complex progression involves a fan-like nested alternation of stability phases whose number of spikes seems to grow indefinitely and to accumulate methodically in cycles. Arithmetic progressions exist abundantly in several control parameter planes and can be observed by tuning just one among several possible rate constants governing the enzyme reaction.

  5. Progresses in the ice formation of glaciers in China

    Institute of Scientific and Technical Information of China (English)

    Xiangying LI; Shiyin LIU; ,Donghui SHANGGUAN1; Aigang LU

    2008-01-01

    Glaciers,formed by snowfall and characterized by movement and size,are the most sensitive indicators to climate change.The ice formation of glaciers(the processes,mechanisms and results of transformation from snow to ice)can indicate the growth condition,the formation process and the physical characteristics of glaciers.Its spatial variation can also reflect glacier change,and further reveal climate change.Studies on ice formation of glaciers in China were initiated in 1962,when Xie and others studied the ice formation of Glacier No.1 at the Urumqi River head,Tianshan Mountain.Other researchers followed suit and did studies on ice formation of glaciers in Qilian Mountain.As time goes by,the concept of ice formation came into being in China.This paper reviews the development history of glacier zones,and the studies of ice formation of glaciers in China since the 1960s.These studies mainly focus on Qilian Mountain,Tianshan Mountain,Altay Mountain,and the western Kunlun Mountain,Himalaya Mountain,the southeastern Tibetan and Hengduan Mountains.The paper also discusses the significance of ice formation studies,the limitation and deficiency of previous studies,and the prospects and suggestions for future studies.

  6. The Influence of Item Formats when Locating a Student on a Learning Progression in Science

    Directory of Open Access Journals (Sweden)

    Jing Chen

    2016-07-01

    Full Text Available Learning progressions are used to describe how students’ understanding of a topic progresses over time. This study evaluates the effectiveness of different item formats for placing students into levels along a learning progression for carbon cycling. The item formats investigated were Constructed Response (CR items and two types of two-tier items: (1 Ordered Multiple-Choice (OMC followed by CR items and (2 Multiple True or False (MTF followed by CR items. Our results suggest that estimates of students’ learning progression level based on OMC and MTF responses are moderately predictive of their level based on CR responses. With few exceptions, CR items were effective for differentiating students among learning progression levels. Based on the results, we discuss how to design and best use items in each format to more accurately measure students’ level along learning progressions in science.

  7. Concept and progress in coupling of dehydrogenation and hydrogenation reactions through catalysts

    Indian Academy of Sciences (India)

    C V Pramod; C Raghavendra; K Hari Prasad Reddy; G V Ramesh Babu; K S Rama Rao; B David Raju

    2014-03-01

    This review focuses on the importance of coupling of catalytic reactions which involves dehydrogenation and hydrogenation simultaneously and the study of catalytic materials that are designed, adopted and/or modified for these reactions. The special features of these reactions are minimization of H2 utilization and reduction in production cost. Structural and textural properties also play a decisive role in this kind of coupled reactions. This particular review although not comprehensive discusses the significant progress made in the area of coupled reactions and also helps future researchers or engineers to find out the improvements required in areas such as advancements in catalytic material preparation, design of the new reactors and the application of new technologies.

  8. Reaction path and crystallograpy of cobalt silicide formation on silicon(001) by reaction deposition epitaxy

    Science.gov (United States)

    Lim, Chong Wee

    CaF2-structure CoSi2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi2 layers obtained by conventional solid phase growth (SPG). In the case of RDE, CoSi 2 formation occurred during Co deposition at elevated temperature while for SPG, Co was deposited at 25°C and silicidation took place during subsequent annealing. My results demonstrate that RDE CoSi2 layers are epitaxial with a cube-on-cube relationship, 001CoSi2 ‖001Si and 100CoSi2 ‖100 Si . In contrast, SPG films are polycrystalline with a mixed 111/002/022/112 orientation. I attribute the striking difference to rapid Co diffusion during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. Initial formation of CoSi2(001) follows the Volmer-Weber mode with two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal directions, bounded by four {111} CoSi2/Si interfaces, and grow with a cube-on-cube orientation with respect to Si(001). Platelet-shaped islands are bounded across their long directions by {111} twin planes and their narrow directions by 511CoSi2 ‖111Si interfaces. The top and bottom surfaces are {22¯1}, with 22¯1 CoSi2‖001 Si , and {1¯1¯1}, with 1¯1¯ 1CoSi2‖ 11¯1Si , respectively. The early stages of film growth (tCo ≤ 13 A) are dominated by the twinned platelets due to a combination of higher nucleation rates and rapid elongation along preferred directions. However, at tCo ≥ 13 A, island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. Further island growth becomes dominated by the untwinned islands. I show that high-flux low-energy Ar+ ion irradiation during RDE growth dramatically increases the area fraction of untwinned regions from 0.17 in films grown under standard magnetically balanced conditions in which the ratio

  9. Mean-field instabilities and cluster formation in nuclear reactions

    CERN Document Server

    Colonna, M; Baran, V

    2016-01-01

    We review recent results on intermediate mass cluster production in heavy ion collisions at Fermi energy and in spallation reactions. Our studies are based on modern transport theories, employing effective interactions for the nuclear mean-field and incorporating two-body correlations and fluctuations. Namely we will consider the Stochastic Mean Field (SMF) approach and the recently developed Boltzmann-Langevin One Body (BLOB) model. We focus on cluster production emerging from the possible occurrence of low-density mean-field instabilities in heavy ion reactions. Within such a framework, the respective role of one and two-body effects, in the two models considered, will be carefully analysed. We will discuss, in particular, fragment production in central and semi-peripheral heavy ion collisions, which is the object of many recent experimental investigations. Moreover, in the context of spallation reactions, we will show how thermal expansion may trigger the development of mean-field instabilities, leading to...

  10. Progress in NMR Applications to Well Logging and Formation Evaluation

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    @@ Since its discovery in 1946, NMR has become a valuable tool in physics, chemistry, biology, and medicine. With the invention of NMR logging tools that take the medical MRI or laboratory NMR equipment and turn it inside-out, the application of sophisticated laboratory techniques to determine formation properties in situ is now available. The capability has opened a new era in formation evaluation just as the introduction of NMR has revolutionized the other scientific areas.

  11. Alcali-silica reactions: Mechanisms for crack formations

    DEFF Research Database (Denmark)

    Goltermann, Per

    2006-01-01

    Alkali-silica reactions (ASR) are found all over the world and cause a large number of damage, which have lead to different sets of requirements in the different countries for the aggregates, the cements and the admixtures. One of the reasons for the damage and the different requirements is that ...

  12. An Investigation of Model Catalyzed Hydrocarbon Formation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tysoe, W. T.

    2001-05-02

    Work was focused on two areas aimed at understanding the chemistry of realistic catalytic systems: (1) The synthesis and characterization of model supported olefin metathesis catalysts. (2) Understanding the role of the carbonaceous layer present on Pd(111) single crystal model catalysts during reaction.

  13. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    Energy Technology Data Exchange (ETDEWEB)

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969. As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: that is machine-readable (for checking and indicating possible errors); that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  14. Luminosity progression in dart-stepped leader step formation

    Science.gov (United States)

    Wang, D.; Takagi, N.; Uman, M. A.; Jordan, D. M.

    2016-12-01

    Using a high-speed optical imaging system, we have observed the step formation bright pulse discharges occurring at the tip of dart-stepped leaders of rocket triggered lightning with a time resolution of 0.1 µs and a spatial resolution of about 1.4 m. Each of the step formation pulse discharges appeared to initiate at a location immediately below the bottom of its previous pulse discharge and to propagate in bidirectional (upward and downward) waves with a speed on the order of 107 m/s. The downward waves of the pulse discharges tended to slow down significantly after they propagated a distance of about 2 m. Based on the results observed in this study and those published in literatures, we propose a conceptual view of leader step formation.

  15. Progress in spondylarthritis. Mechanisms of new bone formation in spondyloarthritis

    OpenAIRE

    2009-01-01

    Targeted therapies that neutralize tumour necrosis factor are often able to control the signs and symptoms of spondyloarthritis. However, recent animal model data and clinical observations indicate that control of inflammation may not be sufficient to impede disease progression toward ankylosis in these patients. Bone morphogenetic proteins and WNTs (wingless-type like) are likely to play an important role in ankylosis and could be therapeutic targets. The relationship between inflammation an...

  16. Fluctuation-Induced Pattern Formation in a Surface Reaction

    DEFF Research Database (Denmark)

    Starke, Jens; Reichert, Christian; Eiswirth, Markus

    2006-01-01

    Spontaneous nucleation, pulse formation, and propagation failure have been observed experimentally in CO oxidation on Pt(110) at intermediate pressures ($\\approx 10^{-2}$mbar). This phenomenon can be reproduced with a stochastic model which includes temperature effects. Nucleation occurs randomly...

  17. STUDY OF REACTION SEQUENCES FOR FORMATION OF SOLID ...

    African Journals Online (AJOL)

    31 déc. 2012 ... phase intermédiaire PbTiO3 et la formation de PZT à 800 °C. ... matériau céramique de type PZT de formule chimique: 0,48PbZrO3-0 .... (ATG) relative au mélange par un changement de perte visible équivalente à 3%.

  18. Interfacing supercritical fluid reaction apparatus with on-line liquid chromatography: monitoring the progress of a synthetic organic reaction performed in supercritical fluid solution.

    Science.gov (United States)

    Ramsey, Edward D; Li, Ben; Guo, Wei; Liu, Jing Y

    2015-04-03

    An interface has been developed that connects a supercritical fluid reaction (SFR) vessel directly on-line to a liquid chromatograph. The combined SFR-LC system has enabled the progress of the esterification reaction between phenol and benzoyl chloride to synthesize phenyl benzoate in supercritical fluid carbon dioxide solution to be dynamically monitored. This was achieved by the periodic SFR-LC analysis of samples directly withdrawn from the esterification reaction mixture. Using the series of SFR-LC analysis results obtained for individual esterification reactions, the reaction progress profile for each esterification reaction was obtained by expressing the measured yield of phenyl benzoate as a function of reaction time. With reaction temperature fixed at 75°C, four sets (n=3) of SFR-LC reaction progress profiles were obtained at four different SFR pressures ranging from 13.79 to 27.58 MPa. The maximum SFR yield obtained for phenyl benzoate using a standard set of reactant concentrations was 85.2% (R.S.D. 4.2%) when the reaction was performed at 13.79 MPa for 90 min. In comparison, a phenyl benzoate yield of less than 0.3% was obtained using the same standard reactant concentrations after 90 min reaction time at 75°C using either: heptane, ethyl acetate or acetonitrile as conventional organic reaction solvents.

  19. FORMATION OF MANGANESE SILICIDE THIN FILMS BY SOLID PHASE REACTION

    Institute of Scientific and Technical Information of China (English)

    E.Q. Xie; W.W. Wang; N. Jiang; D.Y. He

    2002-01-01

    Manganese silicide MnSi2-x thin films have been prepared on n-type silicon substratesthrough solid phase reaction. The heterostructures were analyzed by X-ray diffraction,Rutherford backscattering spectroscopy, Fourier transform infrared transmittance spec-troscopy and the four-point probe technique. The results show that two manganese sili-cides have been formed sequentially via the reaction of thin layer Mn with Si substrateat different irradiation annealing stages, i.e., MnSi at 450℃ and MnSi1.73 at 550℃.MnSi1.73 phase exhibits preferred growth after irradiation with infrared. In situ four-point probe measurements of sheet resistance during infrared irradiation annealingshow that nucleation of MnSi and phase transformation of MnSi to MnSi1. 73 occur at410℃ and 530℃, respectively; the MnSi phase shows metallic behavior, while MnSi1.73exhibits semiconducting behavior. Characteristic phonon bands of MnSi2-x silicides,which can be used for phase identification along with conventional XRD techniques,have been observed by FTIR spectroscopy.

  20. Are We There Yet? Using Rubrics to Support Progress toward Proficiency and Model Formative Assessment

    Science.gov (United States)

    Kinne, Lenore J.; Hasenbank, Jon F.; Coffey, David

    2014-01-01

    Classroom assessment, especially formative assessment, is one of the most challenging areas for new teachers, so it is imperative that teacher educators model effective classroom assessment practices. This article describes the use of rubrics in formative assessment, to support candidates in their progress toward mastery of course outcomes and to…

  1. Development of a Learning Progression for the Formation of the Solar System

    Science.gov (United States)

    Plummer, Julia D.; Palma, Christopher; Flarend, Alice; Rubin, KeriAnn; Ong, Yann Shiou; Botzer, Brandon; McDonald, Scott; Furman, Tanya

    2015-01-01

    This study describes the process of defining a hypothetical learning progression (LP) for astronomy around the big idea of "Solar System formation." At the most sophisticated level, students can explain how the formation process led to the current Solar System by considering how the planets formed from the collapse of a rotating cloud of…

  2. Development of a Learning Progression for the Formation of the Solar System

    Science.gov (United States)

    Plummer, Julia D.; Palma, Christopher; Flarend, Alice; Rubin, KeriAnn; Ong, Yann Shiou; Botzer, Brandon; McDonald, Scott; Furman, Tanya

    2015-01-01

    This study describes the process of defining a hypothetical learning progression (LP) for astronomy around the big idea of "Solar System formation." At the most sophisticated level, students can explain how the formation process led to the current Solar System by considering how the planets formed from the collapse of a rotating cloud of…

  3. Clay surface catalysis of formation of humic substances: potential role of maillard reactions

    Science.gov (United States)

    The mechanisms of the formation of humic substances are poorly understood, especially the condensation of amino acids and reducing sugars products (Maillard reaction) in soil environments. Clay minerals behave as Lewis and Brönsted acids and catalyze several reactions and likely to catalyze the Mai...

  4. Quasifission in heavy and superheavy element formation reactions

    Science.gov (United States)

    Hinde, D. J.; Dasgupta, M.; Jeung, D. Y.; Mohanto, G.; Prasad, E.; Simenel, C.; Walshe, J.; Wahkle, A.; Williams, E.; Carter, I. P.; Cook, K. J.; Kalkal, Sunil; Rafferty, D. C.; Rietz, R. du; Simpson, E. C.; David, H. M.; Düllmann, Ch. E.; Khuyagbaatar, J.

    2016-12-01

    Superheavy elements are created in the laboratory by the fusion of two heavy nuclei. The large Coulomb repulsion that makes superheavy elements decay also makes the fusion process that forms them very unlikely. Instead, after sticking together for a short time, the two nuclei usually come apart, in a process called quasifission. Mass-angle distributions give the most direct information on the characteristics and time scales of quasifission. A systematic study of carefully chosen mass-angle distributions has provided information on the global trends of quasifission. Large deviations from these systematics reveal the major role played by the nuclear structure of the two colliding nuclei in determining the reaction outcome, and thus implicitly in hindering or favouring superheavy element production.

  5. Charged particle-induced nuclear fission reactionsProgress and prospects

    Indian Academy of Sciences (India)

    S Kailas; K Mahata

    2014-12-01

    The nuclear fission phenomenon continues to be an enigma, even after nearly 75 years of its discovery. Considerable progress has been made towards understanding the fission process. Both light projectiles and heavy ions have been employed to investigate nuclear fission. An extensive database of the properties of fissionable nuclei has been generated. The theoretical developments to describe the fission phenomenon have kept pace with the progress in the corresponding experimental measurements. As the fission process initiated by the neutrons has been well documented, the present article will be restricted to charged particle-induced fission reactions. The progress made in recent years and the prospects in the area of nuclear fission research will be the focus of this review.

  6. TORUS: Theory of Reactions for Unstable iSotopes - Year 1 Continuation and Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Arbanas, G; Elster, C; Escher, J; Mukhamedzhanov, A; Nunes, F; Thompson, I J

    2011-02-24

    The TORUS collaboration derives its name from the research it focuses on, namely the Theory of Reactions for Unstable iSotopes. It is a Topical Collaboration in Nuclear Theory, and funded by the Nuclear Theory Division of the Office of Nuclear Physics in the Office of Science of the Department of Energy. The funding started on June 1, 2010, it will have been running for nine months by the date of submission of this Annual Continuation and Progress Report on March 1, 2011. The extent of funding was reduced from the original application, and now supports one postdoctoral researcher for the years 1 through 3. The collaboration brings together as Principal Investigators a large fraction of the nuclear reaction theorists currently active within the USA. The mission of the TORUS Topical Collaboration is to develop new methods that will advance nuclear reaction theory for unstable isotopes by using three-body techniques to improve direct-reaction calculations, and, by using a new partial-fusion theory, to integrate descriptions of direct and compound-nucleus reactions. This multi-institution collaborative effort is directly relevant to three areas of interest: the properties of nuclei far from stability; microscopic studies of nuclear input parameters for astrophysics, and microscopic nuclear reaction theory.

  7. Nickel-Catalyzed Reactions Directed toward the Formation of Heterocycles.

    Science.gov (United States)

    Kurahashi, Takuya; Matsubara, Seijiro

    2015-06-16

    Heterocycles have garnered significant attention because they are important functional building blocks in various useful molecules, such as pharmaceuticals, agricultural chemicals, pesticides, and materials. Several studies have been conducted regarding the preparation of heterocyclic skeletons with an emphasis on selectivity and efficiency. Three strategies are typically employed to construct cyclic molecules, namely, cyclization, cycloaddition, and ring-size alterations. Although each method has certain advantages, cycloaddition may be superior from the viewpoint of divergence. Specifically, cycloadditions enable the construction of rings from several pieces. However, the construction of heterocycles via cycloadditions is more challenging than the construction of carbocycles. For heterocycle construction, simple pericyclic reactions rarely work smoothly because of the large HOMO-LUMO gap unless well-designed combinations, such as electron-rich dienes and aldehydes, are utilized. Thus, a different approach should be employed to prepare heterocycles via cycloadditions. To this end, the use of metallacycles containing heteroatoms is expected to serve as a promising solution. In this study, we focused on the preparation of heteroatom-containing nickelacycles. Because nickel possesses a relatively high redox potential and an affinity for heteroatoms, several methods were developed to synthesize heteronickelacycles from various starting materials. The prepared nickelacycles were demonstrated to be reasonable intermediates in cycloaddition reactions, which were used to prepare various heterocycles. In this Account, we introduce the following four methods to prepare heterocycles via heteronickelacycles. (1) Direct oxidative insertion of Ni(0) to α,β-unsaturated enone derivatives: treatment of 3-ethoxycarbonyl-4-phenyl-3-buten-2-one with Ni(0) afforded an oxa-nickelacycle, which reacted with alkynes to give pyrans. (2) Substitution of a part of a cyclic compound with

  8. The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

    Science.gov (United States)

    Jaisi, D.P.; Eberl, D.D.; Dong, H.; Kim, J.

    2011-01-01

    The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65??C) were the most favorable conditions forthe formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

  9. A reaction diffusion model of pattern formation in clustering of adatoms on silicon surfaces

    Directory of Open Access Journals (Sweden)

    Trilochan Bagarti

    2012-12-01

    Full Text Available We study a reaction diffusion model which describes the formation of patterns on surfaces having defects. Through this model, the primary goal is to study the growth process of Ge on Si surface. We consider a two species reaction diffusion process where the reacting species are assumed to diffuse on the two dimensional surface with first order interconversion reaction occuring at various defect sites which we call reaction centers. Two models of defects, namely a ring defect and a point defect are considered separately. As reaction centers are assumed to be strongly localized in space, the proposed reaction-diffusion model is found to be exactly solvable. We use Green's function method to study the dynamics of reaction diffusion processes. Further we explore this model through Monte Carlo (MC simulations to study the growth processes in the presence of a large number of defects. The first passage time statistics has been studied numerically.

  10. Formation of eta'(958) Meson Bound States by the 6Li(gamma,d) reaction

    CERN Document Server

    Miyatani, M; Nagahiro, H; Hirenzaki, S

    2016-01-01

    We have investigated the 6Li(gamma,d) reaction theoretically for the formation of the eta'(958) mesic nucleus close to the recoilless kinematics. We have developed the theoretical formula and reported the quantitative results of the formation spectra for various cases in this article. We have found that the formation cross sections are reduced by the effects of the fragile deuteron form factor.

  11. Polycyclic aromatic hydrocarbon (PAH) formation from benzyl radicals: a reaction kinetics study.

    Science.gov (United States)

    Sinha, Sourab; Raj, Abhijeet

    2016-03-21

    The role of resonantly stabilized radicals such as propargyl, cyclopentadienyl and benzyl in the formation of aromatic hydrocarbons such as benzene and naphthalene in the high temperature environments has been long known. In this work, the possibility of benzyl recombination to form three-ring aromatics, phenanthrene and anthracene, is explored. A reaction mechanism for it is developed, where reaction energetics are calculated using density functional theory (B3LYP functional with 6-311++G(d,p) basis set) and CBS-QB3, while temperature-dependent reaction kinetics are evaluated using transition state theory. The mechanism begins with barrierless formation of bibenzyl from two benzyl radicals with the release of 283.2 kJ mol(-1) of reaction energy. The further reactions involve H-abstraction by a H atom, H-desorption, H-migration, and ring closure to gain aromaticity. Through mechanism and rate of production analyses, the important reactions leading to phenanthrene and anthracene formation are determined. Phenanthrene is found to be the major product at high temperatures. Premixed laminar flame simulations are carried out by including the proposed reactions for phenanthrene formation from benzyl radicals and compared to experimentally observed species profiles to understand their effects on species concentrations.

  12. 'Would you eat cultured meat?': Consumers' reactions and attitude formation in Belgium, Portugal and the United Kingdom.

    Science.gov (United States)

    Verbeke, Wim; Marcu, Afrodita; Rutsaert, Pieter; Gaspar, Rui; Seibt, Beate; Fletcher, Dave; Barnett, Julie

    2015-04-01

    Cultured meat has evolved from an idea and concept into a reality with the August 2013 cultured hamburger tasting in London. Still, how consumers conceive cultured meat is largely an open question. This study addresses consumers' reactions and attitude formation towards cultured meat through analyzing focus group discussions and online deliberations with 179 meat consumers from Belgium, Portugal and the United Kingdom. Initial reactions when learning about cultured meat were underpinned by feelings of disgust and considerations of unnaturalness. Consumers saw few direct personal benefits but they were more open to perceiving global societal benefits relating to the environment and global food security. Both personal and societal risks were framed in terms of uncertainties about safety and health, and possible adverse societal consequences dealing with loss of farming and eating traditions and rural livelihoods. Further reflection pertained to skepticism about 'the inevitable' scientific progress, concern about risk governance and control, and need for regulation and proper labeling.

  13. EXFOR basics: A short guide to the nuclear reaction data exchange format

    Energy Technology Data Exchange (ETDEWEB)

    McLane, V.

    1996-07-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data.

  14. Simulations of Pore Formation in Lipid Membranes: Reaction Coordinates, Convergence, Hysteresis, and Finite-Size Effects.

    Science.gov (United States)

    Awasthi, Neha; Hub, Jochen S

    2016-07-12

    Transmembrane pores play an important role in various biophysical processes such as membrane permeation, membrane fusion, and antimicrobial peptide activity. In principal, all-atom molecular dynamics (MD) simulations provide an accurate model of pore formation in lipid membranes. However, the free energy landscape of transmembrane pore formation remains poorly understood, partly because potential of mean force (PMF) calculations of pore formation strongly depend on the choice of the reaction coordinate. In this study, we used umbrella sampling to compute PMFs for pore formation using three different reaction coordinates, namely, (i) a coordinate that steers the lipids in the lateral direction away from the pore center, (ii) the distance of a single lipid phosphate group from the membrane center, and (iii) the average water density inside a membrane-spanning cylinder. Our results show that while the three reaction coordinates efficiently form pores in membranes, they suffer from strong hysteresis between pore-opening and pore-closing simulations, suggesting that they do not restrain the systems close to the transition state for pore formation. The two reaction coordinates that act via restraining the lipids lead to more pronounced hysteresis compared with the coordinate acting on the water molecules. By comparing PMFs computed from membranes with different numbers of lipids, we observed significant artifacts from the periodic boundary conditions in small simulation systems. Further analysis suggests that the formation and disruption of a continuous hydrogen-bonding network across the membrane corresponds to the transition state for pore formation. Our study provides molecular insights into the critical steps of transmembrane pore formation, and it may guide the development of efficient reaction coordinates for pore formation.

  15. Sequence-Fenton Reaction for Decreasing Phenol Formation during Benzene Chemical Conversion in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    SB Mortazavi, A Sabzali, A Rezaee

    2005-04-01

    Full Text Available Advanced oxidation processes such as Fenton reagent generates highly reactive hydroxyl free radicals to oxidize various compounds in the water and wastewater. The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton, UV-Fenton and Fenton reactions in different batch reactors was examined using benzene as pollutant in aqueous solutions. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration, temperature, reaction time and ferrous ion concentration governing the Fenton process. The concentrations of produced phenol were measured at the end of the reactions. The role of sequence reaction was tested for decreasing phenol formation during benzene conversion. At optimum conditions, different Fenton-related processes were compared for the degradation of benzene. Increased degradation efficiency was observed in photo-Fenton processes as compared to conventional Fenton process. The formation of phenol in Fenton reaction depended on reaction time, sequence in reaction, purity of hydrogen peroxide and other compounds such as alcohols that contributed into the reaction. In the Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as the end products during the complete degradation of benzene. With the increase in mono-valence, two-valence ions and hardness, Fenton's efficiency decreased, respectively. Sequence Fenton reaction produced less phenol and its end products had smaller COD as compared to conventional Fenton process.

  16. Isolation and characterization of unusual multinuclear Schiff base complexes: rearrangements reactions and octanuclear cluster formation.

    Science.gov (United States)

    Martínez Belmonte, Marta; Escudero-Adán, Eduardo C; Martin, Eddy; Kleij, Arjan W

    2012-05-07

    The isolation and full characterization of multinuclear Schiff base complexes is reported, and their relevance as precursors for octanuclear Zn(8) salen cluster complex formation is discussed. Starting from simple precursors, three tetranuclear Zn(4) complexes were accessed that incorporate typical half-salen units and comprise of bridging acetates. The use of alternative reaction conditions or a step-wise approach smoothly leads to Zn(8) cluster formation. In addition, the tetranuclear Zn(4) complexes themselves may also serve as precursors toward Zn(8) cluster formation when treated under appropriate reaction conditions. The influence of the solvent medium in the latter Zn(4) → Zn(8) conversion was separately studied and revealed the formation of unusual pyridine-ligated multinuclear structures with fully condensed salen coordination pockets, providing a possible prelude to octanuclear cluster formation.

  17. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    Energy Technology Data Exchange (ETDEWEB)

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  18. Progress and prospects in nanoscale dry processes: How can we control atomic layer reactions?

    Science.gov (United States)

    Ishikawa, Kenji; Karahashi, Kazuhiro; Ichiki, Takanori; Chang, Jane P.; George, Steven M.; Kessels, W. M. M.; Lee, Hae June; Tinck, Stefan; Um, Jung Hwan; Kinoshita, Keizo

    2017-06-01

    In this review, we discuss the progress of emerging dry processes for nanoscale fabrication. Experts in the fields of plasma processing have contributed to addressing the increasingly challenging demands in achieving atomic-level control of material selectivity and physicochemical reactions involving ion bombardment. The discussion encompasses major challenges shared across the plasma science and technology community. Focus is placed on advances in the development of fabrication technologies for emerging materials, especially metallic and intermetallic compounds and multiferroic, and two-dimensional (2D) materials, as well as state-of-the-art techniques used in nanoscale semiconductor manufacturing with a brief summary of future challenges.

  19. Deduction of compound nucleus formation probability from the fragment angular distributions in heavy-ion reactions

    Science.gov (United States)

    Yadav, C.; Thomas, R. G.; Mohanty, A. K.; Kapoor, S. S.

    2015-07-01

    The presence of various fissionlike reactions in heavy-ion induced reactions is a major hurdle in the path to laboratory synthesis of heavy and super-heavy nuclei. It is known that the cross section of forming a heavy evaporation residue in fusion reactions depends on the three factors—the capture cross section, probability of compound nucleus formation PCN, and the survival probability of the compound nucleus against fission. As the probability of compound nucleus formation, PCN is difficult to theoretically estimate because of its complex dependence on several parameters; attempts have been made in the past to deduce it from the fission fragment anisotropy data. In the present work, the fragment anisotropy data for a number of heavy-ion reactions are analyzed and it is found that deduction of PCN from the anisotropy data also requires the knowledge of the ratio of relaxation time of the K degree of freedom to pre-equilibrium fission time.

  20. Optimized Reaction Conditions for Amide Bond Formation in DNA-Encoded Combinatorial Libraries.

    Science.gov (United States)

    Li, Yizhou; Gabriele, Elena; Samain, Florent; Favalli, Nicholas; Sladojevich, Filippo; Scheuermann, Jörg; Neri, Dario

    2016-08-08

    DNA-encoded combinatorial libraries are increasingly being used as tools for the discovery of small organic binding molecules to proteins of biological or pharmaceutical interest. In the majority of cases, synthetic procedures for the formation of DNA-encoded combinatorial libraries incorporate at least one step of amide bond formation between amino-modified DNA and a carboxylic acid. We investigated reaction conditions and established a methodology by using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide, 1-hydroxy-7-azabenzotriazole and N,N'-diisopropylethylamine (EDC/HOAt/DIPEA) in combination, which provided conversions greater than 75% for 423/543 (78%) of the carboxylic acids tested. These reaction conditions were efficient with a variety of primary and secondary amines, as well as with various types of amino-modified oligonucleotides. The reaction conditions, which also worked efficiently over a broad range of DNA concentrations and reaction scales, should facilitate the synthesis of novel DNA-encoded combinatorial libraries.

  1. Numerical Study on the Impacts of Heterogeneous Reactions on Ozone Formation in the Beijing Urban Area

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area.The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination,resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.

  2. Open problems in formation and decay of composite systems in heavy ion reactions

    Indian Academy of Sciences (India)

    G Viesti; V Rizzi; M Barbui; D Fabris; M Lunardon; G Nebbia; S Moretto; S Pesente; M Cinausero; E Fioretto; G Prete; D Shetty

    2001-08-01

    New highly exclusive experiments in the field of formation and decay of composite systems in heavy ion reactions are presented. Dynamical effects are reviewed in the light of recent works on the role of the / asymmetry between projectile and target. The possibility of extracting directly from the experimental data the emission barrier of alpha particles emitted from highly excited nuclei is discussed. Finally, the first experimental evidence of double giant resonance excitation in fusion-evaporation reaction is presented.

  3. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms.

    Science.gov (United States)

    Rasmussen, Helena; Sørensen, Hanne R; Meyer, Anne S

    2014-02-19

    The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes for the formation of HMF from glucose and three routes for furfural formation from xylose are possible. In addition, new findings show that biomass monosaccharides themselves can react further to form pseudo-lignin and humins as well as a wide array of other compounds when exposed to high temperatures. Hence, several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing strategies and forms an important basis for the development of new biorefinery products from lignocellulosic biomass as well.

  4. Substrate decomposition in galvanic displacement reaction: Contrast between gold and silver nanoparticle formation

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Tapas; Satpati, Biswarup, E-mail: biswarup.satpati@saha.ac.in [Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata-700 064 (India); Kabiraj, D. [Inter-University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi-110067 (India)

    2015-06-24

    We have investigated substrate decomposition during formation of silver and gold nanoparticles in galvanic displacement reaction on germanium surfaces. Silver and gold nanoparticles were synthesized by electroless deposition on sputter coated germanium thin film (∼ 200 nm) grown initially on silicon substrate. The nanoparticles formation and the substrate corrosion were studied using scanning transmission electron microscopy (STEM) and the energy dispersive X-ray (EDX) spectroscopy.

  5. An alternative approach to aldol reactions: gold-catalyzed formation of boron enolates from alkynes.

    Science.gov (United States)

    Körner, Cindy; Starkov, Pavel; Sheppard, Tom D

    2010-05-05

    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh(3)AuNTf(2) at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or intramolecular Chan-Lam coupling, respectively. A combined gold/boronic acid catalyzed aldol condensation reaction of an alkynyl aldehyde was also successfully achieved.

  6. Recent Progress on Fe/N/C Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jing Liu

    2015-07-01

    Full Text Available In order to reduce the overall system cost, the development of inexpensive, high-performance and durable oxygen reduction reaction (ORRN, Fe-codoped carbon-based (Fe/N/C electrocatalysts to replace currently used Pt-based catalysts has become one of the major topics in research on fuel cells. This review paper lays the emphasis on introducing the progress made over the recent five years with a detailed discussion of recent work in the area of Fe/N/C electrocatalysts for ORR and the possible Fe-based active sites. Fe-based materials prepared by simple pyrolysis of transition metal salt, carbon support, and nitrogen-rich small molecule or polymeric compound are mainly reviewed due to their low cost, high performance, long stability and because they are the most promising for replacing currently used Pt-based catalysts in the progress of fuel cell commercialization. Additionally, Fe-base catalysts with small amount of Fe or new structure of Fe/Fe3C encased in carbon layers are presented to analyze the effect of loading and existence form of Fe on the ORR catalytic activity in Fe-base catalyst. The proposed catalytically Fe-centered active sites and reaction mechanisms from various authors are also discussed in detail, which may be useful for the rational design of high-performance, inexpensive, and practical Fe-base ORR catalysts in future development of fuel cells.

  7. EXFOR systems manual: Nuclear reaction data exchange format. Revision 97/1

    Energy Technology Data Exchange (ETDEWEB)

    McLane, V. [ed.] [comp.

    1997-07-01

    This document describes EXFOR, the exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Center Network. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility rather than optimization of data processing in order to meet the diverse needs of the nuclear reaction data centers. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, is designed to allow a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine).

  8. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    Science.gov (United States)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  9. The effects of phytic acid on the Maillard reaction and the formation of acrylamide.

    Science.gov (United States)

    Wang, Huan; Zhou, Yamin; Ma, Jimei; Zhou, Yuanyuan; Jiang, Hong

    2013-11-01

    Phytic acid, myo-inositol hexaphosphoric acid, exists in substantial (1-5%) amounts in edible plant seeds. In this study the effects of phytic acid on the Maillard reaction and the formation of acrylamide were investigated. Both phytic acid and phosphate enhanced browning in glucose/β-alanine system, but phytic acid was less effective than phosphate. Higher pH favoured the catalytic activities for both of them. The influence of the types of sugar and amino acid on the reaction was also examined. Browning was suppressed by the addition of calcium and magnesium ions, but an additive effect was observed for ferrous ions and phytic acid in glucose/β-alanine solution at pH 8.0. Both phytic acid and phosphate promoted the polymerisation of the reaction intermediates. The kinetics of Maillard reaction was first-ordered reaction in the presence of phytic acid. Phytic acid was less effective than phosphate in the formation of acrylamide. When potato slices were treated with sodium phytate and calcium chloride successively, the formation of acrylamide was greatly suppressed.

  10. Reactions and SEI Formation during Charging of Li-O2 Cells

    DEFF Research Database (Denmark)

    Højberg, Jonathan; Knudsen, Kristian Bastholm; Hjelm, Johan

    2015-01-01

    chemical formation of a solid electrolyte interface (SEI) layer as the first monolayer of Li2O2 is oxidized, leading to a voltage increase. The first electrochemical degradation reaction is identified between 3.3 V and 3.5 V, and the chemical degradation is limited above 3.5 V, suggesting that a chemically...

  11. Effects of online advertising format and persuasion knowledge on audience reactions

    NARCIS (Netherlands)

    Tutaj, K.; van Reijmersdal, E.A.

    2012-01-01

    In an experiment (N = 99), effects of subtle and prominent online advertising formats, respectively sponsored content and banner ads, on audience reactions toward the advertisement are tested. In addition, the role of several persuasion knowledge elements such as understanding of persuasive intent a

  12. Effects of online advertising format and persuasion knowledge on audience reactions

    NARCIS (Netherlands)

    Tutaj, K.; van Reijmersdal, E.A.

    2012-01-01

    In an experiment (N = 99), effects of subtle and prominent online advertising formats, respectively sponsored content and banner ads, on audience reactions toward the advertisement are tested. In addition, the role of several persuasion knowledge elements such as understanding of persuasive intent a

  13. Silver(Ⅰ)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides: Unexpected formation of vinyl sulfones

    Institute of Scientific and Technical Information of China (English)

    Gui Sheng Deng; Teng Fei Sun

    2012-01-01

    A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate.Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity.A free radical mechanism has been proposed to account for the formation of the products.

  14. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  15. On adduct formation and reactivity in the OCS plus OH reaction

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht; Kyte, Mildrid; Østerstrøm, Freja From

    2017-01-01

    The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We...

  16. Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

    Institute of Scientific and Technical Information of China (English)

    Kebing Wang; Jie Yao; Yue Wang; Gongying Wang

    2007-01-01

    The coupling reaction of formaldehyde (FA) and methyl formate (MF) to form methyl glycolate (MG) and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH) as well as assisted by different kinds of solvents or Ni-containing compounds.had been investigated.The results showed that when the reaction was carried out at 140℃ with a molar ratio of FA to MF of 0.65:1,molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc Was 31.1% and 17.1%.respectively.p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system Was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl2<NiBr2<NiI2.The present system is less corrosive when compared with the previous system,in which strong inorganic liquid acids were used as catalysts.

  17. Progress in aggresome formation%蛋白聚集体形成研究进展

    Institute of Scientific and Technical Information of China (English)

    李清华; 李清华

    2011-01-01

    神经退行性疾病(neurodegenerative disorder)是由于神经元进行性变性死亡导致的以中枢神经系统损害为主的神经系统疾病.其中包括帕金森病、阿尔茨海默症、亨廷顿舞蹈病等.当错误折叠的蛋白超过分子伴侣的重新折叠和泛素-蛋白酶体系降解能力的时候,错误折叠的蛋白质可以通过被介导的动力蛋白马达逆向转运至微管组织中心周围形成蛋白聚集体.蛋白聚集体的形成被认为是细胞的一种防御反应,隔离有毒的错误折叠蛋白进而进行清除.蛋白聚集体通路的研究可为多种神经退变性疾病提供治疗靶点.%Neurodegenerative disorders are a gruop of combined nervous system diseases,due to progressive degenerative necrosis of neurons,and their main features are central nervous system damage.These include Parkinsonˊs disease,Alzheimerˊs disease,and Huntington' s disease.When the production of misfolded proteins exceeds the capacity of the chaperone refolding system and the ubiquitin-proteasome degradation pathway,misfolded proteins are actively transported by dynein/dynactin-mediated microtubulebased to a cytoplasmic juxtanuclear structure called an aggresome.The formation of aggresome is thought a kind of defensive reaction to segregate and clear the cytotoxicity of misfolded and aggregated proteins.Characterization of the molecular mechanisms underlying aggresome formation and its regulation has begun to provide promising therapeutic targets that may be relevant to neurodegenerative diseases.

  18. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

    Science.gov (United States)

    George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

    2016-12-01

    The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

  19. Synthesis and spectral characterization of 2,2-diphenylethyl glucosinolate and HPLC-based reaction progress curve data for the enzymatic hydrolysis of glucosinolates by Sinapis alba myrosinase

    Directory of Open Access Journals (Sweden)

    Chase A. Klingaman

    2017-02-01

    Full Text Available The data presented in this article are related to the research article, “HPLC-based enzyme kinetics assay for glucosinolate hydrolysis facilitate analysis of systems with both multiple reaction products and thermal enzyme denaturation” (C.K. Klingaman, M.J. Wagner, J.R. Brown, J.B. Klecker, E.H. Pauley, C.J. Noldner, J.R. Mays, [1]. This data article describes (1 the synthesis and spectral characterization data of a non-natural glucosinolate analogue, 2,2-diphenylethyl glucosinolate, (2 HPLC standardization data for glucosinolate, isothiocyanate, nitrile, and amine analytes, (3 reaction progress curve data for enzymatic hydrolysis reactions with variable substrate concentration, enzyme concentration, buffer pH, and temperature, and (4 normalized initial velocities of hydrolysis/formation for analytes. These data provide a comprehensive description of the enzyme-catalyzed hydrolysis of 2,2-diphenylethyl glucosinolate (5 and glucotropaeolin (6 under widely varied conditions.

  20. Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms

    DEFF Research Database (Denmark)

    Rasmussen, Helena; Sørensen, Hanne R.; Meyer, Anne S.

    2014-01-01

    , several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes......The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5...... and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing...

  1. Digging Up the Human Genome: Current Progress in Deciphering Adverse Drug Reactions

    Directory of Open Access Journals (Sweden)

    Shih-Chi Su

    2014-01-01

    Full Text Available Adverse drug reactions (ADRs are a major clinical problem. In addition to their clinical impact on human health, there is an enormous cost associated with ADRs in health care and pharmaceutical industry. Increasing studies revealed that genetic variants can determine the susceptibility of individuals to ADRs. The development of modern genomic technologies has led to a tremendous advancement of improving the drug safety and efficacy and minimizing the ADRs. This review will discuss the pharmacogenomic techniques used to unveil the determinants of ADRs and summarize the current progresses concerning the identification of biomarkers for ADRs, with a focus on genetic variants for genes encoding drug-metabolizing enzymes, drug-transporter proteins, and human leukocyte antigen (HLA. The knowledge gained from these cutting-edge findings will form the basis for better prediction and management for ADRs, ultimately making the medicine personalized.

  2. Spatial Heterogeneity and Imperfect Mixing in Chemical Reactions: Visualization of Density-Driven Pattern Formation

    Directory of Open Access Journals (Sweden)

    Sabrina G. Sobel

    2009-01-01

    Full Text Available Imperfect mixing is a concern in industrial processes, everyday processes (mixing paint, bread machines, and in understanding salt water-fresh water mixing in ecosystems. The effects of imperfect mixing become evident in the unstirred ferroin-catalyzed Belousov-Zhabotinsky reaction, the prototype for chemical pattern formation. Over time, waves of oxidation (high ferriin concentration, blue propagate into a background of low ferriin concentration (red; their structure reflects in part the history of mixing in the reaction vessel. However, it may be difficult to separate mixing effects from reaction effects. We describe a simpler model system for visualizing density-driven pattern formation in an essentially unmixed chemical system: the reaction of pale yellow Fe3+ with colorless SCN− to form the blood-red Fe(SCN2+ complex ion in aqueous solution. Careful addition of one drop of Fe(NO33 to KSCN yields striped patterns after several minutes. The patterns appear reminiscent of Rayleigh-Taylor instabilities and convection rolls, arguing that pattern formation is caused by density-driven mixing.

  3. Aromatics oxidation and soot formation in flames. Progress report, August 15, 1990--August 14, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T.

    1993-04-01

    This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify, and to confirm or determine rate constants for, the main benzene oxidation reactions in flames, and to characterize soot and fullerenes and their formation mechanisms and kinetics. Stable and radical species profiles in the aromatics oxidation study are measured using molecular beam sampling with on-line mass spectrometry. The rate of soot formation measured by conventional optical techniques is found to support the hypotheses that particle inception occurs through reactive coagulation of high molecular weight PAH in competition with destruction by OHattack, and that the subsequent growth of the soot mass occurs through addition reactions of PAH and C{sub 2}H{sub 2} with the soot particles. During the first year of this reporting period, fullerenes C{sub 60} and C{sub 70} in substantial quantities were found in the flames being studied. The fullerenes were recovered, purified and spectroscopically identified. The yields of C{sub 60} and C{sub 70} were then determined over ranges of conditions in low-pressure premixed flames of benzene and oxygen.

  4. Impact of high-intensity ultrasound on the formation of lactulose and Maillard reaction glycoconjugates.

    Science.gov (United States)

    Corzo-Martínez, Marta; Montilla, Antonia; Megías-Pérez, Roberto; Olano, Agustín; Moreno, F Javier; Villamiel, Mar

    2014-08-15

    The impact of high-intensity ultrasound (US) on the formation of lactulose during lactose isomerization and on the obtention of lysine-glucose glycoconjugates during Maillard reaction (MR) has been studied, respectively, in basic and neutral media. As compared to equivalent conventional heat treatments, a higher formation of furosine, as indicator of initial steps of MR, was observed together with more advance of the reaction in US treated samples, this effect being more pronounced with the increase of US amplitude (50-70%) and temperature (25-40 °C). Regarding the influence of US on lactulose formation, in general, in a buffered system (pH 10.0), US at 70% of amplitude and 60 °C increased the rate of lactose isomerization, higher values of lactulose, epilactose and galactose being observed in comparison to conventional heating. The results of this work showed an acceleration of both reactions by US, indicating its usefulness to promote the formation of functional ingredients.

  5. Chemistry of polycyclic aromatic hydrocarbons formation from phenyl radical pyrolysis and reaction of phenyl and acetylene.

    Science.gov (United States)

    Comandini, A; Malewicki, T; Brezinsky, K

    2012-03-15

    An experimental investigation of phenyl radical pyrolysis and the phenyl radical + acetylene reaction has been performed to clarify the role of different reaction mechanisms involved in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) serving as precursors for soot formation. Experiments were conducted using GC/GC-MS diagnostics coupled to the high-pressure single-pulse shock tube present at the University of Illinois at Chicago. For the first time, comprehensive speciation of the major stable products, including small hydrocarbons and large PAH intermediates, was obtained over a wide range of pressures (25-60 atm) and temperatures (900-1800 K) which encompass the typical conditions in modern combustion devices. The experimental results were used to validate a comprehensive chemical kinetic model which provides relevant information on the chemistry associated with the formation of PAH compounds. In particular, the modeling results indicate that the o-benzyne chemistry is a key factor in the formation of multi-ring intermediates in phenyl radical pyrolysis. On the other hand, the PAHs from the phenyl + acetylene reaction are formed mainly through recombination between single-ring aromatics and through the hydrogen abstraction/acetylene addition mechanism. Polymerization is the common dominant process at high temperature conditions.

  6. Contrasting reactions of hydrated electron and formate radical with 2-thio analogues of cytosine and uracil.

    Science.gov (United States)

    Prasanthkumar, Kavanal P; Alvarez-Idaboy, Juan R; Kumar, Pavitra V; Singh, Beena G; Priyadarsini, K Indira

    2016-10-19

    2-Thiocytosine (TC) and 2-thiouracil (TU) were subjected to hydrated electron (eaq(-)), formate radical (CO2˙(-)) and 2-hydroxypropan-2-yl radical ((CH3)2˙COH) reactions in aqueous medium. Transients were characterized by absorption spectroscopy and the experimental findings were rationalized by DFT calculations at LC-ωPBE and M06-2X levels using a 6-311+G(d,p) basis set and SMD solvation. In eaq(-) reactions, a ring N-atom protonated radical of TC and an exocyclic O-atom protonated radical of TU were observed via addition of eaq(-) and subsequent protonation by solvent molecules. However, two competing but simultaneous mechanisms are operative in CO2˙(-) reactions with TC and TU. The first one corresponds to formations of N(O)-atom protonated radicals (similar to eaq(-) reactions); the second mechanism led to 2 center-3 electron, sulfur-sulfur bonded neutral dimer radicals, TCdim˙ and TUdim˙. DFT calculations demonstrated that H-abstraction by CO2˙(-) from TC(TU) results in S-centered radical which upon combination with TC(TU) provide the dimer radical. In some cases, DFT energy profiles were further validated by CBS-QB3//M06-2X calculations. This is the first time report for a contradictory behavior in the mechanisms of eaq(-) and CO2˙(-) reactions with any pyrimidines or their thio analogues.

  7. Early stages of particle formation in precipitation reactions-quinacridone and boehmite as generic examples.

    Science.gov (United States)

    Haberkorn, H; Franke, D; Frechen, Th; Goesele, W; Rieger, J

    2003-03-01

    For many products, such as nanoparticulate systems, particle formation by precipitation is an essential procedural step. To learn more about the processes involved in precipitation, we investigated particle formation during precipitation reactions by means of online and offline methods. As model systems we chose the catalyst boehmite and the organic pigment quinacridone. The reactants were mixed in a mixing device and led into a reaction tube. At the end of the tube, a free jet of the suspension was produced. By varying the length of the reaction tube the time between mixing the reactants and the moment of observation was varied. Thus a time resolution down to 10 ms from the beginning of the reaction was obtained. Small-angle X-ray scattering on the free jet yielded online information about the structural inhomogeneities within the reacting systems. Transmission electron microscopy patterns obtained from quenched samples, which were taken by shooting copper grids through the free jet into liquid nitrogen, provided complementary information about structural features. Immediately after mixture an emulsion-like structure develops indicating that classical nucleation theory does not apply in the present systems. This finding can be explained by assuming instantaneous reaction at the interfaces of the two reactants that meet in the mixing device. From this preliminary state primary particles form with a size in the nanometer range. The observations can be rationalized by considering the underlying hydrodynamics of turbulent mixing of the reactants.

  8. Quantifying the ionic reaction channels in the Secondary Organic Aerosol formation from glyoxal

    Science.gov (United States)

    Maxut, Aurelia; Nozière, Barbara; Rossignol, Stéphanie; George, Christian; Waxman, Eleanor Marie; Laskin, Alexander; Slowik, Jay; Dommen, Josef; Prévôt, André; Baltensperger, Urs; Volkamer, Rainer

    2014-05-01

    Glyoxal, a common organic gas in the atmosphere, has been identified in recent years as an important Secondary Organic Aerosol (SOA) precursor (Volkamer et al., 2007). But, unlike with other precursors, the SOA is largely produced by particle-phase reactions (Volkamer et al., 2009) and equilibria (Kampf et al. 2013) that are still not entirely characterized. Since 2009 series of smog chamber experiments have been performed within the Eurochamp program at the Paul Scherrer Institute, Switzerland, to investigate SOA formation from glyoxal. In these experiments, glyoxal was produced by the gas-phase oxidation of acetylene in the presence of seeds, the seed composition and other conditions being varied. The 2011 campaign resulted in the identification of salting processes controlling the glyoxal partitioning in the seeds (Kampf et al. 2013). This presentation will report results of the 2013 campaign focusing on the identification of the various reactions (ionic or photo-induced) contributing to the SOA mass. In particular, the contribution of the ionic reactions, i.e. mediated by NH4+, were investigated by quantifying the formation of imidazoles (imidazole, imidazole-2-carboxaldehyde, 2,2'-biimidazole) from the small condensation channel of glyoxal with ammonia. For this, the SOA produced were collected on quartz filters and analyzed by Orbitrap LC/MS (Q-Exactive Thermo Fisher). The formation of other products such as organic acids was also investigated to determine potential competing reactions. Time-resolved MOUDI sampling coupled with nano-DESY/ESI-MS/MS analysis was also used to identify nitrogen- and sulphur-containing products from all the reactions. The results obtained for a range of conditions will be presented and compared with recent mechanistic information on the ionic reaction channels (Nozière et al., in preparation, 2013). The implementation of all this new information into a glyoxal-SOA model will be discussed.

  9. Radionuclide reactions with groundwater and basalts from Columbia River basalt formations

    Energy Technology Data Exchange (ETDEWEB)

    Barney, G.S.

    1981-06-01

    Chemical reactions of radionuclides with geologic materials found in Columbia River basalt formations were studied. The objective was to determine the ability of these formations to retard radionuclide migration from a radioactive waste repository located in deep basalt. Reactions that can influence migration are precipitation, ion-exchange, complexation, and oxidation-reduction. These reactions were studied by measuring the effects of groundwater composition and redox potential (Eh) on radionuclide sorption on fresh basalt surfaces, a naturally altered basalt, and a sample of secondary minerals associated with a Columbia River basalt flow. In addition, radionuclide sorption isotherms were measured for these materials and reaction kinetics were determined. The radionuclides studied were /sup 137/Cs, /sup 85/Sr, /sup 75/Se, /sup 95m/Tc, /sup 237/Np, /sup 241/Am, /sup 226/Ra and /sup 237/Pu. The Freundlich equation accurately describes the isotherms when precipitation of radionuclides does not occur. In general, sorption increased in the order: basalt < altered basalt < secondary minerals. This increase in sorption corresponds to increasing surface area and cation exchange capacity. The Eh of the system had a large effect on technetium, plutonium, and neptunium sorption. Technetium(VII), Pu(VI), and Np(V) are reduced to Tc(IV), Pu(IV), and Np(IV), respectively, under Eh conditions expected in deep basalt formations. The kinetics of radionuclide sorption and basalt-groundwater reactions were observed over a period of 18 weeks. Most sorption reactions stabilized after about four weeks. Groundwater composition changed the least in contact with altered basalt. Contact with secondary minerals greatly increased Ca, K, and Mg concentrations in the groundwater.

  10. Secondary organic aerosol formation from ozone reactions with single terpenoids and terpenoid mixtures

    Science.gov (United States)

    Waring, Michael S.; Wells, J. Raymond; Siegel, Jeffrey A.

    2011-08-01

    Ozone reacts with indoor-emitted terpenoids to form secondary organic aerosol (SOA). Most SOA research has focused on ozone reactions with single terpenoids or with consumer products, and this paper reports the results from an investigation of SOA formation from ozone reactions with both single terpenoids and mixtures of D-limonene, α-pinene, and α-terpineol. Transient experiments were conducted at low (25 ppb) and high (100 ppb) initial concentrations of ozone. The three terpenoids were tested singly and in combinations in a manner that controlled for their different reaction rates with ozone. The SOA formation was assessed by examining the evolution in time of the resulting number size-distributions and estimates of the mass concentrations. The results suggest that at higher ozone and terpenoid concentrations, SOA number formation follows a linear trend as a function of the initial rate of reaction. This finding was valid for both single terpenoids and mixtures. Generally speaking, higher ozone and terpenoid concentrations also led to larger geometric mean diameters and smaller geometric standard deviations of fitted lognormal distributions of the formed SOA. By assuming a density, mass concentrations were also assessed and did not follow as consistent of a trend. At low ozone concentration conditions, reactions with only D-limonene yielded the largest number concentrations of any experiment, even more than experiments with mixtures containing D-limonene and much higher overall terpenoid concentrations. This finding was not seen for high ozone concentrations. These experiments demonstrate quantifiable trends for SOA forming reactions of ozone and mixtures, and this work provides a framework for expanding these results to more complex mixtures and consumer products.

  11. Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void

    Science.gov (United States)

    Shan, Tzu-Ray; Thompson, Aidan P.

    2014-05-01

    We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N2 and H2O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

  12. Instability and pattern formation in reaction-diffusion systems: a higher order analysis.

    Science.gov (United States)

    Riaz, Syed Shahed; Sharma, Rahul; Bhattacharyya, S P; Ray, D S

    2007-08-14

    We analyze the condition for instability and pattern formation in reaction-diffusion systems beyond the usual linear regime. The approach is based on taking into account perturbations of higher orders. Our analysis reveals that nonlinearity present in the system can be instrumental in determining the stability of a system, even to the extent of destabilizing one in a linearly stable parameter regime. The analysis is also successful to account for the observed effect of additive noise in modifying the instability threshold of a system. The analytical study is corroborated by numerical simulation in a standard reaction-diffusion system.

  13. Condensation reaction of formaldehyde and methyl formate catalyzed by a composite catalyst system

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The condensation reaction of formaldehyde and methyl formate to form methyl glycolate and methyl methoxy acetate catalyzed by p-toluenesulfonic acid and different Lewis acid compounds has been investigated. The composite catalytic system consisting of p-toluenesulfonic acid and NiX2 (X = Cl, Br, I), especially NiI2, exhibited a high catalytic performance for the condensation reaction, the total yield of MG and MMAc was up to 72.37%.(C) 2007 Gong Ying Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  14. Kinetics of contrail particles formation and heterogeneous reactions on such particles

    Energy Technology Data Exchange (ETDEWEB)

    Kogan, M.N.; Butkovsky, A.V.; Erofeev, A.I.; Freedlender, O.G.; Makashev, N.K. [Central Aerohydrodynamic Inst., Zhukovsky (Russian Federation)

    1997-12-31

    The research of impact of aircraft emissions upon the atmosphere is very complex and difficult problem. More than two decades of intensive investigations of the problem of ozone decay do not permit to make definite conclusions. Many important problems still remain unsolved in the aircraft/atmosphere interaction: engine, nozzle, jet, jet/vortex system interaction, vortex breakdown, contrail formation, meso-scale and global processes, their effects on climate. The particles formation and heterogeneous reactions play an important role in some of these processes. These problems are discussed. (author) 11 refs.

  15. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  16. Background defining during the imine formation reaction in FT-IR liquid cell

    Science.gov (United States)

    Namli, Hilmi; Turhan, Onur

    2006-05-01

    Imine formation is a very important chemical reaction because of its relevance to biological process. Therefore, it is crucial to follow whole reaction process in detail. The current work performed to monitor the whole imination reaction in real time in liquid cell by FT-IR spectroscopy. The complex spectral futures due to solvent, unreacted reagents, acid catalysis and other additives are eliminated by defining a background at the beginning or at any time during the reaction. This procedure also makes it possible to monitor the changes in the concentration of each component in the liquid cell. The consumption of the functional groups of the reagents results in absorbance due to the direct difference spectra while the appearance of functional groups is monitored as percentage transmittance. The concentration changes in the cell arising from the reaction gives the product spectra without having to isolate it from the mixture. It is also possible to see the intermediates appearing and disappearing during the reaction. This report also illustrates a brief application of the technique by time dependence of the peak highs in absorption (ABS) mode.

  17. Positronium in a Liquid Phase: Formation, Bubble State and Chemical Reactions

    Directory of Open Access Journals (Sweden)

    Sergey V. Stepanov

    2012-01-01

    Full Text Available The present approach describes the e+ fate since its injection into a liquid until its annihilation. Several stages of the e+ evolution are discussed: (1 energy deposition and track structure of fast positrons: ionization slowing down, number of ion-electron pairs, typical sizes, thermalization, electrostatic interaction between e+ and the constituents of its blob, and effect of local heating; (2 positronium formation in condensed media: the Ore model, quasifree Ps state, intratrack mechanism of Ps formation; (3 fast intratrack diffusion-controlled reactions: Ps oxidation and ortho-paraconversion by radiolytic products, reaction rate constants, and interpretation of the PAL spectra in water at different temperatures; (4 Ps bubble models. Inner structure of positronium (wave function, energy contributions, relationship between the pick-off annihilation rate and the bubble radius.

  18. Turing Bifurcation and Pattern Formation of Stochastic Reaction-Diffusion System

    Directory of Open Access Journals (Sweden)

    Qianiqian Zheng

    2017-01-01

    Full Text Available Noise is ubiquitous in a system and can induce some spontaneous pattern formations on a spatially homogeneous domain. In comparison to the Reaction-Diffusion System (RDS, Stochastic Reaction-Diffusion System (SRDS is more complex and it is very difficult to deal with the noise function. In this paper, we have presented a method to solve it and obtained the conditions of how the Turing bifurcation and Hopf bifurcation arise through linear stability analysis of local equilibrium. In addition, we have developed the amplitude equation with a pair of wave vector by using Taylor series expansion, multiscaling, and further expansion in powers of small parameter. Our analysis facilitates finding regions of bifurcations and understanding the pattern formation mechanism of SRDS. Finally, the simulation shows that the analytical results agree with numerical simulation.

  19. Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+

    Science.gov (United States)

    Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen

    2017-07-01

    Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of

  20. Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose

    Energy Technology Data Exchange (ETDEWEB)

    Assary, Rajeev S.; Curtiss, Larry A.

    2012-02-06

    Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

  1. Thermochemistry and reaction barriers for the formation of levoglucosenone from cellobiose.

    Energy Technology Data Exchange (ETDEWEB)

    Assary, R. S.; Curtiss, L. A. (Center for Nanoscale Materials); ( MSD); (Northwestern Univ.)

    2012-02-06

    Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

  2. Proton Mobility in b2 Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides

    Science.gov (United States)

    Nelson, Carissa R.; Abutokaikah, Maha T.; Harrison, Alex G.; Bythell, Benjamin J.

    2016-03-01

    A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting.

  3. Formation process of liquid in interface of Ti/Cu contact reaction couple

    Institute of Scientific and Technical Information of China (English)

    WU Ming-fang; YU Chun; YU Zhi-shi; LI Rui-feng

    2005-01-01

    By using the Ti/Cu contact reaction couples,the dissolution behavior of Ti and Cu in the eutectic reaction process was investigated under different conditions.The results show that the formation of eutectic liquid phase has a directional property,I.e.the eutectic liquid phase forms first at the Cu side and then spreads along the depth direction of Cu.The width of the eutectic liquid zone when Ti is placed on Cu is wider than that when Ti is placed under Cu.The shape of the upside liquid zone is wave-like.This phenomenon indicates that the formation process and spreading behavior in the upside are different from those in the underside,and there exists void effect in the Cu side of underside liquid zone,this will result in the delaying phenomenon of the contact reaction between Ti and Cu,and distinctly different shapes of the both liquid zones.The formation process of Ti/Cu eutectic liquid zone is similar to that of the traditional solid-state diffusion layer,and the relationship between the width of liquid zone and holding time obeys a square root law.

  4. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    Science.gov (United States)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  5. Effect of reaction time on formation of silica core/shell particles

    Directory of Open Access Journals (Sweden)

    Milan P. Nikolić

    2015-12-01

    Full Text Available The silica core/shell nanostructures were prepared by a wet-chemical process. Silica core particles were prepared by hydrolysis and condensation of tetraethylorthosilicate. The obtained particles (average size ∼0.4 µm were used as templates for assembling of silica nanoparticles generated from highly basic sodium silicate solution. The silica core particles were functionalized with 3-aminopropyltriethoxysilane (APTES to allow electrostatic assembling of silica nanoparticles on the surface of silica core particles. In order to find the optimal conditions for synthesis of silica core/shell particles with mesoporous shells, the effect of reaction time on formation of silica nanoparticles was investigated. The effect of process parameters on generation and aggregation of silica nanoparticles prepared from highly basic sodium silicate solution was also investigated. It was shown that the size of silica nanoparticles and tendency towards aggregation increase with increasing the reaction time and temperature. These behaviours were reflected on the formation of mesoporous silica shell around silica core particles. Thin and uniform mesoporous silica layers were obtained if reaction times were kept short. When the reaction time was prolonged, the thicker and non-uniform shells were obtained.

  6. PCDD/F Formation mechanism: effect of surface composition on chlorination and condensation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sidhu, S.; Nath, P.

    2002-07-01

    The post-combustion zone immediately following the incineration (flame) zone is a potential pollutant formation zone as it contains excess O{sub 2} (3-9%), sufficient residence time (from sub seconds to minutes) and catalytically active fly ash particles. This is an ideal reaction environment for the C{sub 1} and C{sub 2} compounds exiting the flame zone to undergo condensation and chlorination reactions. Heterogeneous reactions of short-chain aliphatic and chlorinated aliphatic combustion products in both high-temperature and low-temperature post-combustion zones can be important in the formation of larger organic pollutants (e. g. polychlorinated biphenyls, polychlorianted dibenzo-p-dioxins/dibenzofurans, chlorohenols, chlorobenzenes, etc). Fly ash formed in the combustion process provides the active surface for chlorination/condensation reactions in the post-combustion zone. The presence of several metals in flay ashes give rise to the question whether there is one specific metal or a complex of metals that is responsoble for the chlorination. Although fly ash contains many metallic species, most researchers investigations the PCDD/F formation mechanisms have used copper as the catalytic surface in their pollutant formation studies because copper is a known commercial oxychloriantion catalyst. The specific catalytic effects of various copper compounds in the formation of PCDD/F from aliphatica and aromatic compounds have been examined by us and a number of other investigators. In limited studies, iron compounds have also been used as PCDD/F formation catalysts, although these iron studies have produced contradictory results. Review of commercially important polymerization reactions shows that at varying temperatures and pressures, c and C{sub 4} olefinic polymerization reactions may be catalyzed by HCI-activated Al{sub 2}O{sub 3} SiO{sub 2} (aromatization also observed), aluminosilicates (1% Al{sub 2}O{sub 3} in SiO{sub 2}), and Fe oxides on aluminosilicates

  7. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    Science.gov (United States)

    Quan, Jiannong; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang; Liu, Yangang

    2015-12-01

    The effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the formation of secondary inorganic aerosols, and led to rapid increase of the PM2.5 concentration.

  8. The 30P(p, γ31S reaction in classical novae: progress and prospects

    Directory of Open Access Journals (Sweden)

    C. Wrede

    2014-01-01

    Full Text Available The unknown thermonuclear rate of the 30P(p, γ31S reaction at classical-nova temperatures currently prohibits the accurate modeling of nova nucleosynthesis in the A ⩾ 30 region. This is hindering the calibration of nova thermometers based on observed O/S, S/Al, O/P, and P/Al abundance ratios in nova ejecta, the calibration of a meter to probe mixing at the core-envelope interface in novae based on the observed Si/H abundance ratio, and the identification of candidate pre-solar nova grains found in primitive meteorites based on laboratory measurements of their 30Si/28Si isotopic ratios. Each of these diagnostics could address key questions in our understanding of classical novae if the 30P(p, γ31S rate were known. We review progress on the determination of the 30P(p, γ31S rate leading to a critical assessment of current interpretations of published data and prospects for future work.

  9. Numerical study of how creep and progressive stiffening affect the growth stress formation in trees

    DEFF Research Database (Denmark)

    Ormarsson, Sigurdur; Dahlblom, O.; Johansson, M.

    2010-01-01

    annual rings is progressively added to the tree during the analysis. The material model used is based on the theory of small strains (where strains refer to the undeformed configuration which is good approximation for strains less than 4%) where so-called biological maturation strains (growth......It is not fully understood how much growth stresses affect the final quality of solid timber products in terms of e.g. shape stability. It is for example difficult to predict the internal growth stress field within the tree stem. Growth stresses are progressively generated during the tree growth...... and they are highly influenced by climate, biologic and material related factors. To increase the knowledge of the stress formation a finite element model was created to study how the growth stresses develop during the tree growth. The model is an axisymmetric general plane strain model where material for all new...

  10. Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Elimelech, Orian [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel; Liu, Jing [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Plonka, Anna M. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Frenkel, Anatoly I. [Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook NY 11794 USA; Banin, Uri [The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904 Israel

    2017-07-19

    Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.

  11. Radiative capture reaction for 17Ne formation within a full three-body model

    Science.gov (United States)

    Casal, J.; Garrido, E.; de Diego, R.; Arias, J. M.; Rodríguez-Gallardo, M.

    2016-11-01

    Background: The breakout from the hot Carbon-Nitrogen-Oxigen (CNO) cycles can trigger the rp-process in type I x-ray bursts. In this environment, a competition between 15O(α ,γ )19Ne and the two-proton capture reaction 15O(2 p ,γ )17Ne is expected. Purpose: Determine the three-body radiative capture reaction rate for 17Ne formation including sequential and direct, resonant and nonresonant contributions on an equal footing. Method: Two different discretization methods have been applied to generate 17Ne states in a full three-body model: the analytical transformed harmonic oscillator method and the hyperspherical adiabatic expansion method. The binary p -15O interaction has been adjusted to reproduce the known spectrum of the unbound 16F nucleus. The dominant E 1 contributions to the 15O(2 p ,γ )17Ne reaction rate have been calculated from the inverse photodissociation process. Results: Three-body calculations provide a reliable description of 17Ne states. The agreement with the available experimental data on 17Ne is discussed. It is shown that the 15O(2 p ,γ )17Ne reaction rates computed within the two methods agree in a broad range of temperatures. The present calculations are compared with a previous theoretical estimation of the reaction rate. Conclusions: It is found that the full three-body model provides a reaction rate several orders of magnitude larger than the only previous estimation. The implications for the rp-process in type I x-ray bursts should be investigated.

  12. Formation of hydrogen peroxide and water from the reaction of cold hydrogen atoms with solid oxygen at 10K

    CERN Document Server

    Miyauchi, N; Chigai, T; Nagaoka, A; Watanabe, N; Kouchi, A

    2008-01-01

    The reactions of cold H atoms with solid O2 molecules were investigated at 10 K. The formation of H2O2 and H2O has been confirmed by in-situ infrared spectroscopy. We found that the reaction proceeds very efficiently and obtained the effective reaction rates. This is the first clear experimental evidence of the formation of water molecules under conditions mimicking those found in cold interstellar molecular clouds. Based on the experimental results, we discuss the reaction mechanism and astrophysical implications.

  13. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    Science.gov (United States)

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  14. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  15. Dichotomous-noise-induced pattern formation in a reaction-diffusion system

    Science.gov (United States)

    Das, Debojyoti; Ray, Deb Shankar

    2013-06-01

    We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system.

  16. Redirection of the Reaction Specificity of a Thermophilic Acetolactate Synthase toward Acetaldehyde Formation.

    Directory of Open Access Journals (Sweden)

    Maria Cheng

    Full Text Available Acetolactate synthase and pyruvate decarboxylase are thiamine pyrophosphate-dependent enzymes that convert pyruvate into acetolactate and acetaldehyde, respectively. Although the former are encoded in the genomes of many thermophiles and hyperthermophiles, the latter has been found only in mesophilic organisms. In this study, the reaction specificity of acetolactate synthase from Thermus thermophilus was redirected to catalyze acetaldehyde formation to develop a thermophilic pyruvate decarboxylase. Error-prone PCR and mutant library screening led to the identification of a quadruple mutant with 3.1-fold higher acetaldehyde-forming activity than the wild-type. Site-directed mutagenesis experiments revealed that the increased activity of the mutant was due to H474R amino acid substitution, which likely generated two new hydrogen bonds near the thiamine pyrophosphate-binding site. These hydrogen bonds might result in the better accessibility of H+ to the substrate-cofactor-enzyme intermediate and a shift in the reaction specificity of the enzyme.

  17. Reversible Formation and Transmetalation of Schiff-Base Complexes in Subcomponent Self-Assembly Reactions.

    Science.gov (United States)

    Lewing, Dennis; Koppetz, Hannah; Hahn, F Ekkehardt

    2015-08-03

    Dinuclear complexes [Zn2(NS,NS)2] 3 and [Ni2(NS,NS)2] 6 bearing Schiff-base ligands featuring two NS donor groups were obtained in subcomponent self-assembly reactions using nickel or zinc as template metals. Several transmetalation reactions starting from 3 or 6 yielded the complexes [Pd2(NS,NS)2] 4 and [Co2(NS,NS)2] 5, and their molecular structures were determined by X-ray diffraction. Starting from the mononuclear complex [Ni(NS/NOH)2] 9 featuring a coordinated NS Schiff base and a free NOH Schiff base, completely reversible thermodynamically controlled imine bond formation was observed leading to complex [Ni2(NS,NS)2] 6 and the free Schiff -base ligand NOH,NOH 10.

  18. Chemo-Marangoni convection driven by an interfacial reaction: pattern formation and kinetics.

    Science.gov (United States)

    Eckert, K; Acker, M; Tadmouri, R; Pimienta, V

    2012-09-01

    A combined study devoted to chemo-Marangoni convection and the underlying kinetics is presented for a biphasic system in which surfactants are produced in situ by an interfacial reaction. The pattern formation studied in a Hele-Shaw cell in both microgravity and terrestrial environments initially shows an ensemble of chemo-Marangoni cells along a nearly planar interface. Soon, a crossover occurs to periodic large-scale interfacial deformations which coexist with the Marangoni cells. This crossover can be correlated with the autocatalytic nature of the interfacial reaction identified in the kinetic studies. The drastic increase in the product concentration is associated with an enhanced aggregate-assisted transfer after the critical micellar concentration is approached. In this context, it was possible to conclusively explain the changes in the periodicity of the interfacial deformations depending on the reactant concentration ratio.

  19. On adduct formation and reactivity in the OCS + OH reaction: A combined theoretical and experimental study

    Science.gov (United States)

    Schmidt, Johan A.; Kyte, Mildrid; Østerstrøm, Freja F.; Joelsson, Lars M. T.; Knap, Hasse C.; Jørgensen, Solvejg; Nielsen, Ole John; Murakami, Tatsuhiro; Johnson, Matthew S.

    2017-05-01

    The OCS + OH reaction occurs either via adduct formation or direct S-abstraction. We investigate OH-oxidation of OCS using quantum chemical methods and find that the OC(OH)S adduct reacts rapidly with O2 forming SOOH + CO2. SOOH rapidly dissociates under atmospheric conditions regenerating OH. We interpret earlier experimental results based on monitoring OH-loss, and find that OH-regeneration in presence of O2 may explain the insensitivity of the reaction rate to pressure and O2. We calculate a rate constant of 3.52 ×10-16 cm3 s-1 at 10 Torr increasing to 7.20 ×10-16 cm3 s-1 at 700 Torr. In addition we present a new experimental determination of the OCS + OH rate constant of (5.3 ± 3.6) ×10-15 cm3 s-1 at 296 K and 700 Torr using relative-rate technique.

  20. Iterative reactions of transient boronic acids enable sequential C-C bond formation

    Science.gov (United States)

    Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.

    2016-04-01

    The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

  1. Removal of boron from wastewater by the hydroxyapatite formation reaction using acceleration effect of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Yoshikawa, Eishi [Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jhonan, Yonezawa, Yamagata 992-8510 (Japan); Sasaki, Atsushi [Technical Division of Instrumental Analysis, Faculty of Engineering, Yamagata University, 4-3-16 Jhonan, Yonezawa, Yamagata 992-8510 (Japan); Endo, Masatoshi, E-mail: endomasa@yz.yamagata-u.ac.jp [Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jhonan, Yonezawa, Yamagata 992-8510 (Japan)

    2012-10-30

    Highlights: Black-Right-Pointing-Pointer The removal rate of boron was controlled by the HAp precipitate formation. Black-Right-Pointing-Pointer This method could reduce reaction time to 1/10 that of the conventional one. Black-Right-Pointing-Pointer The addition of ammonia could accelerate boron removal in this proposed method. Black-Right-Pointing-Pointer Sodium alpha-olefin sulfonate was the most effective coagulant in proposed method. Black-Right-Pointing-Pointer The proposed method had applicability to the real waste water sample. - Abstract: The mechanism was discussed for the removal of boron by the hydroxyapatite (HAp) formation reaction using Ca(OH){sub 2} and (NH{sub 4}){sub 2}HPO{sub 4} in room temperature. Time required to remove boron was 20 min by adding Ca(OH){sub 2} and (NH{sub 4}){sub 2}HPO{sub 4} for the remaining boron to below 1 mg/L. The removal rate of boron was controlled by the HAp precipitate formation and the presence of ammonia. From the XRD patterns and SEM images, HAp could be confirmed in the precipitate product. The reaction between borate ions and calcium hydroxide was accelerated by dehydration with ammonia; the borate-calcium hydroxide compound coprecipitated with resulting HAp. Although the removal of boron decreased in the presence of sulfate, phosphate, and aluminum, these effects could be prevented by adding excess Ca(OH){sub 2}. Interference of fluoride ions was eliminated by adding Al{sup 3+}. Sodium alpha-olefin sulfonate was the most effective coagulant for HAp precipitation. The proposed boron removal method has several advantages about treating time and ability of boron removal. The method was successfully applied to the real hot spring wastewater.

  2. Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    Gelencsér

    2005-01-01

    Full Text Available In a simple conceptual cloud-aerosol model the mass of secondary organic aerosol (SOA that may be formed in multiphase reaction in an idealized scenario involving two cloud cycles separated with a cloud-free period is evaluated. The conditions are set to those typical of continental clouds, and each parameter used in the model calculations is selected as a mean of available observational data of individual species for which the multiphase SOA formation route has been established. In the idealized setting gas and aqueous-phase reactions are both considered, but only the latter is expected to yield products of sufficiently low volatility to be retained by aerosol particles after the cloud dissipates. The key variable of the model is the Henry-constant which primarily determines how important multiphase reactions are relative to gas-phase photooxidation processes. The precursor considered in the model is assumed to already have some affinity to water, i.e. it is a compound having oxygen-containing functional group(s. As a principal model output an aerosol yield parameter is calculated for the multiphase SOA formation route as a function of the Henry-constant, and has been found to be significant already above H~103 M atm-1. Among the potential precursors that may be eligible for this mechanism based on their Henry constants, there are a suite of oxygenated compounds such as primary oxidation products of biogenic and anthropogenic hydrocarbons, including, for example, pinonaldehyde. Finally, the analogy of multiphase SOA formation to in-cloud sulfate production is exploited.

  3. Assessment of the potential for ammonium nitrate formation and reaction in Tank 241-SY-101

    Energy Technology Data Exchange (ETDEWEB)

    Pederson, L.R.; Bryan, S.A.

    1994-08-01

    Two principal scenarios by which ammonium nitrate may be formed were considered: (a) precipitation of ammonium nitrate in the waste, and (b) ammonium nitrate formation via the gas phase reaction of ammonia and nitrogen dioxide. The first of these can be dismissed because ammonium ions, which are necessary for ammonium nitrate precipitation, can exist only in negligibly small concentrations in strongly alkaline solutions. Gas phase reactions between ammonia, nitrogen dioxide, and water vapor in the gas phase represent the most likely means by which ammonium nitrate aerosols could be formed in Tank 241-SY-101. Predicted ammonium nitrate formation rates are largely controlled by the concentration of nitrogen dioxide. This gas has not been detected among those gases vented from the wastes using Fourier Transform Infrared Spectrometry (FTIR) or mass spectrometry. While detection limits for nitrogen dioxide have not been established experimentally, the maximum concentration of nitrogen dioxide in the gas phase in Tank 241-SY-101 was estimated at 0.1 ppm based on calculations using the HITRAN data base and on FTIR spectra of gases vented from the wastes. At 50 C and with 100 ppm ammonia also present, less than one gram of ammonium nitrate per year is estimated to be formed in the tank. To date, ammonium nitrate has not been detected on HEPA filters in the ventilation system, so any quantity that has been formed in the tank must be quite small, in good agreement with rate calculations. The potential for runaway exothermic reactions involving ammonium nitrate in Tank 241-SY-101 is minimal. Dilution by non-reacting waste components, particularly water, would prevent hazardous exothermic reactions from occurring within the waste slurry, even if ammonium nitrate were present. 41 refs.

  4. Kinetics and activation thermodynamics of methane monooxygenase compound Q formation and reaction with substrates.

    Science.gov (United States)

    Brazeau, B J; Lipscomb, J D

    2000-11-07

    The transient kinetics of formation and decay of the reaction cycle intermediates of the Methylosinus trichosporium OB3b methane monooxygenase (MMO) catalytic cycle are studied as a function of temperature and substrate type and deuteration. Kinetic evidence is presented for the existence of three intermediates termed compounds O, P, and P forming after the addition of O(2) to diferrous MMO hydroxylase (H(r)) and before the formation of the reactive intermediate compound Q. The Arrhenius plots for these reactions are linear and independent of substrate concentration and type, showing that substrate does not participate directly in the oxygen activation phase of the catalytic cycle. Analysis of the transient kinetic data revealed only small changes relative to the weak optical spectrum of H(r) for any of these intermediates. In contrast, large changes in the 430 nm spectral region are associated with the formation of Q. The decay reaction of Q exhibits an apparent first-order concentration dependence for all substrates tested, and the observed rate constant depends on the substrate type. The kinetics of the decay reaction of Q yield a nonlinear Arrhenius plot when methane is the substrate, and the rates in both segments of the plot increase linearly with methane concentration. Together these observations suggest that at least two reactions with a methane concentration dependence, and perhaps two methane molecules, are involved in the decay process. When CD(4) is used as the substrate, a large isotope effect and a linear Arrhenius plot are observed. Analogous plots for all other MMO substrates tested (e.g., ethane) are linear, and no isotope effect for deuterated analogues is observed. This demonstrates that a step other than C-H bond breaking is rate limiting for alternative MMO substrates. A two step Q decay mechanism is proposed that provides an explanation for the lack of an isotope effect for alternative MMO substrates and the fact that rate of oxidation of

  5. Study of Reaction of Curium Oxy-Compound Formation in Molten Chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Osipenko, A.G.; Mayorshin, A.A.; Bychkov, A.V. [Dimitrovgrad-10, Ulyanovsk region, 433510 (Russian Federation)

    2008-07-01

    The method of potentiometric titration using oxygen sensors with solid electrolyte membrane was applied for the study of the interaction of curium cations with oxygen anions in the molten alkali metal chlorides in the temperature range of 450-850 C degrees depending on oxy-acidity of the environment. Assumptions were made concerning ion and phase composition of the obtained high-temperature compounds and chemical reactions taking place in the melts. This scheme assumes that as the basicity of the melt increases, initially the formation of soluble curium oxychlorides takes place in the melt (presumably CmO{sup -}) that is followed by formation of solid CmOCl and finally sesquioxide Cm{sub 2}O{sub 3}. Basic thermodynamic values were calculated for the resultant curium oxy-compounds.

  6. Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2017-02-01

    Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

  7. Formation of meso, N-diphenylprotoporphyrin IX by an aerobic reaction of phenylhydrazine with oxyhemoglobins.

    Directory of Open Access Journals (Sweden)

    Nakanishi A

    2003-10-01

    Full Text Available Administration of phenylhydrazine to rabbits resulted in the denaturation of hemoglobins in erythrocytes, causing the formation of intracellular precipitates known as Heinz bodies, severe hemolytic anemia, and reticulocytosis. To elucidate the molecular mechanism of the destabilization, we allowed human oxyhemoglobins to react aerobically with phenylhydrazine. After treatment with acetic acid/HCl and H2SO4/methanol, the chloroform extract contained blue-green pigments of major products accompanied by different minor products. Each product was isolated by column chromatography. By fast-atom-bombardment mass spectrometry (FAB-MS and proton nuclear magnetic resonance (1H-NMR spectrometry, dimethyl esters of N-phenylprotoporphyrin IX and meso, N-diphenylprotoporphyrin IX were determined. Other major products also were determined to be dimethyl esters of triphenyl-and tetraphenyl-substituted protoporphyrins by FAB-MS. The formation of meso, N-diphenylprotoporphyrin indicated that the addition of a phenyl radical to the meso-carbon atom of the protoporphyrin ring occurred. Triphenyl and tetraphenyl adducts also indicated the formation of phenyl radicals in the aerobic reaction of phenylhydrazine with oxyhemoglobins. From these results, we suggest that the formation of phenyl radicals and the replacement of heme with phenyl-substituted protoporphyrins cause the destabilization of hemoglobins to induce Heinz bodies and hemolytic anemia with phenylhydrazine.

  8. Recent progress in lanthanide-catalyzed organic reactions in protic media

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Lanthanide triflates are stable in water. It is possible for lanthanides to undergo many organic reactions in environmentally friendly solvents. This makes lanthanides very promising in the field of green chemistry. This review describes the recent development of the lanthanidecatalyzed organic reactions in protic solvents. Those reactions include Diels-Alder, Aldol, Allylation, acetalization,pericyclization, radical reactions as well as some newly-developed lanthnides-based catalysts.

  9. FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

    Science.gov (United States)

    The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

  10. 固态化学反应研究进展%The Progress on Solid State Chemical Reaction

    Institute of Scientific and Technical Information of China (English)

    康新平

    2012-01-01

    综述了固态化学反应的定义、研究范围、分类,以及低热固态反应的实验方法、优点、反应机理,分析了固态化学反应的应用进展,展望了此类研究的发展前景。%The article reviewed the definition, scope, classification of solid state chemical reaction, and the experimental method, advantage, reaction mechanism of solid state reaction at low- heating temperatures, and analyzed the application progress of solid state chemical reaction. Some suggestions on the development prospect of such research in the future are presented.

  11. Temperature perturbations evolution as a possible mechanism of exothermal reaction kernels formation in shock tubes

    Science.gov (United States)

    Drakon, A. V.; Kiverin, A. D.; Yakovenko, I. S.

    2016-11-01

    The basic question raised in the paper concerns the origins of exothermal reaction kernels and the mechanisms of detonation onset behind the reflected shock wave in shock-tube experiments. Using the conventional experimental technique, it is obtained that in the certain diapason of conditions behind the reflected shocks a so-called “mild ignition” arises which is characterized by the detonation formation from the kernel distant from the end-wall. The results of 2-D and 3-D simulations of the flow evolution behind the incident and reflected shocks allow formulation of the following scenario of ignition kernels formation. Initial stage during and after the diaphragm rupture is characterized by a set of non-steady gasdynamical processes. As a result, the flow behind the incident shock occurs to be saturated with temperature perturbations. Further evolution of these perturbations provides generating of the shear stresses in the flow accompanied with intensification of velocity and temperature perturbations. After reflection the shock wave interacts with the formed kernels of higher temperature and more pronounced kernels arise on the background of reactivity profile determined by moving reflected shock. Exothermal reaction starts inside such kernels and propagates into the ambient medium as a spontaneous ignition wave with minimum initial speed equal to the reflected shock wave speed.

  12. Formation of complex organic molecules in cold objects: the role of gas phase reactions

    CERN Document Server

    Balucani, Nadia; Taquet, Vianney

    2015-01-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain surface and gas phase chemistry. We propose here a new model to form DME and MF with gas phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthetized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairy well the observations towards L1544. It also...

  13. Interlaboratory reaction rate program. 12th progress report, November 1976-October 1979

    Energy Technology Data Exchange (ETDEWEB)

    Lippincott, E.P.; McElroy, W.N.; Preston, C.C. (comps.)

    1980-09-01

    The Interlaboratory Reaction Rate UILRR) program is establishing the capability to accurately measure neutron-induced reactions and reaction rates for reactor fuels and materials development programs. The goal for the principal fission reactions, /sup 235/U, /sup 238/U and /sup 239/Pu, is an accuracy to within +- 5% at the 95% confidence level. Accurate measurement of other fission and nonfission reactions is also required, but to a lesser accuracy, between +- 5% and 10% at the 95% confidence level. A secondary program objective is improvement in knowledge of the nuclear parameters involved in the standarization of fuels and materials dosimetry measurements of neutron flux, spectra, fluence and burnup.

  14. Peptide bond formation through gas-phase reactions in the interstellar medium: formamide and acetamide as prototypes

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-09-20

    A theoretical study of the reactions of NH{sub 4}{sup +} with formaldehyde and CH{sub 5}{sup +} with formamide is carried out. The viability of these gas-phase ion-molecule reactions as possible sources of formamide and acetamide under the conditions of interstellar medium is evaluated. We report a theoretical estimation of the reaction enthalpies and an analysis of their potential energy surfaces. Formation of protonated formamide from the reaction between ammonium cation and formaldehyde is an exothermic process, but all the channels located on the potential energy surface leading to this product present net activation energies. For the reaction between methanium and formamide, different products are possible from a thermodynamic point of view. An analysis of its potential energy surface showed that formation of protonated acetamide and amino acetaldehyde takes place through barrier-free paths. Therefore, this reaction could be a feasible source of acetamide and amino acetaldehyde in space.

  15. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    Science.gov (United States)

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E

    2014-12-16

    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  16. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun

    2017-08-03

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  17. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    Science.gov (United States)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  18. Radiative capture reaction for $^{17}$Ne formation within a full three-body model

    CERN Document Server

    Casal, J; de Diego, R; Arias, J M; Rodríguez-Gallardo, M

    2016-01-01

    Background: The breakout from the hot CNO cycles can trigger the rp-process in type I X-ray bursts. In this environment, a competition between $^{15}\\text{O}(\\alpha,\\gamma){^{19}\\text{Ne}}$ and the two-proton capture reaction $^{15}\\text{O}(2p,\\gamma){^{17}\\text{Ne}}$ is expected. Purpose: Determine the three-body radiative capture reaction rate for ${^{17}\\text{Ne}}$ formation including sequential and direct, resonant and non-resonant contributions on an equal footing. Method: Two different discretization methods have been applied to generate $^{17}$Ne states in a full three-body model: the analytical transformed harmonic oscillator method and the hyperspherical adiabatic expansion method. The binary $p$--$^{15}$O interation has been adjusted to reproduce the known spectrum of the unbound $^{16}$F nucleus. The dominant E1 contributions to the $^{15}\\text{O}(2p,\\gamma){^{17}\\text{Ne}}$ reaction rate have been calculated from the inverse photodissociation process. Results: Three-body calculations provide a rel...

  19. Emotional reactions of different interface formats: Comparing digital and traditional board games

    Directory of Open Access Journals (Sweden)

    Yu-Min Fang

    2016-03-01

    Full Text Available Some games provide both traditional board games and digital versions at the same time in the market. Why the rise of virtual games has not forced traditional physical board games to disappear? Do traditional physical games evoke different emotional reactions and interpersonal relationships? This article explored the subjects’ preferences toward traditional and digital versions of the same game and investigated social interaction while playing games. Based on Norman’s three emotional design levels—visceral, behavioral, and reflective levels—this study examined players’ satisfaction degree. This study also applied Positive and Negative Affect Schedule to measure subjects’ emotional reactions. Monopoly and Jenga games were selected as stimuli. A total of 77 subjects received tests of three different interface formats (physical, desktop, and tablet and then filled out the questionnaire. The findings successfully evidenced the significant differences between digital and traditional board games. The statistical results indicated that satisfaction degrees of digital games declined in visceral, behavioral, and reflective levels. Traditional games not only evoked users’ stronger emotional reactions but also received higher preferences. Traditional games could improve interpersonal relationships as well.

  20. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    Science.gov (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  1. Turing pattern formation on the sphere for a morphochemical reaction-diffusion model for electrodeposition

    Science.gov (United States)

    Lacitignola, Deborah; Bozzini, Benedetto; Frittelli, Massimo; Sgura, Ivonne

    2017-07-01

    The present paper deals with the pattern formation properties of a specific morpho-electrochemical reaction-diffusion model on a sphere. The physico-chemical background to this study is the morphological control of material electrodeposited onto spherical particles. The particular experimental case of interest refers to the optimization of novel metal-air flow batteries and addresses the electrodeposition of zinc onto inert spherical supports. Morphological control in this step of the high-energy battery operation is crucial to the energetic efficiency of the recharge process and to the durability of the whole energy-storage device. To rationalise this technological challenge within a mathematical modeling perspective, we consider the reaction-diffusion system for metal electrodeposition introduced in [Bozzini et al., J. Solid State Electr.17, 467-479 (2013)] and extend its study to spherical domains. Conditions are derived for the occurrence of the Turing instability phenomenon and the steady patterns emerging at the onset of Turing instability are investigated. The reaction-diffusion system on spherical domains is solved numerically by means of the Lumped Surface Finite Element Method (LSFEM) in space combined with the IMEX Euler method in time. The effect on pattern formation of variations in the domain size is investigated both qualitatively, by means of systematic numerical simulations, and quantitatively by introducing suitable indicators that allow to assign each pattern to a given morphological class. An experimental validation of the obtained results is finally presented for the case of zinc electrodeposition from alkaline zincate solutions onto copper spheres.

  2. Visible-light induced isoindoles formation to trigger intermolecular Diels-Alder reactions in the presence of air.

    Science.gov (United States)

    Lin, Chao; Zhen, Le; Cheng, Yong; Du, Hong-Jin; Zhao, Hui; Wen, Xiaoan; Kong, Ling-Yi; Xu, Qing-Long; Sun, Hongbin

    2015-06-05

    Visible-light induced isoindole formation triggered an intermolecular Diels-Alder reaction with dienophiles such as acetylenedicarboxylate and maleimides in the presence of air. The reaction resulted in excellent diastereoselctivity and high yields under mild reaction conditions. This protocol provides an atom-economical, transition-metal-free (TM-free) and straightforward approach to structurally diverse bridged-ring heterocycles from easily accessible molecules.

  3. Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.

    Science.gov (United States)

    Verhamme, Ingrid M; Bock, Paul E

    2008-09-19

    Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.

  4. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    Science.gov (United States)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  5. Formation of η{sup '} (958) meson bound states by the {sup 6}Li(γ,d) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Miyatani, M.; Nagahiro, H.; Hirenzaki, S. [Nara Women' s University, Department of Physics, Nara (Japan); Ikeno, N. [Tottori University, Department of Regional Environment, Tottori (Japan)

    2016-07-15

    We have investigated the {sup 6}Li(γ,d) reaction theoretically for the formation of the η{sup '}(958) mesic nucleus close to the recoilless kinematics. We have developed the theoretical formula and reported the quantitative results of the formation spectra for various cases in this article. We have found that the formation cross sections are reduced by the effects of the fragile deuteron form factor. (orig.)

  6. Coke formation on HFAU and HEMT zeolites. Influence of the reaction temperature and propene pressure

    Science.gov (United States)

    Doka Nassionou, G. A.; Magnoux, P.; Guisnet, M.

    1999-02-01

    The formation of coke from propene (Pp = 1.3 kPa and 13 kPa) was investigated on HFAU and HEMT zeolites in a microbalance for temperatures ranging from 120 °C to 450 °C. For both zeolites, the greater the propene pressure and the lower the temperature the faster the initial coke formation. However for high propene pressure, initial coke formation is faster with HEMT zeolite. This can be related to the stronger acidity of the HEMT sample. For low propene pressure and after 420 minutes of coking, a minimum in coke is observed for T = 350 ^circC, which can be related to the difference between the rate of formation and the rate of retention of coke molecules. At low temperature, due to their low volatility, oligomers are easily formed and retained in the zeolite pores. These molecules can be totally eliminated by an adequate thermal treatment in vacuum. At higher temperature, only aromatic or polyaromatic compounds which present a size larger than the pore apertures can be retained in the cavities of the zeolites. The greater the reaction time, the faster the retention. Whatever the reaction temperature, coke molecules are more homogeneously distributed in the HEMT crystallites than in those of HFAU samples. For this latter zeolite coke molecules are preferentially formed in the cavities located near the outer surface of the crystallites (shell coking). La formation de coke à partir du propène (Pp = 1,3 et 13 kPa) a été étudiée en microbalance sur zéolithes HFAU et HEMT dans une gamme de température variant de 120 à 450°C. La vitesse initiale de formation de coke dépend de la pression du propène, de la température et également de la zéolithe. Ainsi, pour une forte pression en propène, la vitesse initiale de formation de coke est toujours plus importante sur HEMT que sur HFAU. Ceci est à relier à la plus grande acidité et à la présence de sites acides plus forts sur HEMT. Après 420 minutes de réaction, et pour une faible pression en propène le

  7. Reaction mechanism between "memory effect" and induction time of gas hydrate formation

    Institute of Scientific and Technical Information of China (English)

    SUN Deng-lin; WU Qiang; ZHANG Bao-yong

    2008-01-01

    Using visual experimental apparatus,one system(T40,1×10-3 mol/L,nonadded with coal)and another system(T40,2×10-3 mol/L,added with coal)were experimented with for three times and two times.respectively.Five groups of P-T experimental parameters were obtained using the data logger system and analyzed combined with the video information of the experiments.Maior conclustions show that the induction time is shortened by 10-20 times in the experimental system containing residual pentahedral ring structures;"memory effect"can accelerate the dynamic progress and improve the thermodynamic conditions of gas hydrate formation.

  8. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: putative formation of a copper(I)-peroxynitrite intermediate.

    Science.gov (United States)

    Kalita, Apurba; Kumar, Pankaj; Mondal, Biplab

    2012-05-14

    The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.

  9. [Mechanisms of formation and progression of non-alcoholic fatty liver disease in type 2 diabetics].

    Science.gov (United States)

    Kravchun, N; Dorosh, E

    2014-03-01

    Currently, study of the mechanisms of formation and progression of non-alcoholic fatty liver disease (NAFLD) in the patients with type 2 diabetes mellitus (DM) is a topical problem in endocrinology. Prognosis for the disease depends on NAFLD stage and it determines the necessity to study the origin and mostly the progression in NAFLD course. It will favour the enhancement of efficacy of the treatment for this cohort of patients. The object of this work was to study the mechanisms of formation of NAFLD phasic course in type 2 diabetics via determining the levels of lipid peroxidation (LPO), 8-isoprostaglandin as components of oxidative stress. LPO indices and liver functional activity parameters (general cholesterol, high-density lipoproteids cholesterol, triglycerides, β-lipoproteids, very-low-density lipoproteids cholesterol, atherogenicity coefficient, thymol test, alanine aminotransferase, aspartate aminotransferase) were determined in the examined individuals. The carried research allowed, that changes in biochemical parameters levels is connected with increasing of diene conjugates (DC) activity and the carried correlation analysis of the studied values proved this relevance. The subgroup of the patients with DC levels of 200-400 nmol/l has no inflammatory alterations (cytolysis syndrome) that gives evidence of steatosis phase. The group of patients with DC levels of 400-600 nmol/l demonstrated the stage of non-alcoholic steatohepatitis with the most expressed shifts in functional liver condition. The greatest lipid, carbohydrate metabolic changes were found in the subgroup of the patients with DC level of 600 nmol/l and more that gives evidence of fibrotic processes.

  10. The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

    Science.gov (United States)

    Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.

    2013-12-01

    The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

  11. The Wnt11 Signaling Pathway in Potential Cellular EMT and Osteochondral Differentiation Progression in Nephrolithiasis Formation.

    Science.gov (United States)

    He, Deng; Lu, Yuchao; Hu, Henglong; Zhang, Jiaqiao; Qin, Baolong; Wang, Yufeng; Xing, Shuai; Xi, Qilin; Wang, Shaogang

    2015-07-17

    The molecular events leading to nephrolithiasis are extremely complex. Previous studies demonstrated that calcium and transforming growth factor-β1 (TGF-β1) may participate in the pathogenesis of stone formation, but the explicit mechanism has not been defined. Using a self-created genetic hypercalciuric stone-forming (GHS) rat model, we observed that the increased level of serous/uric TGF-β1 and elevated intracellular calcium in primary renal tubular epithelial cells (PRECs) was associated with nephrolithiasis progression in vivo. In the setting of high calcium plus high TGF-β1 in vitro, PRECs showed great potential epithelial to mesenchymal transition (EMT) progression and osteochondral differentiation properties, representing the multifarious increased mesenchymal and osteochondral phenotypes (Zeb1, Snail1, Col2A1, OPN, Sox9, Runx2) and decreased epithelial phenotypes (E-cadherin, CK19) bythe detection of mRNAs and corresponding proteins. Moreover, TGF-β-dependent Wnt11 knockdown and L-type Ca2+ channel blocker could greatly reverse EMT progression and osteochondral differentiation in PRECs. TGF-β1 alone could effectively promote EMT, but it had no effect on osteochondral differentiation in NRK cells (Rat kidney epithelial cell line). Stimulation with Ca2+ alone did not accelerate differentiation of NRK. Co-incubation of extracellular Ca2+ and TGF-β1 synergistically promotes EMT and osteochondral differentiation in NRK control cells. Our data supplied a novel view that the pathogenesis of calcium stone development may be associated with synergic effects of TGF-β1 and Ca2+, which promote EMT and osteochondral differentiation via Wnt11 and the L-type calcium channel.

  12. The Wnt11 Signaling Pathway in Potential Cellular EMT and Osteochondral Differentiation Progression in Nephrolithiasis Formation

    Directory of Open Access Journals (Sweden)

    Deng He

    2015-07-01

    Full Text Available The molecular events leading to nephrolithiasis are extremely complex. Previous studies demonstrated that calcium and transforming growth factor-β1 (TGF-β1 may participate in the pathogenesis of stone formation, but the explicit mechanism has not been defined. Using a self-created genetic hypercalciuric stone-forming (GHS rat model, we observed that the increased level of serous/uric TGF-β1 and elevated intracellular calcium in primary renal tubular epithelial cells (PRECs was associated with nephrolithiasis progression in vivo. In the setting of high calcium plus high TGF-β1 in vitro, PRECs showed great potential epithelial to mesenchymal transition (EMT progression and osteochondral differentiation properties, representing the multifarious increased mesenchymal and osteochondral phenotypes (Zeb1, Snail1, Col2A1, OPN, Sox9, Runx2 and decreased epithelial phenotypes (E-cadherin, CK19 bythe detection of mRNAs and corresponding proteins. Moreover, TGF-β-dependent Wnt11 knockdown and L-type Ca2+ channel blocker could greatly reverse EMT progression and osteochondral differentiation in PRECs. TGF-β1 alone could effectively promote EMT, but it had no effect on osteochondral differentiation in NRK cells (Rat kidney epithelial cell line. Stimulation with Ca2+ alone did not accelerate differentiation of NRK. Co-incubation of extracellular Ca2+ and TGF-β1 synergistically promotes EMT and osteochondral differentiation in NRK control cells. Our data supplied a novel view that the pathogenesis of calcium stone development may be associated with synergic effects of TGF-β1 and Ca2+, which promote EMT and osteochondral differentiation via Wnt11 and the L-type calcium channel.

  13. Mechanism of electron transfer reaction for xanthene dye-sensitized formation of methyl viologen radical

    Energy Technology Data Exchange (ETDEWEB)

    Usui, Y.; Misawa, H.; Sakuragi, H.; Tokumaru, K.

    1987-05-01

    Sensitized reduction of methyl viologen, MV/sup 2 +/, occurs efficiently through electron transfer from triplet xanthene dyes to MV/sup 2 +/ followed by electron transfer to the resulting semioxidized dyes from a reductant like triethanolamine. Unreactive ion pair complexes between these dyes and MV/sup 2 +/ are formed (formation constant: 1.2 x 10/sup 3/ M/sup -1/ for Eosine Y and MV/sup 2 +/ in 50% aqueous ethanol solution). The quantum yield for the reduced methyl viologen radical depends on the concentrations of MV/sup 2 +/ and the amine and on the ionic strength of solution. The efficiency of the electron transfer from triplet dyes to MV/sup 2 +/ is increased by addition of alcohol, and solvent effects on the reaction mechanism are discussed. 38 references, 5 figures, 2 tables.

  14. Application of Fractional Calculus to Reaction-Subdiffusion Processes and Morphogen Gradient Formation

    CERN Document Server

    Yuste, S B; Lindenberg, K

    2010-01-01

    It is a well known fact that subdiffusion equations in terms of fractional derivatives can be obtained from Continuous Time Random Walk (CTRW) models with long-tailed waiting time distributions. Over the last years various authors have shown that extensions of such CTRW models incorporating reactive processes to the mesoscopic transport equations may lead to non-intuitive reaction-subdiffusion equations. In particular, one such equation has been recently derived for a subdiffusive random walker subject to a linear (first-order) death process. We take this equation as a starting point to study the developmental biology key problem of morphogen gradient formation, both for the uniform case where the morphogen degradation rate coefficient (reactivity) is constant and for the non-uniform case (position-dependent reactivity). In the uniform case we obtain exponentially decreasing stationary concentration profiles and we study their robustness with respect to perturbations in the incoming morphogen flux. In the non...

  15. Age-related characteristics of risky decision-making and progressive expectation formation.

    Science.gov (United States)

    Kardos, Zsófia; Kóbor, Andrea; Takács, Ádám; Tóth, Brigitta; Boha, Roland; File, Bálint; Molnár, Márk

    2016-10-01

    During daily encounters, it is inevitable that people take risks. Investigating the sequential processing of risk hazards involve expectation formation about outcome contingencies. The present study aimed to explore risk behavior and its neural correlates in sequences of decision making, particularly in old age, which represents a critical period regarding risk-taking propensity. The Balloon Analogue Risk Task was used in an electrophysiological setting with young and elderly age groups. During the task each additional pump on a virtual balloon increased the likelihood of a balloon burst but also increased the chance to collect more reward. Event-related potentials associated with rewarding feedback were analyzed based on the forthcoming decisions (whether to continue or to stop) in order to differentiate between states of expectation towards gain or loss. In the young, the reward positivity ERP component increased as a function of reward contingencies with the largest amplitude for rewarding feedback followed by the decision to stop. In the elderly, however, reward positivity did not reflect the effect of reward structure. Behavioral indices of risk-taking propensity suggest that the performance of the young and the elderly were dissociable only with respect to response times: The elderly was characterized by hesitation and more deliberative decision making throughout the experiment. These findings signify that sequential tracking of outcome contingencies has a key role in cost-efficient action planning and progressive expectation formation.

  16. ATM prevents DSB formation by coordinating SSB repair and cell cycle progression.

    Science.gov (United States)

    Khoronenkova, Svetlana V; Dianov, Grigory L

    2015-03-31

    DNA single-strand breaks (SSBs) arise as a consequence of spontaneous DNA instability and are also formed as DNA repair intermediates. Their repair is critical because they otherwise terminate gene transcription and generate toxic DNA double-strand breaks (DSBs) on replication. To prevent the formation of DSBs, SSB repair must be completed before DNA replication. To accomplish this, cells should be able to detect unrepaired SSBs, and then delay cell cycle progression to allow more time for repair; however, to date there is no evidence supporting the coordination of SSB repair and replication in human cells. Here we report that ataxia-telangiectasia mutated kinase (ATM) plays a major role in restricting the replication of SSB-containing DNA and thus prevents DSB formation. We show that ATM is activated by SSBs and coordinates their repair with DNA replication. SSB-mediated ATM activation is followed by a G1 cell cycle delay that allows more time for repair and thus prevents the replication of damaged DNA and DSB accrual. These findings establish an unanticipated role for ATM in the signaling of DNA SSBs and provide important insight into the molecular defects leading to genetic instability in patients with ataxia-telangiectasia.

  17. Formation of cysteine-S-conjugates in the Maillard reaction of cysteine and xylose.

    Science.gov (United States)

    Cerny, Christoph; Guntz-Dubini, Renée

    2013-11-15

    Cysteine-S-conjugates (CS-conjugates) occur in foods derived from plant sources like grape, passion fruit, onion, garlic, bell pepper and hops. During eating CS-conjugates are degraded into aroma-active thiols by β-lyases that originate from oral microflora. The present study provides evidence for the formation of the CS-conjugates S-furfuryl-l-cysteine (FFT-S-Cys) and S-(2-methyl-3-furyl)-l-cysteine (MFT-S-Cys) in the Maillard reaction of xylose with cysteine at 100°C for 2h. The CS-conjugates were isolated using cationic exchange and reversed-phase chromatography and identified by (1)H NMR, (13)C NMR and LC-MS(2). Spectra and LC retention times matched those of authentic standards. To the best of our knowledge, this is the first time that CS-conjugates are described as Maillard reaction products. Furfuryl alcohol (FFA) is proposed as an intermediate which undergoes a nucleophilic substitution with cysteine. Both FFT-S-Cys and MFT-S-Cys are odourless but produce strong aroma when tasted in aqueous solutions, supposedly induced by β -lyases from the oral microflora. The perceived aromas resemble those of the corresponding aroma-active thiols 2-furfurylthiol (FFT) and 2-methyl-3-furanthiol (MFT) which smell coffee-like and meaty, respectively.

  18. Formation of early and advanced Maillard reaction products correlates to the ripening of cheese.

    Science.gov (United States)

    Spanneberg, Robert; Salzwedel, Grit; Glomb, Marcus A

    2012-01-18

    The present study deals with the characterization of the ripening of cheese. A traditional German acid curd cheese was ripened under defined conditions at elevated temperature, and protein and amino acid modifications were investigated. Degree of proteolysis and analysis of early [Amadori compound furosine (6)] and advanced [N(ε)-carboxymethyllysine (4), N(ε)-carboxyethyllysine (5)] Maillard reaction products confirmed the maturation to proceed from the rind to the core of the cheese. Whereas 6 was decreased, 4 and 5 increased over time. Deeper insight into the Maillard reaction during the ripening of cheese was achieved by the determination of selected α-dicarbonyl compounds. Especially methylglyoxal (2) showed a characteristic behavior during storage of the acid curd cheese. Decrease of this reactive structure was directly correlated to the formation of 5. To extend the results of experimental ripening to commercial cheeses, different aged Gouda types were investigated. Maturation times of the samples ranged from 6 to 8 weeks (young) to more than 1 year (aged). Again, increase of 5 and decrease of 2 were able to describe the ripening of this rennet coagulated cheese. Therefore, both chemical parameters are potent markers to characterize the degree of maturation, independent of coagulation.

  19. Formation of photosystem II reaction centers that work as energy sinks in lichen symbiotic Trebouxiophyceae microalgae.

    Science.gov (United States)

    Guéra, Alfredo; Gasulla, Francisco; Barreno, Eva

    2016-04-01

    Lichens are poikilohydric symbiotic organisms that can survive in the absence of water. Photosynthesis must be highly regulated in these organisms, which live under continuous desiccation-rehydration cycles, to avoid photooxidative damage. Analysis of chlorophyll a fluorescence induction curves in the lichen microalgae of the Trebouxiophyceae Asterochloris erici and in Trebouxia jamesii (TR1) and Trebouxia sp. (TR9) phycobionts, isolated from the lichen Ramalina farinacea, shows differences with higher plants. In the presence of the photosynthetic electron transport inhibitor DCMU, the kinetics of Q(A) reduction is related to variable fluorescence by a sigmoidal function that approaches a horizontal asymptote. An excellent fit to these curves was obtained by applying a model based on the following assumptions: (1) after closure, the reaction centers (RCs) can be converted into "energy sink" centers (sRCs); (2) the probability of energy leaving the sRCs is very low or zero and (3) energy is not transferred from the antenna of PSII units with sRCs to other PSII units. The formation of sRCs units is also induced by repetitive light saturating pulses or at the transition from dark to light and probably requires the accumulation of reduced Q(A), as well as structural changes in the reaction centers of PSII. This type of energy sink would provide a very efficient way to protect symbiotic microalgae against abrupt changes in light intensity.

  20. Formation of phosphonates and pyrophosphates in the reactions of chlorophosphate esters with strong organic bases

    Indian Academy of Sciences (India)

    K V P Pavan Kumar; K Praveen Kumar; M Vijjulatha; K C Kumara Swamy

    2004-11-01

    The compounds S(6--Bu-4-Me-C6H2O)2P(O)Cl (1), CH2(6--Bu-4-Me-C6H2O)2P(O)Cl (2) and (2,2'-C20H12O2)P(O)Cl (3) react with diazabicycloundecene (DBU) to give rise to, predominantly, the phosphonate compounds [S(6--Bu-4-Me-C6H2O)2P(O)(DBU)]+[Cl]- (4), [CH2(6--Bu-4-Me-C6H2O)2P(O) (DBU)]+[Cl]- (5) and [(2,2'-C20H12O2)P(O)(DBU)]+[Cl]- (6). The first two compounds could be isolated in the pure state. In analogous reactions of 1 and 2 with diazabicyclononene (DBN) or N-methyl imidazole, only the pyrophosphates [S(6--Bu-4-Me-C6H2O)2P(O)]2O (7) and [CH2(6--Bu-4-Me-C6H2O)2P(O)]2O (8) could be isolated, although the reaction mixture showed several other compounds in the phosphorus NMR. A possible pathway for the formation of phosphonate salts is proposed. The X-ray crystal structures of 4, 7 and 8 are also discussed.

  1. Turing pattern formation in the chlorine dioxide-iodine- malonic acid reaction-diffusion system

    Science.gov (United States)

    Setayeshgar, Sima

    The formation of localized structures in the chlorine dioxide-idodine-malonic acid (CDIMA) reaction-diffusion system is investigated numerically using a realistic model of this system. We analyze the one-dimensional patterns formed along the gradients imposed by boundary feeds, and study their linear stability to symmetry- breaking perturbations (the Turing instability) in the plane transverse to these gradients. We establish that an often-invoked simple local linear analysis which neglects longitudinal diffusion is inappropriate for predicting the linear stability of these patterns. Using a fully nonuniform analysis, we investigate the structure of the patterns formed along the gradients and their stability to transverse Turing pattern formation as a function of the values of two control parameters: the malonic acid feed concentration and the size of the reactor in the dimension along the gradients. The results from this investigation are compared with existing experimental results. We also verify that the two-variable reduction of the chemical model employed in the linear stability analysis is justified. Finally, we present numerical solution of the CDIMA system in two dimensions which is in qualitative agreement with experiments. This result also confirms our linear stability analysis, while demonstrating the feasibility of numerical exploration of realistic chemical models.

  2. Photochemical reactions of divalent mercury with thioglycolic acid: formation of mercuric sulfide particles.

    Science.gov (United States)

    Si, Lin; Ariya, Parisa A

    2015-01-01

    Mercury (Hg) is a key toxic global pollutant. Studies in aquatic environment have suggested that thiols could be important for mercury speciation. Thioglycolic acid has been detected in various natural water systems and used as a model compound to study the complicated interaction between mercury and polyfunctional dissolved organic matter (DOM). We herein presented the first evidence for mercury particle formation during kinetic and product studies on the photochemistry of divalent mercury (Hg(2+)) with thioglycolic acid at near environmental conditions. Mercuric sulfide (HgS) particles formed upon photolysis were identified by high-resolution transmission electron microscopy coupled with energy dispersive spectrometry and select area electron diffraction. Kinetic data were obtained using UV-visible spectrophotometry and cold vapour atomic fluorescent spectrometry. The apparent first-order reaction rate constant under our experimental conditions was calculated to be (2.3±0.4)×10(-5) s(-1) at T=296±2 K and pH 4.0. It was found that (89±3)% of the reactants undergo photoreduction to generate elemental mercury (Hg(0)). The effects of ionic strengths, pH and potassium ion were also investigated. The formation of HgS particles pointed to the possible involvement of heterogeneous processes. Our kinetic results indicated the importance of weak binding sites on DOM to Hg in photoreduction of Hg(2+) to Hg(0). The potential implications of our data on environmental mercury transformation were discussed.

  3. Fundamental studies of high-temperature corrosion reactions. Fifth annual progress report

    Energy Technology Data Exchange (ETDEWEB)

    Rapp, R.A.

    1980-02-01

    The in-situ study of metal oxidation reactions and the mechanism of the sulfidation of molybdenum by sulfur gases were studied. Equipment including a SEM microscope, heater and power supply which were used is described. (FS)

  4. Supercritical fluid reactions for coal processing. Quarterly progress report, April 1, 1996--June 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Eckert, C.A.

    1996-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

  5. Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions.

    Science.gov (United States)

    Liu, Wenxia; Shen, Lianfeng; Zhang, Fawen; Liu, Wenbin; Zheng, Minghui; Yang, Xitian

    2013-08-01

    Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2',3,4,4',5,5',6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl4Bz) is the predominant congener formed on the SiO2/Fe2O3 surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl4Bz molecules formed 2,2',3,4,4',5,5',6-OCDE in the presence of Fe2O3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO2/CuO surface without oxygen, although the 2,2',3,4,4',5,5',6-OCDE was the dominant product on the SiO2/CuO surface with oxygen. Therefore, the presence of Fe2O3 and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe2O3 can promote both the condensation and dechlorination reaction without oxygen. On the contrary, with oxygen, Fe2O3 suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.

  6. Severe inflammatory reaction induced by peritoneal trauma is the key driving mechanism of postoperative adhesion formation

    Directory of Open Access Journals (Sweden)

    Pismensky Sergei V

    2011-11-01

    Full Text Available Abstract Background Many factors have been put forward as a driving mechanism of surgery-triggered adhesion formation (AF. In this study, we underline the key role of specific surgical trauma related with open surgery (OS and laparoscopic (LS conditions in postoperative AF and we aimed to study peritoneal tissue inflammatory reaction (TIR, remodelling specific complications of open surgery (OS versus LS and subsequently evaluating AF induced by these conditions. Methods A prospective randomized study was done in 80 anaesthetised female Wistar rats divided equally into 2 groups. Specific traumatic OS conditions were induced by midline incision line (MIL extension and tissue drying and specific LS conditions were remodelled by intraperitoneal CO2 insufflation at the 10 cm of water. TIR was evaluated at the 24th, 72nd, 120th and 168th hour by scoring scale. Statistical analysis was performed by the non-parametric t test and two-way ANOVA using Bonferroni post-tests. Results More pronounced residual TIR was registered after OS than after LS. There were no significant TIR interactions though highly significant differences were observed between the OS and LS groups (p th and 72nd; p th and p th hrs. Adhesion free wounds were observed in 20.0 and 31.0% of cases after creation of OS and LS conditions respectively; with no significant differences between these values (p > 0.05. However larger adhesion size (41.67 ± 33.63 was observed after OS in comparison with LS (20.31 ± 16.38. The upper-lower 95% confidential limits ranged from 60.29 to 23.04 and from 29.04 to 11.59 respectively after OS and LS groups with significant differences (p = 0.03. Analogous changes were observed in adhesion severity values. Subsequently, severe TIR parameters were followed by larger sizes of severe postoperative adhesions in the OS group than those observed in the LS group. Conclusions MIL extension and tissue drying seem to be the key factors in the pathogenesis of

  7. 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.

  8. Experimental Study on Hydrocarbon Formation Due to Reactions Between Carbonates and Water or Water—Bearing Minerals in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    翁克难; 汪本善; 等

    1999-01-01

    In order to investigate the mechanism of formation of abiogenetic hydrocarbons at the depth of the Earth,experimental research on reactions between carbonates and water or waterbearing minerals was carried out at the pressure of about 1GPa and the temperature range of 800-1500℃.The reactions took place in an open and nonequilibrium state.Chromatographic analyses of the gas products indicate that in the experiments there were generated CH4-dominated hydrocarbons,along with some CO2 and CO.Accordingly,we think there is no essential distinction between free-state water and hydroxy in the minerals in the process of hydrocarbon formation.This study indicates that reactions between carbonates and water or water-bearing minerals should be an important factor leading to the formation of abiogenetic hydrocarbons at the Earth's depth.

  9. Pattern formation of reaction-diffusion system having self-determined flow in the amoeboid organism of Physarum plasmodium

    CERN Document Server

    Yamada, H; Ito, M

    1998-01-01

    The amoeboid organism, the plasmodium of Physarum polycephalum, behaves on the basis of spatio-temporal pattern formation by local contraction-oscillators. This biological system can be regarded as a reaction-diffusion system which has spatial interaction by active flow of protoplasmic sol in the cell. Paying attention to the physiological evidence that the flow is determined by contraction pattern in the plasmodium, a reaction-diffusion system having self-determined flow arises. Such a coupling of reaction-diffusion-advection is a characteristic of the biological system, and is expected to relate with control mechanism of amoeboid behaviours. Hence, we have studied effects of the self-determined flow on pattern formation of simple reaction-diffusion systems. By weakly nonlinear analysis near a trivial solution, the envelope dynamics follows the complex Ginzburg-Landau type equation just after bifurcation occurs at finite wave number. The flow term affects the nonlinear term of the equation through the critic...

  10. Application of diffusion-reaction equations to model carious lesion progress

    Science.gov (United States)

    Lewandowska, Katarzyna D.; Kosztołowicz, Tadeusz

    2012-04-01

    Nonlinear equations that describe the diffusion-reaction process with one static and one mobile substance are used to model a carious lesion process. The system under consideration consists of two initially separated substances A (an acid causing caries) and C (a static enamel mineral) which react chemically according to the formula A+C→0̸(inert). The so-called surface layer, which is formed in this process and in which chemical reactions can be neglected, is also included in this model. Changes in the substance concentrations are calculated approximately using the perturbation method. We show that the experimental data on the enamel mineral concentrations are well described by the analytical solutions of the diffusion-reaction equations.

  11. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    Science.gov (United States)

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  12. Quantum chemical approach for condensed-phase thermochemistry (II): Applications to formation and combustion reactions of liquid organic molecules

    Science.gov (United States)

    Ishikawa, Atsushi; Nakai, Hiromi

    2015-03-01

    The harmonic solvation model (HSM), which was recently developed for evaluating condensed-phase thermodynamics by quantum chemical calculations (Nakai and Ishikawa, 2014), was applied to formation and combustion reactions of simple organic molecules. The conventional ideal gas model (IGM) considerably overestimated the entropies of the liquid molecules. The HSM could significantly improve this overestimation; mean absolute deviations for the Gibbs energies of the formation and combustion reactions were (49.6, 26.7) for the IGM and (9.7, 5.4) for the HSM in kJ/mol.

  13. THE FORMATION OF ENTS ADAPTIVE REACTIONS DEPENDING ON THE TYPE OF PSYCHO-VEGETATIVE REGULATION

    Directory of Open Access Journals (Sweden)

    E. M. Kazin

    2014-01-01

    Full Text Available The purpose of the students (12 to 15 years old examination was to identify the integrative criteria of assessing the nature of the functional relationships between the parameters of the psychosocial and physiological adaptation of students, depending on age, individual-typological peculiarities of vegetative regulation, personal potential at different stages of school education.The study of the characteristics of vegetative regulation of the cardiovascular system was made with a help of an automatic cardiac-rhythm programs. The research of psychophysiological parameters was fulfiled using an automatic complex. The measurement of the speed of simple visual-motor reaction (PSMR, reaction to a moving object (WFD, the level of functional mobility of nervous processes (WFP and health brain (DDM were made before. Features psychosocial adaptation was analyzed using 8-color Luscher test.All examinee were divided into three groups on the basis of the statistical characteristics of the cardiac rhythm by the tone source autonomic tone: “vagotonia” (with a predominance of parasympathetic sistems, “somatotonic” (with domination of the sympatholytic effects, “atonic” (balanced type of vegetative nervous system.Based on the analysis of psychodynamic, neurodynamic and vegetative functions showed that students with initial vagotonies tone are characterized by high levels of situational and personal anxiety, low psychosocial adaptation, decreased activity of neurodynamic functions and psychodynamic processes in the learning dynamics, whereas the individuals with dominance of sympatotonics type regulation have high level of neurodynamic processes, psychosocial adaptation, against the background of significant stress mechanisms of vegetative regulation.Students with initial vegetative tone demonstrate a sufficient level of psychosocial adaptation, activity psychodynamic and neuromotor processes, accompanied by the preservation of the functionality of

  14. Formation of magnetic microstructure of the nanosized NiFe2O4 synthesized via solid-state reaction

    Directory of Open Access Journals (Sweden)

    Žák T.

    2012-01-01

    Full Text Available Magnetic NiFe2O4 structure formation was studied through structural, compositional and magnetic characterization of obtained reaction products of a simple, high yielding and low-cost solid-state reaction. Initial annealing of the starting oxides mixture at 700ºC did not allow us to observe formation of the desired magnetic phase. In contrast, subsequent thermomagnetic measurements up to 800ºC indicated the considerable increase of the magnetic moment, which can be reasonably assigned to the changes in phase composition and formation of magnetic NiFe2O4 structure during the heating cycle of measurements. Nanosized NiFe2O4 phase formation has been confirmed by the following XRD and MS phase analyses and its nanocrystalline structure by XRD and SEM/TEM techniques. The obtained hysteresis loop taken after TM measurements suggest the increased volume of magnetically active material and thus additionally support the previous findings.

  15. Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

    Science.gov (United States)

    Borrowman, Cuyler K; Zhou, Shouming; Burrow, Timothy E; Abbatt, Jonathan P D

    2016-01-01

    In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter.

  16. Cholesterol is essential for mitosis progression and its deficiency induces polyploid cell formation.

    Science.gov (United States)

    Fernández, Carlos; Lobo Md, María del Val T; Gómez-Coronado, Diego; Lasunción, Miguel A

    2004-10-15

    As an essential component of mammalian cell membranes, cells require cholesterol for proliferation, which is either obtained from plasma lipoproteins or synthesized intracellularly from acetyl-CoA. In addition to cholesterol, other non-sterol mevalonate derivatives are necessary for DNA synthesis, such as the phosphorylated forms of isopentane, farnesol, geranylgeraniol, and dolichol. The aim of the present study was to elucidate the role of cholesterol in mitosis. For this, human leukemia cells (HL-60) were incubated in a cholesterol-free medium and treated with SKF 104976, which inhibits cholesterol biosynthesis by blocking sterol 14alpha-demethylase, and the expression of relevant cyclins in the different phases of the cell cycle was analyzed by flow cytometry. Prolonged cholesterol starvation induced the inhibition of cytokinesis and the formation of polyploid cells, which were multinucleated and had mitotic aberrations. Supplementing the medium with cholesterol completely abolished these effects, demonstrating they were specifically due to cholesterol deficiency. This is the first evidence that cholesterol is essential for mitosis completion and that, in the absence of cholesterol, the cells fail to undergo cytokinesis, entered G1 phase at higher DNA ploidy (tetraploidy), and then progressed through S (rereplication) into G2, generating polyploid cells.

  17. Overexpression of the protein tyrosine phosphatase PRL-2 correlates with breast tumor formation and progression.

    Science.gov (United States)

    Hardy, Serge; Wong, Nau Nau; Muller, William J; Park, Morag; Tremblay, Michel L

    2010-11-01

    The PRL-1, PRL-2, and PRL-3 phosphatases are prenylated protein tyrosine phosphatases with oncogenic activity that are proposed to drive tumor metastasis. We found that PRL-2 mRNA is elevated in primary breast tumors relative to matched normal tissue, and also dramatically elevated in metastatic lymph nodes compared with primary tumors. PRL-2 knockdown in metastatic MDA-MB-231 breast cancer cells decreased anchorage-independent growth and cell migration, suggesting that the malignant phenotype of these cells is mediated at least in part through PRL-2 signaling. In different mouse mammary tumor-derived cell lines overexpressing PRL-2, we confirmed its role in anchorage-independent growth and cell migration. Furthermore, injection of PRL-2-overexpressing cells into the mouse mammary fat pad promoted extracellular signal-regulated kinase 1/2 activation and tumor formation. MMTV-PRL-2 transgenic mice engineered to overexpress the enzyme in mammary tissue did not exhibit spontaneous tumorigenesis, but they exhibited an accelerated development of mammary tumors initiated by introduction of an MMTV-ErbB2 transgene. Together, our results argue that PRL-2 plays a role in breast cancer progression.

  18. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  19. Electrochemical detection of protein based on hybridization chain reaction-assisted formation of copper nanoparticles.

    Science.gov (United States)

    Zhao, Jing; Hu, Suisui; Cao, Ya; Zhang, Bin; Li, Genxi

    2015-04-15

    In this paper, we report an electrochemical method for highly sensitive and specific detection of protein based on hybridization chain reaction (HCR)-assisted formation of copper nanoparticles by using small molecule such as folate-linked DNA as probe. In the presence of target protein, taking folate receptor (FR) as the model protein in this study, its binding with folate can protect the probe DNA from exonuclease I-catalyzed degradation, thus the probe DNA can be immobilized onto the electrode surface through the hybridization with capture DNA, triggering HCR on the electrode surface. Subsequently, copper nanoparticles can be formed on the electrode surface by using long duplex DNA oligomers from HCR as templates. Furthermore, copper ions released from acid-dissolution of copper nanoparticles can catalyze the oxidation of ο-phenylenediamine by dissolved oxygen, leading to significant electrochemical responses. As a result, our method can sensitively detect FR in the linear range from 0.01ng/mL to 100ng/mL with a detection limit of 3pg/mL. It can also specifically distinguish the target protein in both buffer and complex serum samples. Since many other proteins can be assayed by changing the corresponding small molecule, this method may be promising for the development of the technique for protein detections. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions.

    Science.gov (United States)

    Hayashi, Masahiko

    2016-12-01

    In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals.

  1. Stochastic Modeling of CO2 Migrations and Chemical Reactions in Deep Saline Formations

    Science.gov (United States)

    Ni, C.; Lee, I.; Lin, C.

    2013-12-01

    Carbon capture and storage (CCS) has been recognized the feasible technology that can significant reduce the anthropogenic CO2 emissions from large point sources. The CO2 injection in geological formations is one of the options to permanently store the captured CO2. Based on this concept a large number of target formations have been identified and intensively investigated with different types of techniques such as the hydrogeophysical experiments or numerical simulations. The numerical simulations of CO2 migrations in saline formations recently gather much attention because a number of models are available for this purpose and there are potential sites existing in many countries. The lower part of Cholan Formation (CF) near Changhua Coastal Industrial Park (CCIP) in west central Taiwan was identified the largest potential site for CO2 sequestration. The top elevations of the KF in this area varies from 1300 to 1700m below the sea level. Laboratory experiment showed that the permeability of CF is 10-14 to 10-12 m2. Over the years the offshore seismic survey and limited onshore borehole logs have provided information for the simulation of CO2 migration in the CF although the original investigations might not focus on the purpose of CO2 sequestration. In this study we modify the TOUGHREACT model to consider the small-scale heterogeneity in target formation and the cap rock of upper CF. A Monte Carlo Simulation (MCS) approach based on the TOUGHREACT model is employed to quantify the effect of small-scale heterogeneity on the CO2 migrations and hydrochemical reactions in the CF. We assume that the small-scale variability of permeability in KF can be described with a known Gaussian distribution. Therefore, the Gaussian type random field generator such as Sequential Gaussian Simulation (SGSIM) in Geostatistical Software Library (GSLIB) can be used to provide the random permeability realizations for the MCS. A variety of statistical parameters such as the variances and

  2. The effects of stress concentrations on reaction progress: an example from experimental growth of magnesio-aluminate spinel at corundum - periclase interfaces under uniaxial load

    Science.gov (United States)

    Jerabek, Petr; Abart, Rainer; Rybacki, Erik; Habler, Gerlinde

    2014-05-01

    The study aims to understand the reaction progress and chemical, microstructural and textural evolution of magnesio-aluminate spinel reaction rims formed at varying experimental settings (load, temperature and experiment duration). The spinel rims were grown at the contacts between periclase and corundum at temperatures of 1250°C to 1350°C and dry atmosphere, maintained by a constant argon gas flow, under uniaxial load of 0.026 and 0.26 kN per 9 mm2 of initial contact area. Single crystals of periclase with [100] and of corundum with [0001] perpendicular to the polished reaction interface as well as polycrystalline corundum were used as starting materials. Two loading procedures, immediate application of the load before heating and loading after the desired temperature had been reached, were used. An important byproduct of our experiments stemmed from the immediate application of the load, which led to deformation twinning and fracturing of corundum. This internal deformation of corundum disturbed the reaction interface and introduced loci of concentrated stress due to opening of void spaces in between the reactant crystals. Whenever cracks formed in the initial stages of an experiment, the void space opened immediately and no spinel formed along these interface segments. In the case of deformation twinning, the decreased rim thickness indicates later opening of void spaces. This is because next to twins, the reaction interface is characterized by tight physical contact on the one side and less tight contact on the other side of the twin individual. The tight contacts are characterized by enhanced reaction progress which together with the overall positive volume change of the reaction and limits on plasticity of the studied phases led to the opening of void spaces at places characterized by less tight contacts. The thickness variations are less pronounced in our high load (0.26 kN) experiments where periclase behaves plastically and to some extent reduces the

  3. Osteoblastic response as a healing reaction to chemotherapy mimicking progressive disease in patients with small cell lung cancer

    Energy Technology Data Exchange (ETDEWEB)

    Stattaus, Joerg [University Hospital of the University of Duisburg-Essen, Department of Diagnostic and Interventional Radiology and Neuroradiology, West German Cancer Center, Essen (Germany); University Hospital Essen, Department of Diagnostic and Interventional Radiology and Neuroradiology, Essen (Germany); Hahn, Steffen; Forsting, Michael; Ladd, Susanne C. [University Hospital of the University of Duisburg-Essen, Department of Diagnostic and Interventional Radiology and Neuroradiology, West German Cancer Center, Essen (Germany); Gauler, Thomas; Eberhardt, Wilfried [University Hospital of the University of Duisburg-Essen, Department of Internal Medicine (Cancer Research), West German Cancer Center, Essen (Germany); Mueller, Stefan P. [University Hospital of the University of Duisburg-Essen, Department of Nuclear Medicine, West German Cancer Center, Essen (Germany)

    2009-01-15

    The osteoblastic response (OR) phenomenon as a healing reaction during effective chemotherapy - defined by the appearance of new osteoblastic bone lesions while disease response in other tumor sites was well documented - has previously been described for breast and prostate cancer. The purpose of this study was to investigate this phenomenon that could erroneously be interpreted as progressive disease in patients with small cell lung cancer (SCLC) and to establish guidelines for interpretation of follow-up computed tomography (CT) examinations in this situation. Twenty-four patients with newly diagnosed SCLC and bone metastases were retrospectively included in this study. The characteristics of bone lesions in CT examinations were correlated with bone scintigraphy and magnetic resonance imaging, if available. In target lesions the CT density quantified in Hounsfield units (HU) was evaluated at baseline and during follow-up. New osteoblastic lesions occurred during follow-up in 17 of 24 patients. OR was proven in 4 patients and considered most likely in 11 patients; mean density increase in target lesions was 153 HU. The study indicates that osteoblastic response as a healing reaction seems to occur in the majority of patients with SCLC and bone metastases and should not be misinterpreted as progressive disease. (orig.)

  4. Can You Relate? The Importance of Need Satisfaction for the Quality and Progressive Union Formation Process of Intimate Relationships

    Directory of Open Access Journals (Sweden)

    Franziska Schmahl

    2012-10-01

    Full Text Available This article deals with the significance of autonomy and relatedness as central needs in intimate relationships. It examines the influences of need satisfaction on relationship quality and progressive union formation (“institutionalisation” processes of intimate relationships. Using a random sample of 1,914 couples in a longitudinal, dyadic survey design, we ascertained the actor and partner effects of autonomy and relatedness on relationship quality and the union formation process. A cluster analysis resulted in four types of relationship need satisfaction, distinguished by high values in both domains, high values in only one of the domains, or low need satisfaction in both domains. Balanced fulfilment of autonomy and relatedness predicts the comparatively highest values of relationship satisfaction and future orientation (commitment. Moreover, low need satisfaction in relationships reduces the progress of union formation processes (cohabitation, marriage, childbirth. Women demonstrate more intense actor and partner effects of relationship need satisfaction than men.

  5. Formations of Bacteria-like Textures by dynamic reactions in Meteorite and Syntheses

    Science.gov (United States)

    Miura, Y.

    2009-05-01

    fixings on iron plates at author's laboratory [4]. 5. Summary 1) Spherule- chained texture with Fe, Ni and Cl has been obtained at the fusion crust of the Kuga iron meteorite found in Japan. 2) As the Kuga iron meteorite is different with the Martian meteorite ALH84001 with composition and formation steps, bacteria-like texture of the Kuga meteorite is first significant example to form fossil-like texture by dynamic reaction of materials in the Solar System. Acknowledgements Author thanks to Dr. T. Kato, Yamaguchi University, for interpretation on bacteria-like texture. References: [1] Miura Y.(2008) 5th AOGS (Asia- Oceania Geosciences Society) Annual Meet. (Busan, Korea), CD#PS07- ST31-A22. [2] Miura Y.(2008). Meteoritics & Planetary Science (USA), 43-7, #5203. [3] McKay D.S. et al. (1996): Science, 273, 924-930. [4]Miura Y. (2009): 6th AGOS (submitted )

  6. In vivo formation of Maillard reaction free radicals in mouse skin

    National Research Council Canada - National Science Library

    Lloyd, R V; Fong, A J; Sayre, R M

    2001-01-01

    The Maillard browning reaction between carbohydrates and amines is part of an extensive series of reactions that is the basis for the brown color caused by the "sunless tanning" agent dihydroxyacetone...

  7. Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

    Directory of Open Access Journals (Sweden)

    A. W. H. Chan

    2007-05-01

    Full Text Available The distinguishing mechanism of formation of secondary organic aerosol (SOA is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics, of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

  8. Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

    Directory of Open Access Journals (Sweden)

    A. W. H. Chan

    2007-08-01

    Full Text Available The distinguishing mechanism of formation of secondary organic aerosol (SOA is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics, of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

  9. Reaction of Ynamides with Iminoiodinane-Derived Nitrenes: Formation of Oxazolones and Polyfunctionalized Oxazolidinones.

    Science.gov (United States)

    Rey-Rodriguez, Romain; Grelier, Gwendal; Habert, Loïc; Retailleau, Pascal; Darses, Benjamin; Gillaizeau, Isabelle; Dauban, Philippe

    2017-09-01

    This article describes the reaction of ynamides with metallanitrenes generated in the presence of an iodine(III) oxidant. N-(Boc)-Ynamides are converted to oxazolones via a cyclization reaction. The reaction is mediated by a catalytic dirhodium-bound nitrene species that first behaves as a Lewis acid. The oxazolones can be converted in a one pot manner to functionalized oxazolidinones following a regio- and stereoselective oxyamination reaction with the same nitrene reagent generated in stoichiometric amounts.

  10. An investigation on the formation mechanism of nano ZrB{sub 2} powder by a magnesiothermic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jalaly, M., E-mail: maisam_jalaly@iust.ac.ir [School of Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran 16846-13114 (Iran, Islamic Republic of); Bafghi, M.Sh.; Tamizifar, M. [School of Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran 16846-13114 (Iran, Islamic Republic of); Gotor, F.J. [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Americo Vespucio 49, 41092 Sevilla (Spain)

    2014-03-05

    Highlights: • Synthesis of zirconium diboride by magnesiothermic reduction. • Using high energy ball milling to perform mechanochemical reactions. • Study of mechanism of ZrB{sub 2} synthesis by studying subreactions and thermal analysis. -- Abstract: Nanocrystalline zirconium diboride (ZrB{sub 2}) powder was produced by mechanochemistry from the magnesiothermic reduction in the Mg/ZrO{sub 2}/B{sub 2}O{sub 3} system. The use of high-energy milling conditions was essential to induce a mechanically induced self-sustaining reaction (MSR) and significantly reduce the milling time required for complete conversion. Under these conditions, it was found that the ignition time for ZrB{sub 2} formation was only about a few minutes. In this study, the mechanism for the formation of ZrB{sub 2} in this system was determined by studying the relevant sub-reactions, the effect of stoichiometry, and the thermal behavior of the system.

  11. The C(3P) + NH3 reaction in interstellar chemistry: I. Investigation of the product formation channels

    CERN Document Server

    Bourgalais, Jeremy; Kailasanathan, Ranjith Kumar Abhinavam; Osborn, David L; Hickson, Kevin M; Loison, Jean-Christophe; Wakelam, Valentine; Goulay, Fabien; Picard, Sébastien D Le

    2016-01-01

    The product formation channels of ground state carbon atoms, C(3P), reacting with ammonia, NH3, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable VUV photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH3 reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states and complexes formed along the reaction coordinate. The combination of photoionization and laser induced fluorescence experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H2CN production channel represents ...

  12. Aldimine Formation Reaction, the First Step of the Maillard Early-phase Reaction, Might be Enhanced in Variant Hemoglobin, Hb Himeji.

    Science.gov (United States)

    Koga, Masafumi; Inada, Shinya; Shimizu, Sayoko; Hatazaki, Masahiro; Umayahara, Yutaka; Nishihara, Eijun

    2015-01-01

    Hb Himeji (β140Ala→Asp) is known as a variant hemoglobin in which glycation is enhanced and HbA1c measured by immunoassay shows a high value. The phenomenon of enhanced glycation in Hb Himeji is based on the fact that the glycation product of variant hemoglobin (HbX1c) shows a higher value than HbA1c. In this study, we investigated whether aldimine formation reaction, the first step of the Maillard early-phase reaction, is enhanced in Hb Himeji in vitro. Three non-diabetic subjects with Hb Himeji and four non-diabetic subjects without variant hemoglobin were enrolled. In order to examine aldimine formation reaction, whole blood cells were incubated with 500 mg/dl of glucose at 37°C for 1 hour and were analyzed by high-performance liquid chromatography. Both HbA1c and HbX1c were not increased in this condition. After incubation with glucose, labile HbA1c (LA1c) fraction increased in the controls (1.1±0.3%). In subjects with Hb Himeji increases in the labile HbX1c (LX1c) fraction as well as the LA1c fraction were observed, and the degree of increase in the LX1c fraction was significantly higher than that of the LA1c fraction (1.8±0.1% vs. 0.5±0.2%, PHb Himeji in vitro. The 140th amino acid in β chain of hemoglobin is suggested to be involved in aldimine formation reaction.

  13. Gas-phase enthalpies of formation and enthalpies of sublimation of amino acids based on isodesmic reaction calculations.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2014-05-15

    Accurate gas-phase enthalpies of formation (ΔfH298°) of 20 common α-amino acids, seven uncommon amino acids, and three small peptides were calculated by combining G4 theory calculations with an isodesmic reaction approach. The internal consistency over a set of ΔfH298°(g) values was achieved by sequential adjustment of their values through the isodesmic reactions. Four amino acids, alanine, β-alanine, sarcosine, and glycine, with reliable internally self-consistent experimental data, were chosen as the key reference compounds. These amino acids together with about 100 compounds with reliable experimental data (their accuracy was supported by G4 calculations) were used to estimate the enthalpies of formation of remaining amino acids. All of the amino acids with the previously established enthalpies of formation were later used as the reference species in the isodesmic reactions for the other amino acids. A systematic comparison was made of 14 experimentally determined enthalpies of formation with the results of calculations. The experimental enthalpies of formation for 10 amino acids were reproduced with good accuracy, but the experimental and calculated values for 4 compounds differed by 11–21 kJ/mol. For these species, the theoretical ΔfH298°(g) values were suggested as more reliable than the experimental values. On the basis of theoretical results, the recommended values for the gas-phase enthalpies of formation were also provided for amino acids for which the experimental ΔfH298°(g) were not available. The enthalpies of sublimation were evaluated for all compounds by taking into account the literature data on the solid-phase enthalpies of formation and the ΔfH298°(g) values recommended in our work. A special attention was paid to the accurate prediction of enthalpies of formation of amino acids from the atomization reactions. The problems associated with conformational flexibility of these compounds and harmonic treatment of low frequency torsional

  14. [Cancer Cells as Dynamic System - Molecular and Phenotypic Changes During Tumor Formation, Progression and Dissemination].

    Science.gov (United States)

    Sommerová, L; Ondroušková, E; Hrstka, R

    Dynamic, punctual and perfectly coordinated cellular response to internal and external stimuli is a crucial prerequisite for adaptation of mammalian cells to all changes that occur during cellular development under physiological conditions. Hijacking this ability is characteristic for tumor cells that are capable to adapt to unfavorable conditions which contribute to the formation and development of cancer during the process of tumor formation and progression. By changing key mechanisms, malignant cells can avoid cell death and thus allow development and spread of the tumor. The changes at the genetic level are manifested by various phenotypic characteristics, through which tumor cells are able to escape defense mechanisms, to acquire resistance to treatment, to invade and to create secondary tumors. In recent years, one of the most studied properties include changes in energy metabolism, when tumor cells specifically control reprogramming of the main metabolic pathways for their own benefit and to satisfy their increased needs not only for energy, but also for building materials required for increased proliferation. To adapt to extracellular conditions, it is necessary that cells undergo morphological changes, where modifications in the cell shape through reorganization of cytoskeletal filaments allow tumor cells to increase their invasiveness and other aggressive features. Clarifying these changes together with understanding of the switch in the genetic program within cancer cells, which allows them to overcome different stages of differentiation from cancer stem cells to fully differentiated cells, would be an important prerequisite for identification of the cancer cell "weaknesses" and may lead to improved cancer treatment. The ability of tumor cells to alter the rules of their own organism thus represents an important challenge for oncological research.Key words: cellular reprogramming - cancer cell plasticity - cancer metabolism - tumor heterogeneity

  15. Ozone consumption and volatile byproduct formation from surface reactions with aircraft cabin materials and clothing fabrics

    Science.gov (United States)

    Coleman, Beverly K.; Destaillats, Hugo; Hodgson, Alfred T.; Nazaroff, William W.

    We measured ozone consumption and byproduct formation on materials commonly found in aircraft cabins at flight-relevant conditions. Two series of small-chamber experiments were conducted, with most runs at low relative humidity (10%) and high air-exchange rate (˜20 h -1). New and used cabin materials (seat fabric, carpet, and plastic) and laundered and worn clothing fabrics (cotton, polyester, and wool) were studied. We measured ozone deposition to many material samples, and we measured ozone uptake and primary and secondary emissions of volatile organic compounds (VOCs) from a subset of samples. Deposition velocities ranged from 0.06 to 0.54 cm s -1. Emissions of VOCs were higher with ozone than without ozone in every case. The most commonly detected secondary emissions were C 1 through C 10 saturated aldehydes and the squalene oxidation products 6-methyl-5-hepten-2-one and acetone. For the compounds measured, summed VOC emission rates in the presence of 55-128 ppb (residual level) ozone ranged from 1.0 to 8.9 μmol h -1 m -2. Total byproduct yield ranged from 0.07 to 0.24 moles of product volatilized per mole of ozone consumed. Results were used to estimate the relative contribution of different materials to ozone deposition and byproduct emissions in a typical aircraft cabin. The dominant contributor to both was clothing fabrics, followed by seat fabric. Results indicate that ozone reactions with surfaces substantially reduce the ozone concentration in the cabin but also generate volatile byproducts of potential concern for the health and comfort of passengers and crew.

  16. Development of an apparatus to study chemical reactions at high temperature - a progress report

    Energy Technology Data Exchange (ETDEWEB)

    Sturzenegger, M.; Schelling, Th.; Steiner, E.; Wuillemin, D. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    TREMPER is an apparatus that was devised to study kinetic and thermodynamic aspects of high-temperature reactions under concentrated solar irradiation. The design allows investigations on solid or liquid samples under inert or reactive atmospheres. The working temperature is adjustable; the upper limit that has yet been reached is about 1900 K. TREMPER will facilitate chemical reactivity studies on a temperature level that is difficult to access by other means. First experiments were conducted to study the decomposition of manganese oxide MnO{sub 2}. Chemical analysis of exposed samples confirmed that the parent MnO{sub 2} was decomposed to mixtures of Mn O and Mn{sub 3}O{sub 4}. The amount of Mn O ranged from 60 mol-% in air to 86 mol-% under inert atmosphere. (author) 1 fig., 1 tab., 2 refs.

  17. Diagnosis of Progressive Spinal Muscular Atrophy by Using Polymerase Chain Reaction

    Institute of Scientific and Technical Information of China (English)

    姚娟; 丁新生; 陈克连; 程虹; 邓晓萱; 沈鸣九; 王颖

    2001-01-01

    Objective To understand the deletion in the survival motor neuron gene (SMN) of childhood-onset spinal muscular atrophy (SMA) in Chinese, and the value of diagnosis of SMA using polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP)method. Methods Deletions of SMN gene of exon 7 and 8 in 10 cases of presumed SMA, and 20 normal controls from 6 families and 30 unrelated controls were performed by PCR-RFLP analysis. Results Deletions of SMN gene detected in 9 of 10 (90%) cases of presumed SMA . No deletions of SMN in the telomere were found in the other members of families and controls.Conclusion PCR-RFLP is a sensitive, specific and simple method in diagnosis of SMA.

  18. An innovative approach to the formation of a progressive taxation probabilistic model on personal incomes

    National Research Council Canada - National Science Library

    Kalinina Olga

    2016-01-01

      This article suggests a mathematical justification of the possibility of transition to progressive taxation on personal incomes, allowing socially redistribute the tax burden between different groups...

  19. Formation of iodo-trihalomethanes, iodo-acetic acids, and iodo-acetamides during chloramination of iodide-containing waters: Factors influencing formation and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shaogang [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Li, Zhenlin [Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Dong, Huiyu [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Goodman, Bernard A. [College of Physical Science and Engineering, State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources, Guangxi University, Nanning, 520004, Guangxi (China); Qiang, Zhimin, E-mail: qiangz@rcees.ac.cn [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China)

    2017-01-05

    This study investigated systematically the factors influencing the formation of iodinated disinfection by-products (I-DBPs) during chloramination of I{sup −}-containing waters, including reaction time, NH{sub 2}Cl dose, I{sup −} concentration, pH, natural organic matter (NOM) concentration, Br{sup −}/I{sup −} molar ratio, and water matrix. Among the I-DBPs detected, iodoform (CHI{sub 3}), iodoacetic acid (IAA), diiodoacetic acid (DIAA), triiodoacetic acid (TIAA), and diiodoacetamide (DIAcAm) were the major species produced from reactions between reactive iodine species (HOI/I{sub 2}) and NOM. A kinetic model involving the reactions of NH{sub 2}Cl auto-decomposition, iodine species transformation and NOM consumption was developed, which could well describe NH{sub 2}Cl decay and HOI/I{sub 2} evolution. Higher concentrations of CHI{sub 3}, IAA, DIAA, TIAA, and DIAcAm were observed in chloramination than in chlorination, whereas IO{sub 3}{sup −} was only formed significantly in chlorination. Maximum formation of I-DBPs occurred at pH 8.0, but acidic conditions favored the formation of iodinated haloacetic acids and DIAcAm. Increasing Br{sup −}/I{sup −} molar ratio from 1 to 10 did not increase the total amount of I-DBPs, but produced more bromine-substituting species. In addition, chloramination of 18 model compounds indicated that low-SUVA{sub 254} (specific ultraviolet absorbance at 254 nm) NOM generally favored the formation of I-DBPs compared to high-SUVA{sub 254} NOM. Finally, potential pathways for I-DBPs formation from chloramination of NOM were proposed.

  20. Cellular Automata for Spatiotemporal Pattern Formation from Reaction-Diffusion Partial Differential Equations

    Science.gov (United States)

    Ohmori, Shousuke; Yamazaki, Yoshihiro

    2016-01-01

    Ultradiscrete equations are derived from a set of reaction-diffusion partial differential equations, and cellular automaton rules are obtained on the basis of the ultradiscrete equations. Some rules reproduce the dynamical properties of the original reaction-diffusion equations, namely, bistability and pulse annihilation. Furthermore, other rules bring about soliton-like preservation and periodic pulse generation with a pacemaker, which are not obtained from the original reaction-diffusion equations.

  1. Large scale synthesis and formation mechanism of silver nanoparticles in solid-state reactions at ambient temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Aiqin, E-mail: zhangaiqin@zzuli.edu.cn [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Tian, Yakun; Xiao, Yuanhua; Sun, Yuan [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); Li, Feng [State Laboratory of Surface and Interface Science and Technology, Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, Zhengzhou 450002 (China); American Advanced Nanotechnology, Houston, TX 77459 (United States)

    2015-07-15

    Highlights: • AgNPs were prepared by solid state reaction at ambient temperature. • Only silver nitrate and ascorbic acid were needed in this reaction. • The size of the AgNPs can be tuned conveniently. • Formation mechanism of the AgNPs was investigated. - Abstract: A one-step strategy for preparing Ag nanoparticles (AgNPs) on large scale is demonstrated successfully, based on solid-state reactions at ambient temperature. The environmentally friendly synthesis can be achieved by simply grinding AgNO{sub 3} and ascorbic acid (AA) for about 30 min without adding any solvent and organic protectors. The size of AgNPs can be readily controlled by adjusting the reaction parameters such as AgNO{sub 3}/AA molar ratio and reaction time. The nanostructures of AgNPs and their formation mechanism have been also investigated with XRD, FTIR, FESEM, HRTEM and HPLC–MS. It was found that AA can reduce Ag{sup +} into Ag{sup 0} to form AgNPs directly in accompanying with its first oxidation into 2,3-diketogulonic acid (2,3-DKG) and then a series of fragmentary species of 2,3-DKG.

  2. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    Science.gov (United States)

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.

  3. Molecular treatment of the ion-pair formation reaction in H(1s) + H(1s) collisions

    Energy Technology Data Exchange (ETDEWEB)

    Borondo, F.; Martin, F.; Yaez, M.

    1987-01-01

    All the available theoretical calculations of the cross section for the ion-pair formation reaction H(1s)+H(1s)..-->..H/sup +/H/sup -/(1s/sup 2/) have been performed using methods that are only valid at high collision energies. They get good agreement with the experiments for impact energies greater than 25 keV, but fail completely at smaller energies. In this work we report the cross section for this reaction at impact energies less than 10 keV, calculated in the framework of the impact-parameter approximation and using the molecular method with a common translation factor.

  4. A novel high-throughput format assay for HIV-1 integrase strand transfer reaction using magnetic beads

    Institute of Scientific and Technical Information of China (English)

    Hong-qiu HE; Xiao-hui MA; Bin LIU; Wei-zu CHEN; Cun-xin WANG; Shao-hui CHENG

    2008-01-01

    Aim:To develop a novel high-throughput format assay to monitor the integrase (IN) strand transfer (ST) reaction in vitro and apply it to a reaction character study and the identification of antiviral drugs.Methods:The donor DNA duplex,with a sequence identical to the U5 end of HIV-1 long terminal repeats,is labeled at its 5' end with biotin (BIO).The target DNA duplex is labeled at its 3' end with digoxin (DIG).IN mediates the integration of donor DNA into target DNA and results in a 5' BIO and 3' DIG-labeled duplex DNA product.Streptavidin-coated magnetic beads were used to capture the product,and the amount of DIG was measured as the ST reaction product.The assay was optimized in 96-well microplate format for high-throughput screening purpose.Moreover,the assay was applied in a ST reaction character study,and the efficiency of the assay in the identification of antiviral compounds was tested.Results:The end-point values,measured as absorbance at 405 nm was approximately 1.5 for the IN-mediated ST reaction as compared with no more than 0.05 of background readings.The ST reaction char-acter and the half maximal inhibitory concentration (IC50) values of 2 known IN inhibitors obtained in our assay were similar to previously reported results using other assays.The evaluation parameter Z' factor for this assay ranged from 0.6 to 0.9.Conclusion:The assay presented here has been proven to be rapid,sensitive,and specific for the detection of IN ST activity,the reaction character study,as well as for the identification of antiviral drugs targeting IN.

  5. Stereoselective differentiation in the Salt-induced Peptide Formation reaction and its relevance for the origin of life.

    Science.gov (United States)

    Plankensteiner, Kristof; Reiner, Hannes; Rode, Bernd M

    2005-04-01

    All living organisms on earth are almost totally made up of biomolecules of only one chiral form. For example, proteins are built almost exclusively of L-amino acids, and sugars are composed of D-saccharides, a fact that is usually referred to as biohomochirality. Its origin is the center of numerous investigations and theories but is not really elucidated yet. The results of experimental investigations of peptide formation in a prebiotically relevant scenario, as described in this paper, give indications on a possible pathway for the synthesis of homochiral L-peptides in the course of the Salt-induced Peptide Formation (SIPF) reaction.

  6. Differential effects of mindful breathing, progressive muscle relaxation, and loving kindness meditation on decentering and negative reactions to repetitive thoughts

    Science.gov (United States)

    Feldman, Greg; Greeson, Jeff; Senville, Joanna

    2010-01-01

    Decentering has been proposed as a potential mechanism of mindfulness-based interventions but has received limited empirical examination to date in experimental studies comparing mindfulness meditation to active comparison conditions. In the present study, we compared the immediate effects of mindful breathing (MB) to two alternative stress management techniques: progressive muscle relaxation (PMR) and loving kindness meditation (LKM) to test whether decentering is unique to mindfulness meditation or common across approaches. Novice meditators (190 female undergraduates) were randomly assigned to complete one of three 15-minute stress-management exercises (MB, PMR, or LKM) presented by audio recording. Immediately after the exercise, participants completed measures of decentering, frequency of repetitive thoughts during the exercise, and degree of negative reaction to thoughts. As predicted, participants in the MB condition reported greater decentering relative to the other two conditions. The association between frequency of repetitive thought and negative reactions to thoughts was relatively weaker in the MB condition than in the PMR and LKM conditions, in which these two variables were strongly and positively correlated. Consistent with the construct of decentering, the relative independence between these two variables in the MB condition suggests that mindful breathing may help to reduce reactivity to repetitive thoughts. Taken together, results help to provide further evidence of decentering as a potential mechanism that distinguishes mindfulness practice from other credible stress-management approaches. PMID:20633873

  7. Influence of l-pyroglutamic acid on the color formation process of non-enzymatic browning reactions.

    Science.gov (United States)

    Wegener, Steffen; Kaufmann, Martin; Kroh, Lothar W

    2017-10-01

    Heating aqueous d-glucose model reactions with l-glutamine and l-alanine yielded similar colored solutions. However, size-exclusion chromatography (SEC) revealed that both non-enzymatic browning reactions proceeded differently. Due to a fast occurring cyclization of l-glutamine to pyroglutamic acid, the typical amino-carbonyl reaction was slowed down. However, l-glutamine and l-alanine model reactions showed the same browning index. Closer investigations could prove that l-pyroglutamic acid was able to influence non-enzymatic browning reactions. SEC analyses of d-glucose model reactions with and without l-pyroglutamic acid revealed an increase of low molecular colored compounds in the presence of l-pyroglutamic acid. Polarimetric measurements showed a doubling of d-glucose mutarotation velocity and HPLC analyses of d-fructose formation during thermal treatment indicated a tripling of aldose-ketose transformation in the presence of l-pyroglutamic acid, which are signs of a faster proceeding non-enzymatic browning process. 2-Pyrrolidone showed no such behavior, thus the additional carboxylic group should be responsible for the observed effects. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. The formation and decay of superheavy nuclei produced in sup 4 sup 8 Ca-induced reactions

    CERN Document Server

    Kumar, S; Gupta, R K; Münzenberg, G; Scheid, W

    2003-01-01

    The formation of superheavy nuclei in sup 4 sup 8 Ca+ sup 2 sup 3 sup 2 Th, sup 2 sup 3 sup 8 U, sup 2 sup 4 sup 2 sup , sup 2 sup 4 sup 4 Pu and sup 2 sup 4 sup 8 Cm reactions and their subsequent decay are studied within the quantum mechanical fragmentation theory (QMFT) and the QMFT-based preformed cluster decay model (PCM) of Gupta and collaborators. According to QMFT, all these sup 4 sup 8 Ca-induced reactions are cold fusion reactions with relative excitation energies larger than those for the Pb-induced cold fusion reactions and smaller than those for the lighter beam, i.e. Mg, Si or S-induced hot fusion reactions. The same reactions were first suggested by Gupta et al in 1977 on the basis of QMFT, and this study re-establishes the same result. In fact, for such heavy isotopes of Z = 110 to 116, sup 5 sup 0 Ca is shown to be a better beam for cold fusion, but sup 5 sup 0 Ca is a radioactive nucleus. The alpha-decay half-lives of these nuclei after 3n and/or 4n evaporations, i.e. of the evaporation resi...

  9. Michael-type addition reactions for the in situ formation of poly(vinyl alcohol)-based hydrogels.

    Science.gov (United States)

    Tortora, Mariarosaria; Cavalieri, Francesca; Chiessi, Ester; Paradossi, Gaio

    2007-01-01

    Michael-type addition reactions offer the possibility to obtain in situ formation of polymeric hydrogels in the absence of a radical mechanism for the networking process. We explored such a synthetic route for obtaining a poly(vinyl alcohol) (PVA)-based hydrogel as a potential biomaterial for applications in vitro-retinal replacement surgery. The presence of radicals in the reaction medium can represent a risk for in situ surgical treatment. To circumvent this problem we have applied nucleophilic addition to ad hoc modified PVA macromers. The gel formation has been studied with respect to the timing required in this surgery and in terms of the structural characteristics of the obtained network.

  10. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-01-10

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  11. Statistical characterisation and stochastic parameterisation of sedimentary geological formations on their reaction capacity for sustainable groundwater quality management

    OpenAIRE

    Griffioen, J.; Vermooten, S.; Keijzer, T.; Bakr, M; Valstar, J.

    2012-01-01

    The fate of contaminants in groundwater aquifers is determined by the buffering capacity of those aquifers together with the composition of inflowing groundwater. A nationwide characterisation of the environmental geochemistry of the shallow subsurface (down to 30 m below surface) has been started in the Netherlands. This covers: 1. the reaction capacity of sediments as buffer for contamination, and 2. typical elemental composition of geological formations and the association between trace el...

  12. FTIR investigation of the reaction between pyridine and iodine in a polyethylene host. Formation of N-iodopyridinium polyiodide

    DEFF Research Database (Denmark)

    Karlsen, Eva; Spanget-Larsen, Jens

    2009-01-01

    The reaction between pyridine and I2 in a low-density polyethylene (LDPE) host is investigated by FTIR vibrational spectroscopy in the mid- and far-IR regions. The investigation is supported by linear dichroism measurements on stretched LDPE samples, and by the results of quantum chemical density...... the formation of extended polyiodide chain structures. The spectroscopic analysis indicates that the ionic product is present in the form of a well-defined complex....

  13. Formation, Isolation and Characterization of a New Ruthenium Complex in Reaction of Acetone Masked Terminal Alkynone with Transfer Hydrogenation Catalyst

    Institute of Scientific and Technical Information of China (English)

    郭敏捷; 李到; 孙延辉; 成江; 张兆国

    2004-01-01

    Reaction of [1S,2S-(Ts-diphen)Ru(Ⅱ)(p-cymene)] (1S,2S-Ts-diphen= 1S,2S-N-tosyl-1,2-diphenylethylenediamine) and 2-hydroxy-2-methyl-non-3-yn-5-one under transfer hydrogenation condition gave a ruthenium complex bearing a 2,5-dihydrofuran moiety. The complex was characterized and a possible mechanism for the formation of the complex was proposed.

  14. Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

    Science.gov (United States)

    Sanibondi, Paolo

    2015-09-01

    Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

  15. Water Mediated Wittig Reactions of Aldehydes in the Teaching Laboratory: Using Sodium Bicarbonate for the in Situ Formation of Stabilized Ylides

    Science.gov (United States)

    Kelly, Michael J. B.; Fallot, Lucas B.; Gustafson, Jeffrey L.; Bergdahl, B. Mikael

    2016-01-01

    The synthesis of alkenes using the Wittig reaction is a traditional part of many undergraduate organic chemistry teaching laboratory curricula. The aqueous medium version of the Wittig reaction presented is a reliable adaptation of this alkene formation reaction as a very safe alternative in the introductory organic chemistry laboratory. The…

  16. Reaction of water-saturated supercritical CO2 with forsterite: Evidence for magnesite formation at low temperatures

    Science.gov (United States)

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Zhi; Hu, Mary; Todd Schaef, H.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O-saturated supercritical CO2 (scCO2) at 35 °C and 50 °C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3·3H2O) and magnesite (MgCO3) at short reaction times (˜3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 °C) than previously thought needed to overcome its well-known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 °C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  17. Reaction of Water-Saturated Supercritical CO2 with Forsterite: Evidence for Magnesite Formation at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Hu, Jian Z.; Hu, Mary Y.; Schaef, Herbert T.; Ilton, Eugene S.; Hess, Nancy J.; Pearce, Carolyn I.; Feng, Ju; Rosso, Kevin M.

    2012-08-01

    The nature of the reaction products that form on the surfaces of nanometer-sized forsterite particles during reaction with H2O saturated supercritical CO2 (scCO2) at 35 C and 50 C were examined under in situ conditions and ex situ following reaction. The in situ analysis was conducted by X-ray diffraction (XRD). Ex situ analysis consisted of scanning electron microscopy (SEM) examination of the surface phases and chemical characterization of precipitates using a combination of confocal Raman spectroscopy, 13C and 29Si NMR spectroscopy, and energy-dispersive X-ray Spectroscopy (EDS). The results show that the forsterite surface is highly reactive with the primary reaction products being a mixture of nesquehonite (MgCO3.3H2O) and magnesite (MgCO3) at short reaction times ({approx}3-4 days) and then magnesite (MgCO3) and a highly porous amorphous silica phase at longer reaction times (14 days). After 14 days of reaction most of the original forsterite transformed to reaction products. Importantly, the formation of magnesite was observed at temperatures much lower (35 C) than previously thought needed to overcome its well known sluggish precipitation kinetics. The conversion of nesquehonite to magnesite liberates H2O which can potentially facilitate further metal carbonation, as postulated by previous investigators, based upon studies at higher temperature (80 C). The observation that magnesite can form at lower temperatures implies that water recycling may also be important in determining the rate and extent of mineral carbonation in a wide range of potential CO2 storage reservoirs.

  18. Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation.

    Science.gov (United States)

    De Vera, Glen Andrew; Stalter, Daniel; Gernjak, Wolfgang; Weinberg, Howard S; Keller, Jurg; Farré, Maria José

    2015-12-15

    When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions.

  19. Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation

    Science.gov (United States)

    2016-01-01

    A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C–C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C–C bonds. PMID:27704805

  20. “Lotus” Domain Formation by the Hydrolysis Reaction of Phospholipase D to Phospholipid Monolayer

    Institute of Scientific and Technical Information of China (English)

    Qiang HE; Jun Bai LI

    2003-01-01

    Hydrolysis reaction of L-α-dipalmitoylphosphatidylcholine (L-DPPC) monolayer with phospholipase D (PLD) has been investigated by Brewster angle microscopy (BAM) combined with the film balance. It has been found that the L-DPPC domains were changed into the "lotus" structure by PLD. It suggests that the hydrolysis reaction is incomplete and the products together with the nonreacted materials undergo a molecular rearrangement at the interface.

  1. Predictive Modeling of Flavor Compound Formation in the Maillard Reaction: A SWOT Analysis

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2010-01-01

    The importance of Maillard flavor compounds for food quality is undisputed, but we are far from being able to control such formation quantitatively in food processing. Kinetic models attempt to predict rates of formation as a function of temperature, pH, water activity/content, and chemical reactivi

  2. Predictive Modeling of Flavor Compound Formation in the Maillard Reaction: A SWOT Analysis

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2010-01-01

    The importance of Maillard flavor compounds for food quality is undisputed, but we are far from being able to control such formation quantitatively in food processing. Kinetic models attempt to predict rates of formation as a function of temperature, pH, water activity/content, and chemical

  3. Effects of fruit extracts on the formation of acrylamide in model reactions and fried potato crisps.

    Science.gov (United States)

    Cheng, Ka-Wing; Shi, Jian-Jun; Ou, Shi-Yi; Wang, Mingfu; Jiang, Yue

    2010-01-13

    Natural products extracted from plants and fruits have attracted increasing attention for the development of effective inhibitors against the formation of acrylamide during food processing. In this study, six fruit extracts (apple, blueberry, mangosteen, longan, dragon fruit with white flesh, and dragon fruit with red flesh) were compared for their activities against acrylamide formation in chemical models containing equal molar quantities of glucose and asparagine in distilled water (160 degrees C for 30 min). Apple extract demonstrated potent inhibition on acrylamide formation. Blueberry, mangosteen, and longan extracts did not have significant impact, whereas dragon fruit extracts enhanced acrylamide formation. Column chromatography guided by chemical model analysis showed that the proanthocyanidin-rich subfraction played a key role in mediating the inhibitory activity. The inhibitory activity was finally corroborated in fried potato crisps. The present study identified some natural products that might have important applications in the food industry to inhibit acrylamide formation.

  4. On progress and rate of the peritectic reaction Fo + SiO2 → En in natural andesitic arc magmas

    Science.gov (United States)

    Zellmer, Georg F.; Sakamoto, Naoya; Matsuda, Nozomi; Iizuka, Yoshiyuki; Moebis, Anja; Yurimoto, Hisayoshi

    2016-07-01

    Using a high resolution ion microprobe with SCAPS imaging, the peritectic reaction of forsterite + silica to enstatite was studied down to submicron level in a natural andesitic tephra from the Central Plateau of North Island, New Zealand. The fayalitic component of natural olivines is stable in high-silica melts, and therefore the reaction is in fact a two-step progress: 1. Dissolution of Mg-rich olivine, rate-limited by Fe-Mg interdiffusion at the crystal rim, results in enrichment of Fe in the crystal rim and of Mg in the c. 1 μm wide melt boundary layer around the crystal. 2. Magnesian pyroxenes preferentially but not exclusively nucleate in the melt boundary layer and grow; as soon as these microlites touch the rim of the dissolving olivine, they shield the crystals from the silica-rich melt, thereby preventing further olivine dissolution. At this point, Fe-Mg interdiffusion begins to destroy the Fe-enrichment of the olivine rim. The reaction is completed when the dissolving olivine crystal is completely mantled by magnesian pyroxene microlites. Thick pyroxene mantles are likely the result of pyroxene overgrowth rather than due to peritectic transformation. The morphology of the olivine rim preserves information about the reaction history of the grain. Modeling of Fe-Mg interdiffusion in the olivine rim following its shielding from the melt by pyroxene overgrowth may yield the rates of olivine dissolution and the rates of pyroxene growth if temperature is known. For the tephra we have studied, microlite thermometry yields a temperature of 1137 (±41) °C, indicating an olivine dissolution rate of 3-6 × 10-11 ms-1 and an initially volumetric pyroxene growth rate of 2.2-5.6 × 10-21 m3 s-1. This points to timescales between olivine crystal uptake into the SiO2-rich melt and explosive eruption at the surface of a few hours to at most a day.

  5. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-02-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night during spring and summer in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C105H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  6. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-06-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  7. The initial step of silicate versus aluminosilicate formation in zeolite synthesis: a reaction mechanism in water with a tetrapropylammonium template

    KAUST Repository

    Trinh, Thuat T.

    2012-01-01

    The initial step for silicate and aluminosilicate condensation is studied in water in the presence of a realistic tetrapropylammonium template under basic conditions. The model corresponds to the synthesis conditions of ZSM5. The free energy profile for the dimer formation ((OH) 3Si-O-Si-(OH) 2O - or [(OH) 3Al-O-Si-(OH) 3] -) is calculated with ab initio molecular dynamics and thermodynamic integration. The Si-O-Si dimer formation occurs in a two-step manner with an overall free energy barrier of 75 kJ mol -1. The first step is associated with the Si-O bond formation and results in an intermediate with a five-coordinated Si, and the second one concerns the removal of the water molecule. The template is displaced away from the Si centres upon dimer formation, and a shell of water molecules is inserted between the silicate and the template. The main effect of the template is to slow down the backward hydrolysis reaction with respect to the condensation one. The Al-O-Si dimer formation first requires the formation of a metastable precursor state by proton transfer from Si(OH) 4 to Al(OH) 4 - mediated by a solvent molecule. It then proceeds through a single step with an overall barrier of 70 kJ mol -1. The model with water molecules explicitly included is then compared to a simple calculation using an implicit continuum model for the solvent. The results underline the importance of an explicit and dynamical treatment of the water solvent, which plays a key role in assisting the reaction. © the Owner Societies 2012.

  8. Benchtop monitoring of reaction progress via visual recognition with a handheld UV lamp: in situ monitoring of boronic acids in the Suzuki-Miyaura reaction.

    Science.gov (United States)

    Barder, Timothy E; Buchwald, Stephen L

    2007-01-04

    [reaction: see text] Although boronic acids are widely used in metal-catalyzed reactions, it is difficult to assay their consumption. As such, we developed a reversible fluorescent sensor that is activated upon binding a boronic acid. The sensor can be used to monitor consumption of a boronic acid in Suzuki-Miyaura reactions. Importantly, only a standard handheld long-wave UV lamp (365 nm) is required and fluorescence is easily detectable with the naked eye without disturbing the reaction mixture.

  9. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    Science.gov (United States)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  10. Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

    Science.gov (United States)

    Hussain, Javed; Jónsson, Hannes; Skúlason, Egill

    2016-12-22

    An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO2 as well as H2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H(+) + e(-) → *CO + H2O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO2 using platinum electrodes have produced only H2. A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

  11. Formation of complex organic molecules in cold objects: the role of gas phase reactions

    OpenAIRE

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-01-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) ...

  12. Rapid Determination of HAAs Formation Potential of the Reaction of Humic Acid with Chlorine or Chlorine Dioxide

    Institute of Scientific and Technical Information of China (English)

    ZHU Zhi-liang; GE Yuan-xin; ZHANG Rong-hua; MA Hong-mei; HAO Jian-fu

    2007-01-01

    On the basis of gas chromatography(GC) coupled with a short capillary column and an electron capture detector(ECD), a simple and rapid method for the determination of five haloacetic acids(HAAs) in drinking water was developed by the optimization of derivation conditions and the modification of gas chromatographic program. HAAs formation potential(HAAFP) of the reaction of humic acid with chlorine was determined via this method. The major advantages of the method are the simplicity of chromatographic temperature program and the short run time of GC. Dichloroacetic acid(DCAA) and Trichloroacetic acid(TCAA), which were detected in the determination of HAAFP, were rapidly formed in the first 72 h of the reaction of humic acid with chlorine. HAAFP of the reaction of humic acid with chlorine increased with the increase in the concentrations of humic acid and chlorine. The average HAAFP of the reaction of humic acid with chlorine was 39.9 μg/mg TOC under the experimental conditions. When the concentration of humic acid was 4 mg/L, the concentration of HAAs, which were produced in the reaction of humic acid with chorine, may exceed MCL of 60 μg/L HAAs as the water quality standards for urban water supply of China and the first stage of US EPA disinfection/disinfection by-products(D/DBP) rule; when the concentration of humic acid was 2 mg/L, the concentration of HAAs may exceed MCL of 30 μg/L HAAs for the second stage of US EPA D/DBP rule. When humic acid was reacted with chlorine dioxide, only DCAA was detected with a maximum concentration of 3.3 μg/L at a humic acid content of 6 mg/L. It was demonstrated that the substitution of chlorine dioxide for chorine may entirely or partly control the formation of HAAs and effectively reduce the health risk associated with disinfected drinking water.

  13. The formation of light absorbing insoluble organic compounds from the reaction of biomass burning precursors and Fe(III)

    Science.gov (United States)

    Lavi, Avi; Lin, Peng; Bhaduri, Bhaskar; Laskin, Alexander; Rudich, Yinon

    2017-04-01

    Dust particles and volatile organic compounds from fuel or biomass burning are two major components that affect air quality in urban polluted areas. We characterized the products from the reaction of soluble Fe(III), a reactive transition metal originating from dust particles dissolution processes, with phenolic compounds , namely, guaiacol, syringol, catechol, o- and p- cresol that are known products of incomplete fuel and biomass combustion but also from other natural sources such as humic compounds degradation. We found that under acidic conditions comparable to those expected on a dust particle surface, phenolic compounds readily react with dissolved Fe(III), leading to the formation of insoluble polymeric compounds. We characterized the insoluble products by x-ray photoelectron microscopy, UV-Vis spectroscopy, mass spectrometry, elemental analysis and thermo-gravimetric analysis. We found that the major chromophores formed are oligomers (from dimers to pentamers) of the reaction precursors that efficiently absorb light between 300nm and 500nm. High variability of the mass absorption coefficient of the reaction products was observed with catechol and guaiacol showing high absorption at the 300-500nm range that is comparable to that of brown carbon (BrC) from biomass burning studies. The studied reaction is a potential source for the in-situ production of secondary BrC material under dark conditions. Our results suggest a reaction path for the formation of bio-available iron in coastal polluted areas where dust particles mix with biomass burning pollution plumes. Such mixing can occur, for instance in the coast of West Africa or North Africa during dust and biomass burning seasons

  14. Systematic study of quasifission characteristics and timescales in heavy element formation reactions

    Directory of Open Access Journals (Sweden)

    Hinde D.J.

    2016-01-01

    Full Text Available Superheavy elements can only be created in the laboratory by the fusion of two massive nuclei. Mass-angle distributions give the most direct information on the characteristics and time scales of quasifission, the major competitor to fusion in these reactions. The systematics of 42 mass-angle distributions provide information on the global characteristics of quasifission. Deviations from the systematics reveal the major role played by the nuclear structure of the two colliding nuclei in determining the reaction outcome, and in hindering or favouring heavy element production.

  15. Numerical study of how creep and progressive stiffening affect the growth stress formation in trees

    DEFF Research Database (Denmark)

    Ormarsson, Sigurdur; Dahlblom, O.; Johansson, M.

    2010-01-01

    clearly show how the growth stresses are progressively generated during the tree growth. The inner core becomes more and more compressed whereas the outer sapwood is subjected to slightly increased tension. The parametric study shows that the growth stresses are highly influenced by the creep behaviour...

  16. Thermokinetics on the reaction of formation of Dy[(C5H8NS2)3(C12H8N2)

    Institute of Scientific and Technical Information of China (English)

    GAO Shengli; CHEN Sanping; JIAO Baojuan; SHUAI Qi; SHI Qizhen

    2005-01-01

    The enthalpy change of formation of the reaction of hydrous dysprosium chloride meter. Thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), rate constant and kinetics parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the reaction have also been calculated. The enthalpy change of the solid-phase reaction at 298.15 K has been obtained as (53.59 ± 0.29)liquid-phase and solid-phase reaction indicated that the complex could only be synthesized in liquid-phase reaction.

  17. Kinetics and mechanism of the reaction of OH with the trimethylbenzenes--experimental evidence for the formation of adduct isomers.

    Science.gov (United States)

    Bohn, Birger; Zetzsch, Cornelius

    2012-10-28

    The reversible gas-phase addition of OH radicals to the trimethylbenzenes was investigated in pulsed experiments utilizing VUV flash-photolysis resonance-fluorescence of H(2)O in the temperature range of 275-340 K. Triexponential OH decays were observed in the presence of the trimethylbenzenes, indicating the participation of more than one adduct species. Analytical solutions for the system of differential equations with two adduct isomers were derived, and the OH decay curves were evaluated based on this reaction model. This led to significant improvements of fit qualities and notable changes in OH rate constants compared to a previous model with a single adduct species. The detailed analysis was confined to 1,3,5-trimethylbenzene where reversible formation of two OH-aromatic ortho- and ipso-adduct isomers is feasible in accordance with the extended reaction model. Only after inclusion of additional isomerization reactions, consistent thermochemical data were obtained from the fitted rate constants. Reaction enthalpies of -83 ± 7 kJ mol(-1) and -35 ± 22 kJ mol(-1) were derived for the formation of one adduct isomer and the isomerization into the other, respectively. Based on literature data, the more and less stable adducts were assigned to ipso- and ortho-adduct isomers, respectively. The potential isomerization precluded the determination of primary yields of adduct isomers but formation of the ipso-adduct in any case is a minor process. For the rate constants of the OH + 1,3,5-trimethylbenzene reaction an Arrhenius expression k(OH) = 1.32 × 10(-11) cm(3) s(-1) exp(450 ± 50 K/T) was obtained. Based on the same approach, the rate constants of the OH reactions with 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene were derived as k(OH) = 3.61 × 10(-12) cm(3) s(-1) exp(620 ± 80 K/T) and k(OH) = 2.73 × 10(-12) cm(3) s(-1) exp(730 ± 70 K/T), respectively.

  18. Kinetic modeling of acrylamide formation in aqueous reaction systems and potato crisps : Text & Figures

    NARCIS (Netherlands)

    Knol, J.J.

    2008-01-01

    Acrylamide can be formed in foods that have undergone a high temperature treatment (>120 °C) such as French fries, crisps, coffee and bread, due to the Maillard reaction. The evidence of acrylamide in foods posing a risk for different types of cancer has been strengthened. Mitigation of

  19. Kinetic modeling of acrylamide formation in aqueous reaction systems and potato crisps : Text & Figures

    NARCIS (Netherlands)

    Knol, J.J.

    2008-01-01

    Acrylamide can be formed in foods that have undergone a high temperature treatment (>120 °C) such as French fries, crisps, coffee and bread, due to the Maillard reaction. The evidence of acrylamide in foods posing a risk for different types of cancer has been strengthened. Mitigation of acrylamid

  20. Role of choline and glycine betaine in the formation of N,N-dimethylpiperidinium (mepiquat) under Maillard reaction conditions.

    Science.gov (United States)

    Bessaire, Thomas; Tarres, Adrienne; Stadler, Richard H; Delatour, Thierry

    2014-01-01

    This study is the first to examine the role of choline and glycine betaine, naturally present in some foods, in particular in cereal grains, to generate N,N-dimethylpiperidinium (mepiquat) under Maillard conditions via transmethylation reactions involving the nucleophile piperidine. The formation of mepiquat and its intermediates piperidine - formed by cyclisation of free lysine in the presence of reducing sugars - and N-methylpiperidine were monitored over time (240°C, up to 180 min) using high-resolution mass spectrometry in a model system comprised of a ternary mixture of lysine/fructose/alkylating agent (choline or betaine). The reaction yield was compared with data recently determined for trigonelline, a known methylation agent present naturally in coffee beans. The role of choline and glycine betaine in nucleophilic displacement reactions was further supported by experiments carried out with stable isotope-labelled precursors (¹³C- and deuterium-labelled). The results unequivocally demonstrated that the piperidine ring of mepiquat originates from the carbon chain of lysine, and that either choline or glycine betaine furnishes the N-methyl groups. The kinetics of formation of the corresponding demethylated products of both choline and glycine betaine, N,N-demethyl-2-aminoethanol and N,N-dimethylglycine, respectively, were also determined using high-resolution mass spectrometry.

  1. Deep Eutectic Solvents as Reaction Media for the Palladium-Catalysed C-S Bond Formation: Scope and Mechanistic Studies.

    Science.gov (United States)

    Marset, Xavier; Guillena, Gabriela; Ramón, Diego J

    2017-08-04

    A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles where C-S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows the formation of different types of products in an environmentally friendly medium by selecting the components of the reaction, which engage one with another as pieces in a jigsaw. This simple procedure avoids the use of toxic volatile organic solvents allowing the formation of complex molecules in a one-pot reaction under mild conditions. Despite the fact that only 1 mol % of metal loading is used, the recyclability of the catalytic system is possible. Kinetic experiments were performed and the reaction order for all reagents, catalyst and ligand was determined. The obtained results were compared to palladium nanocrystals of different known shapes in order to shed some light on the properties of the catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Modeling stopped-flow data for nucleic acid duplex formation reactions: the importance of off-path intermediates.

    Science.gov (United States)

    Sikora, Jacqueline R; Rauzan, Brittany; Stegemann, Rachel; Deckert, Alice

    2013-08-01

    Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-path intermediates are shown to involve unimolecular and, in one case, bimolecular structure in one of the single strands of complementary DNA. Three models are developed to account for the observed single-stranded structures that are formed in parallel with duplex formation. These models are applied to the analysis of stopped-flow data for eight different nonself-complementary duplex formation reactions in order to extract the elementary rate constant for formation of the duplex from the complementary random coil single-stranded DNA. The free energy of activation (at 25 °C) for the denaturation of each duplex is calculated from these data and is shown to have a linear correlation to the overall standard free energy for duplex formation (also at 25 °C). Duplexes that contain mismatches obey a parallel linear free-energy (LFE) relationship with a y-intercept that is greater than that of duplexes without mismatches. Slopes near unity for the LFE relationships indicate that all duplexes go through an early, unstructured transition state.

  3. Secondary organic aerosol formation from the gas phase reaction of hydroxyl radicals with m-, o- and p-cresol

    Science.gov (United States)

    Henry, Françoise; Coeur-Tourneur, Cecile; Ledoux, Frédéric; Tomas, Alexandre; Menu, Dominique

    Secondary organic aerosol (SOA) formation during the atmospheric oxidation of cresols was investigated using a large smog chamber (8000 L), at atmospheric pressure, 294±2 K and low relative humidity (6-10%). Cresol oxidation was initiated by irradiation of cresol/CH 3ONO/NO/air mixtures. The cresol loss was measured by gas chromatography with a flame ionization detector (GC-FID) and the temporal evolution of the aerosol was monitored using a scanning mobility particle sizer (SMPS). The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted cresol concentrations assuming a particle density of 1.4 g cm -3. Analysis of the data clearly show that Y is a strong function of Mo and that SOA formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial cresol concentration, which leads to aerosol yields from 9% to 42%. These results are in good agreement with a recent study performed on SOA formation from the photo-oxidation of o-cresol in a smog chamber. To our knowledge, the present work represents the first investigation of SOA formation from OH reaction with m- and p-cresol.

  4. Troglitazone thiol adduct formation in human liver microsomes: enzyme kinetics and reaction phenotyping.

    Science.gov (United States)

    Gan, Jinping; Qu, Qinling; He, Bing; Shyu, Wen C; Rodrigues, A David; He, Kan

    2008-08-01

    Troglitazone (TGZ) induced hepatotoxicity has been linked to cytochrome P450 (CYP)-catalyzed reactive metabolite formation. Therefore, the kinetics and CYP specificity of reactive metabolite formation were studied using dansyl glutathione (dGSH) as a trapping agent after incubation of TGZ with human liver microsomes (HLM) and recombinant human CYP proteins. CYP2C8 exhibited the highest rate of TGZ adduct (TGZ-dGS) formation, followed by CYP3A4, CYP3A5, and CYP2C19. The involvement of CYP2C8 and CYP3A4 was confirmed with CYP form-selective chemical inhibitors. The impact of TGZ concentration on the rate of TGZ-dGS formation was also evaluated. In this instance, two distinctly different profiles were observed with recombinant CYP3A4 and CYP2C8. It is concluded that both CYP3A4/5 and CYP2C8 play a major role in the formation of TGZ adduct in HLM. However, the contribution of these CYPs varies depending on their relative expression and the concentration of TGZ.

  5. Wind-driven gas networks and star formation in galaxies: reaction-advection hydrodynamic simulations

    Science.gov (United States)

    Chappell, David; Scalo, John

    2001-07-01

    The effects of wind-driven star formation feedback on the spatio-temporal organization of stars and gas in galaxies is studied using two-dimensional intermediate-representational quasi-hydrodynamical simulations. The model retains only a reduced subset of the physics, including mass and momentum conservation, fully non-linear fluid advection, inelastic macroscopic interactions, threshold star formation, and momentum forcing by winds from young star clusters on the surrounding gas. Expanding shells of swept-up gas evolve through the action of fluid advection to form a `turbulent' network of interacting shell fragments which have the overall appearance of a web of filaments (in two dimensions). A new star cluster is formed whenever the column density through a filament exceeds a critical threshold based on the gravitational instability criterion for an expanding shell, which then generates a new expanding shell after some time delay. A filament-finding algorithm is developed to locate the potential sites of new star formation. The major result is the dominance of multiple interactions between advectively distorted shells in controlling the gas and star morphology, gas velocity distribution and mass spectrum of high mass density peaks, and the global star formation history. The gas morphology strongly resembles the model envisioned by Norman & Silk, and observations of gas in the Large Magellanic Cloud (LMC)Q1 and local molecular clouds. The dependence of the frequency distribution of present-to-past average global star formation rate on a number of parameters is investigated. Bursts of star formation only occur when the time-averaged star formation rate per unit area is low, or the system is small. Percolation does not play a role. The broad distribution observed in late-type galaxies can be understood as a result of either small size or small metallicity, resulting in larger shell column densities required for gravitational instability. The star formation rate

  6. The {sup 30}P(p, γ){sup 31}S reaction in classical novae: progress and prospects

    Energy Technology Data Exchange (ETDEWEB)

    Wrede, C., E-mail: wrede@nscl.msu.edu [Department of Physics and Astronomy and National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, Michigan 48824 (United States)

    2014-04-15

    The unknown thermonuclear rate of the {sup 30}P(p, γ){sup 31}S reaction at classical-nova temperatures currently prohibits the accurate modeling of nova nucleosynthesis in the A ⩾ 30 region. This is hindering the calibration of nova thermometers based on observed O/S, S/Al, O/P, and P/Al abundance ratios in nova ejecta, the calibration of a meter to probe mixing at the core-envelope interface in novae based on the observed Si/H abundance ratio, and the identification of candidate pre-solar nova grains found in primitive meteorites based on laboratory measurements of their {sup 30}Si/{sup 28}Si isotopic ratios. Each of these diagnostics could address key questions in our understanding of classical novae if the {sup 30}P(p, γ){sup 31}S rate were known. We review progress on the determination of the {sup 30}P(p, γ){sup 31}S rate leading to a critical assessment of current interpretations of published data and prospects for future work.

  7. Statistical characterisation and stochastic parameterisation of sedimentary geological formations on their reaction capacity for sustainable groundwater quality management

    Science.gov (United States)

    Griffioen, J.; Vermooten, S.; Keijzer, T.; Bakr, M.; Valstar, J.

    2012-04-01

    The fate of contaminants in groundwater aquifers is determined by the buffering capacity of those aquifers together with the composition of inflowing groundwater. A nationwide characterisation of the environmental geochemistry of the shallow subsurface (down to 30 m below surface) has been started in the Netherlands. This covers: 1. the reaction capacity of sediments as buffer for contamination, and 2. typical elemental composition of geological formations and the association between trace elements and major minerals. For this purpose, the Netherlands is subdivided into 27 so-called geotop regions each having a unique geological build-up of the shallow subsurface. Here, four types are recognised based on vertical hydrogeological build-up. The regions are statistically characterised on their geochemical composition using combinations of lithological class and geological formation as strata. The statistical data are subsequently coupled with a geological voxel model of the subsurface to stochastically parameterise the geological units on reaction capacity. This combined approach will be illustrated for the Dutch province Zeeland. Reaction capacity is considered as a series of geochemical characteristics that control acid/base condition, redox condition and sorption capacity. Five primary reaction capacity variables are characterised: 1. pyrite, 2. non-pyrite, reactive iron (oxides, siderite and glauconite), 3. clay fraction, 4. organic matter and 5. Ca-carbonate. Important reaction capacity variables that are determined by more than one solid compound are also deduced: 1. potential reduction capacity (PRC) by pyrite and organic matter, 2. cation-exchange capacity (CEC) by organic matter and clay content, 3. carbonate buffering upon pyrite oxidation (CPBO) by carbonate and pyrite. A statistical investigation of several hunderds of sediment analyses is performed that provides the geochemical properties of the sediments. Here, classification based on sedimentary facies

  8. Role of glyoxal in SOA formation from aromatic hydrocarbons: gas-phase reaction trumps reactive uptake

    Directory of Open Access Journals (Sweden)

    S. Nakao

    2011-11-01

    Full Text Available This study evaluates the significance of glyoxal acting as an intermediate species leading to SOA formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH42SO4 seed particles is observed; however, glyoxal did not partition to SOA or SOA coated aqueous seed during all aromatic hydrocarbon experiments (RH up to 80%. Glyoxal is found to only influence SOA formation by raising hydroxyl (OH radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1 increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2 glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase observed SOA volume; (3 SOA formation from toluene + NOx photooxidation with and without deliquesced (NH42SO4 seed resulted in similar SOA growth, consistent with a coating of SOA preventing glyoxal uptake onto deliquesced (NH42SO4 seed; and (4 the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS from SOA formed by 2-tert-butylphenol (BP oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol is minor when the surface (and near-surface of aerosols are primarily composed of secondary organic compounds.

  9. Inhibition of rho-kinase by fasudil suppresses formation and progression of experimental abdominal aortic aneurysms.

    Directory of Open Access Journals (Sweden)

    Chen Peng

    Full Text Available OBJECTIVE: Accumulating evidence suggests that inflammatory cell infiltration is crucial pathogenesis during the initiation and progression of abdominal aortic aneurysm (AAA. Given Rho-kinase (ROCK, an important kinase control the actin cytoskeleton, regulates the inflammatory cell infiltration, thus, we investigate the possibility and mechanism of preventing experimental AAA progression via targeting ROCK in mice porcine pancreatic elastase (PPE model. METHODS AND RESULTS: AAA was created in 10-week-old male C57BL/6 mice by transient intraluminal porcine pancreatic elastase infusion into the infrarenal aorta. The mRNA level of RhoA, RhoC, ROCK1 and ROCK2 were elevated in aneurismal aorta. Next, PPE infusion mice were orally administrated with vehicle or ROCK inhibitor (Fasudil at dose of 200 mg/kg/day during the period of day 1 prior to PPE infusion to day 14 after PPE infusion. PPE infusion mice treated with Fasudil produced significantly smaller aneurysms as compare to PPE infusion mice treated with vehicle. AAAs developed in all vehicle-treated groups within 14 days, whereas AAAs developed in six mice (66%, 6/9 treated with Fasudil within 14 days. Furthermore, our semi-quantitative histological analysis revealed that blood vessels and macrophages were significantly reduced in Fasudil treated mice during the AAA progression. Finally, when mice with existing AAAs were treated with Fasudil, the enlargement was nearly completely suppressed. CONCLUSION: Fasudil inhibits experimental AAA progression and stabilize existing aneurysms, through mechanisms likely related to impaired mural macrophage infiltration and angiogenesis. These findings suggest that ROCK inhibitor may hold substantial translational value for AAA diseases.

  10. Humanized mouse model of ovarian cancer recapitulates patient solid tumor progression, ascites formation, and metastasis.

    Directory of Open Access Journals (Sweden)

    Richard B Bankert

    Full Text Available Ovarian cancer is the most common cause of death from gynecological cancer. Understanding the biology of this disease, particularly how tumor-associated lymphocytes and fibroblasts contribute to the progression and metastasis of the tumor, has been impeded by the lack of a suitable tumor xenograft model. We report a simple and reproducible system in which the tumor and tumor stroma are successfully engrafted into NOD-scid IL2Rγ(null (NSG mice. This is achieved by injecting tumor cell aggregates derived from fresh ovarian tumor biopsy tissues (including tumor cells, and tumor-associated lymphocytes and fibroblasts i.p. into NSG mice. Tumor progression in these mice closely parallels many of the events that are observed in ovarian cancer patients. Tumors establish in the omentum, ovaries, liver, spleen, uterus, and pancreas. Tumor growth is initially very slow and progressive within the peritoneal cavity with an ultimate development of tumor ascites, spontaneous metastasis to the lung, increasing serum and ascites levels of CA125, and the retention of tumor-associated human fibroblasts and lymphocytes that remain functional and responsive to cytokines for prolonged periods. With this model one will be able to determine how fibroblasts and lymphocytes within the tumor microenvironment may contribute to tumor growth and metastasis, and will make it possible to evaluate the efficacy of therapies that are designed to target these cells in the tumor stroma.

  11. Mechanistic investigation into cross-linking reactions in low rank coal: formation and pyrolysis of aryl esters

    Energy Technology Data Exchange (ETDEWEB)

    Britt, P.F.; Buchanan, A.C. III; Kiddern, M.K.; Skeen, J.D. [Oak Ridge National Lab. Oak Ridge, TN (USA). Chemical Sciences Division

    2003-07-01

    In this study, the sealed tube pyrolysis of mixtures of m-phenylphenol and benzoic acid have been investigated at 400{sup o}C to determine if cross-linking reactions can occur, and to determine the low temperature pyrolysis pathways of aryl esters, which are not known. Initial studies show that condensation reactions occur between carboxylic acids and phenols to form aryl esters at temperatures as low as 200{sup o}C. With a 3:1 ratio of m-phenylphenol to benzoic acid, yields of m-phenylphenyl benzoate were as high as 50% at 400{sup o}C. At short reaction times, the dominant products were the aryl ester and benzene, formed by the acid catalyzed decarboxylation of benzoic acid, but at longer times, other arylated products grew in indicating that radical reactions were occurring. These products appear to arise from the induced decomposition of benzoic anhydride to form phenyl radicals. The thermal stability of aryl esters was investigated through the pyrolysis of phenyl benzoate at 400{sup o}C. As predicted, the aryl ester appeared to be thermally stable but hydrolytically unstable. In general, formation of aryl esters could act as a low temperature cross-link in low rank coals. 19 refs., 3 figs., 1 tab.

  12. Formation of composites fabricated by exothermic dispersion reaction in Al-TiO2-B2O3 system

    Institute of Scientific and Technical Information of China (English)

    ZHU He-guo; WANG Heng-zhi; GE Liang-qi; CHEN Shi; WU Shen-qing

    2007-01-01

    The formation of aluminum matrix composites fabricated by exothermic dispersion reaction in Al-TiO2-B2O3 system was investigated. The thermal analysis results show that the reactions are spontaneous and exothermic. The Gibbs free energy of α-Al2O3 is the lowest among all the combustion products, followed by TiB2 and Al3Ti. It is noted that when the B2O3/TiO2 mole ratio is below 1, the reaction products are composed of particle-like α-Al2O3, TiB2 and rod-like Al3Ti. The α-Al2O3 crystallites, resulting from the reaction between Al and TiO2 or B2O3, are segregated at the grain boundaries due to a lower wettability with the matrix. SEM micrographs show that rod-like Al3Ti phase distributes uniformly in the matrix. When the B2O3/TiO2 mole ratio is around 1, the Al3Ti phase almost disappears in the composites, and the distribution of α-Al2O3 particulates is improved evidently.

  13. Theoretical study on the formation of tetraoxygen conformational isomerism in the CO 2 with O 3 reaction

    Science.gov (United States)

    Goodarzi, Moein; Piri, Farideh; Hajari, Nasim; Karimi, Leila

    2010-10-01

    The reaction mechanism of CO 2 with O 3 on the singlet potential energy surface has been investigated at the CBS-QB3//B3LYP/6-311++G(3df, 3pd) level of theory. The reactants are initially associated with adducts IN1 (OOO-OCO) and IN2 (OC-cyclic O 4) in a barrier-less process. Then, adducts undergo isomerization and dissociation processes to produce P 1 (CO + 2 3O 2) and P 2 (CO 3 + 3O 2) with two different mechanisms. The calculated results show that there is no favorable pathway for the formation of these two products in the atmospheric reaction of CO 2 with O 3.

  14. Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo-Polymerization Reaction.

    Science.gov (United States)

    Park, In-Hyeok; Medishetty, Raghavender; Lee, Hyeong-Hwan; Mulijanto, Caroline Evania; Quah, Hong Sheng; Lee, Shim Sung; Vittal, Jagadese J

    2015-06-15

    Getting suitable crystals for single-crystal X-ray crystallographic analysis still remains an art. Obtaining single crystals of metal-organic frameworks (MOFs) containing organic polymers poses even greater challenges. Here we demonstrate the formation of a syndiotactic organic polymer ligand inside a MOF by quantitative [2+2] photopolymerization reaction in a single-crystal-to-single-crystal manner. The spacer ligands with trans,trans,trans-conformation in the pillared-layer MOF with guest water molecules in the channels, undergo pedal motion to trans,cis,trans-conformation prior to [2+2] photo-cycloaddition reaction and yield single crystals of MOF containing two-dimensional coordination polymers fused with the organic polymer ligands. We also show that the organic polymer in the single crystals can be depolymerized reversibly by cleaving the cyclobutane rings upon heating. These MOFs also show interesting photoluminescent properties and sensing of small organic molecules.

  15. Theoretical study on the reaction mechanism of formation of 3,5-diacetyl-1,4-dihydrolutidine

    OpenAIRE

    寺前, 裕之; Maruo, Yasuko Y.

    2013-01-01

    We have studied the reaction path of the formation of 3,5-diacetyl-1,4-dihydrolutidine (DL1), 3,5-dibenzoyl-1,4-dihydro-2,6-dimethylpyridine, and 2,6-dibenzoyl-1,4-dihydro-3,5-dimethylpyridine with the ab initio molecular orbital method at HF/3-21G and HF/6-31G(d,p) levels. For DL1, we also calculated at MP2/6-31G(d,p) level. The barrier heights of H2O elimination elementary reactions are ca. 50-60 kcal/mol and quite high in the gas phase, however, this is well agreed with the experimental re...

  16. Zinc catalyzed Guanylation reaction of Amines with Carbodiimides/ Isocyanate leading to Guanidines/Urea derivatives formation

    Indian Academy of Sciences (India)

    JAYEETA BHATTACHARJEE; MITALI SACHDEVA; INDRANI BANERJEE; TARUN K PANDA

    2016-06-01

    We report the highly chemo-selective catalytic addition of N–H bonds from various aromaticamines to carbodiimides and isocyanates using (Ar-BIAO)ZnCl2 complexes [Ar-BIAO = N-(aryl)iminoacenapthenone,Ar = 2,6-$Me_{2}C_{6}H_{3}$ (1), 2,4,6 $Me_{3}C_{6}H_{2}$ (2), $2,6-^{i}$ $Pr_{2}C_{6}_H{3} (3)] as the pre-catalyst to prepareguanidine and urea derivatives in 55-90% yield. The complex 3 showed higher catalytic activity than analogouscomplexes 1 and 2 under similar reaction conditions. The catalytic guanylation of N–H bonds with heterocumulenesdisplays a broad substrate scope. The amines having electron donating groups underwent higher conversionthan the amines having electron withdrawing groups to afford corresponding guanidine or urea derivatives.A possible mechanism involving penta-coordinated zinc transition state for the catalytic reaction is presented.

  17. Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation.

    Science.gov (United States)

    Librando, Vito; Tringali, Giuseppe

    2005-05-01

    This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.

  18. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

    2016-08-05

    Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

  19. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    Science.gov (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-09-01

    The gas-phase oxidation of doubly protonated peptides containing neutral basic residues to various products, including [M + H + O]+, [M - H]+, and [M - H - NH3]+, is demonstrated here via ion/ion reactions with periodate. It was previously demonstrated that periodate anions are capable of oxidizing disulfide bonds and methionine, tryptophan, and S-alkyl cysteine residues. However, in the absence of these easily oxidized sites, we show here that systems containing neutral basic residues can undergo oxidation. Furthermore, we show that these neutral basic residues primarily undergo different types of oxidation (e.g., hydrogen abstraction) reactions than those observed previously (i.e., oxygen transfer to yield the [M + H + O]+ species) upon gas-phase ion/ion reactions with periodate anions. This chemistry is illustrated with a variety of systems, including a series of model peptides, a cell-penetrating peptide containing a large number of unprotonated basic sites, and ubiquitin, a roughly 8.6 kDa protein.

  20. Progress in the study on the composition and formation mechanism of gallstone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Our serial studies from 1970s on chemical composition, structure determination and formation mechanism of gallstones were reviewed. The chemical component investigation of brown-pigment gallstone demonstrated that it consists of macromolecules such as proteins, glycoproteins, polysaccharides, bilirubin polymers and pigment polymers, and biomolecules such as cholesterol, bile salts, calcium salts of carbonate, phosphate, fatty acids and bilirubinate as well as various metal ions. The binding of metal ions with bile salts and bilirubin plays important roles in gallstone formation, i.e., calcium bilirubinate complex is the major constitute of brown-pigment gallstones, and copper bilirubinate complex is critical in the black color appearance of black-pigment gallstone. The cross section of many gallstones exhibits a concentric ring structure composed of various small particles with a fractal character. This is nonlinear phenomenon in gallstone formation. A typical model system of metal ions-deoxycholate (or cholate)-gel was chosen to mimic an in vitro pattern formation system. The experimental results suggested that a nonlinear scientific concept should be considered in understanding gallstone formation. Minor changes in the chemical composition and/or the microenvironment may lead to very different precipitate patterns with a variety of shapes, colors, appearances, and structures. A new model was suggested that periodical templets of periodical and fractal patterns were formed in the initial stage, then the spatio-temporal patterns grew gradually on it. Furthermore, the interaction between divalent metal ions and bile salts in vitro was investigated, and the results indicated that non-stoichiometric M(DC)2-NaDC mixed complexes with mixed micelles structure can be formed in physiological condition.

  1. Progress in the Study on the Formation of the Summertime Subtropical Anticyclone

    Institute of Scientific and Technical Information of China (English)

    刘屹岷; 吴国雄

    2004-01-01

    The studies in China on the formation of the summertime subtropical anticyclone on the climate timescale are reviewed. New insights in resent studies are introduced. It is stressed that either in the free atmosphere or in the planetary boundary, the descending arm of the Hadley cell cannot be considered as a mechanism for the formation of the subtropical anticyclone. Then the theories of thermal adaptation of the atmosphere to external thermal forcing and the potential vorticity forcing are developed to understand the formation of the subtropical anticyclone in the three-dimensional domain. Numerical experiments are designed to verify these theories. Results show that in the boreal summer, the formation of the strong South Asian High in the upper troposphere and the subtropical anticyclone over the western Pacific in the middle and lower troposphere is, to a great extent, due to the convective latent heating associated with the Asian monsoon, but affected by orography and the surface sensible heating over the continents.On the other hand, the formation of the subtropical anticyclone at the surface over the northern Pacific and in the upper troposphere over North America is mainly due to the strong surface sensible heating over North America, but affected by radiation cooling over the eastern North Pacific. Moreover, in the real atmosphere such individual thermal forcing is well organized. By considering the different diabatic heating in synthesis, a quadruple heating pattern is found over each subtropical continent and its adjacent oceans in summer. A distinct circulation pattern accompanies this heating pattern. The global summer subtropical heating and circulation may be viewed as "mosaics" of such quadruplet heating and circulation patterns respectively. At last, some important issues for further research in understanding and predicting the variations of the subtropical anticyclone are raised.

  2. Formation of residual nuclei with medium mass number in the reaction of protons with separated tin isotopes

    CERN Document Server

    Aleksandryan, V E; Balabekyan, A R; Danagulyan, A S; Kalinnikov, V G; Musulmanbekov, G; Rodionov, V K; Stegailov, V I; Frana, J

    2000-01-01

    The mechanism of formation of residual nuclei in the mass region 42<=A<=81 in the reactions of protons with separated tin isotopes at three protons energies 0.66, 1.0 and 8.1 GeV was investigated. The absolute cross-sections of the residual nuclei were compared with the theoretical ones calculated by the standard cascade-evaporation and the intranuclear cascad plus statistical multifragmentation models (INC+SMM). It was shown that at E sub p =8.1 GeV these nuclei may arise both from disintegration of the nucleus and as partners of several fragments.

  3. Modelling reaction front formation and oscillatory behaviour in a contaminant plume

    Science.gov (United States)

    Cribbin, Laura; Fowler, Andrew; Mitchell, Sarah; Winstanley, Henry

    2013-04-01

    Groundwater contamination is a concern in all industrialised countries that suffer countless spills and leaks of various contaminants. Often, the contaminated groundwater forms a plume that, under the influences of regional groundwater flow, could eventually migrate to streams or wells. This can have catastrophic consequences for human health and local wildlife. The process known as bioremediation removes pollutants in the contaminated groundwater through bacterial reactions. Microorganisms can transform the contaminant into less harmful metabolic products. It is important to be able to predict whether such bioremediation will be sufficient for the safe clean-up of a plume before it reaches wells or lakes. Borehole data from a contaminant plume which resulted from spillage at a coal carbonisation plant in Mansfield, England is the motivation behind modelling the properties of a contaminant plume. In the upper part of the plume, oxygen is consumed and a nitrate spike forms. Deep inside the plume, nitrate is depleted and oscillations of organic carbon and ammonium concentration profiles are observed. While there are various numerical models that predict the evolution of a contaminant plume, we aim to create a simplified model that captures the fundamental characteristics of the plume while being comparable in accuracy to the detailed numerical models that currently exist. To model the transport of a contaminant, we consider the redox reactions that occur in groundwater systems. These reactions deplete the contaminant while creating zones of dominant terminal electron accepting processes throughout the plume. The contaminant is depleted by a series of terminal electron acceptors, the order of which is typically oxygen, nitrate, manganese, iron, sulphate and carbon dioxide. We describe a reaction front, characteristic of a redox zone, by means of rapid reaction and slow diffusion. This aids in describing the depletion of oxygen in the upper part of the plume. To

  4. Glycation of human cortical and cancellous bone captures differences in the formation of Maillard reaction products between glucose and ribose.

    Science.gov (United States)

    Sroga, Grażyna E; Siddula, Alankrita; Vashishth, Deepak

    2015-01-01

    To better understand some aspects of bone matrix glycation, we used an in vitro glycation approach. Within two weeks, our glycation procedures led to the formation of advanced glycation end products (AGEs) at the levels that corresponded to approx. 25-30 years of the natural in vivo glycation. Cortical and cancellous bones from human tibias were glycated in vitro using either glucose (glucosylation) or ribose (ribosylation). Both glucosylation and ribosylation led to the formation of higher levels of AGEs and pentosidine (PEN) in cancellous than cortical bone dissected from all tested donors (young, middle-age and elderly men and women). More efficient glycation of bone matrix proteins in cancellous bone most likely depended on the higher porosity of this tissue, which facilitated better accessibility of the sugars to the matrix proteins. Notably, glycation of cortical bone from older donors led to much higher AGEs levels as compared to young donors. Such efficient in vitro glycation of older cortical bone could result from aging-related increase in porosity caused by the loss of mineral content. In addition, more pronounced glycation in vivo would be driven by elevated oxidation processes. Interestingly, the levels of PEN formation differed pronouncedly between glucosylation and ribosylation. Ribosylation generated very high levels of PEN (approx. 6- vs. 2.5-fold higher PEN level than in glucosylated samples). Kinetic studies of AGEs and PEN formation in human cortical and cancellous bone matrix confirmed higher accumulation of fluorescent crosslinks for ribosylation. Our results suggest that in vitro glycation of bone using glucose leads to the formation of lower levels of AGEs including PEN, whereas ribosylation appears to support a pathway toward PEN formation. Our studies may help to understand differences in the progression of bone pathologies related to protein glycation by different sugars, and raise awareness for excessive sugar supplementation in food and

  5. Thiamine inhibits formation of dityrosine, a specific marker of oxidative injury, in reactions catalyzed by oxoferryl forms of hemoglobin.

    Science.gov (United States)

    Stepuro, A I; Adamchuk, R I; Oparin, A Yu; Stepuro, I I

    2008-09-01

    Effects of thiamine and its derivatives on inhibition of dityrosine formation were studied in reactions catalyzed by oxoferryl forms of hemoglobin. At high thiamine concentrations, a complete inhibition of dityrosine formation was observed due to interaction of tyrosyl radicals with thiamine tricyclic and thiol forms. In neutral and alkaline media, tyrosyl radicals oxidized thiamine to thiochrome, oxodihydrothiochrome, and thiamine disulfide. In the absence of tyrosine, oxoferryl forms of hemoglobin manifested peroxidase activity towards thiamine and its phosphate esters by inducing their oxidation to disulfide compounds, thiochrome, oxodihydrothiochrome, and their phosphate esters, respectively, in neutral media. Thiamine and its phosphate esters were oxidized by both oxoferryl forms of hemoglobin, viz., +*Hb(IV=O) (compound I with an additional radical on the globin) and Hb(IV=O) (compound II). Putative mechanisms of thiamine conversions under oxidative stress and the protective role of hydrophobic thiamine metabolites are discussed.

  6. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  7. Formation of a necklike structure in 35Cl+12C and 197Au reactions at 43 MeV/nucleon

    Science.gov (United States)

    Larochelle, Y.; Gingras, L.; Beaulieu, L.; Qian, X.; Saddiki, Z.; Djerroud, B.; Doré, D.; Laforest, R.; Roy, R.; Samri, M.; St-Pierre, C.; Ball, G. C.; Bowman, D. R.; Galindo-Uribarri, A.; Hagberg, E.; Horn, D.; López, J. A.; Robinson, T.

    1997-04-01

    The experimental signature of the formation of a necklike structure, with a velocity between that of the projectilelike emitter and that of the targetlike emitter, is investigated with the same beam and experimental setup for targets lighter and heavier than the projectile. The reactions are 35Cl on 12C and on 197Au at 43 MeV/nucleon. Particle velocity distributions are compared with two-source statistical simulations and the presence of a necklike structure is inferred from the data. In the second part of the paper, dynamical model simulations with the formation of a necklike structure are presented for the 35Cl+12C system at 43 MeV/nucleon.

  8. Entrance-channel Mass-asymmetry Dependence of Compound-nucleus Formation Time in Light Heavy-ion Reactions

    CERN Document Server

    Szanto de Toledo, A; Beck, C; Thoennessen, M

    1996-01-01

    The entrance-channel mass-asymmetry dependence of the compound nucleus formation time in light heavy-ion reactions has been investigated within the framework of semiclassical dissipative collision models. the model calculations have been succesfully applied to the formation of the $^{38}$Ar compound nucleus as populated via the $^{9}$Be+$^{29}$Si, $^{11}$B+$^{27}$Al, $^{12}$C+$^{26}$Mg and $^{19}$F+$^{19}$F entrance channels. The shape evolution of several other light composite systems appears to be consistent with the so-called "Fusion Inhibition Factor" which has been experimentally observed. As found previously in more massive systems for the fusion-evaporation process, the entrance-channel mass-asymmetry degree of freedom appears to determine the competition between the different mechanisms as well as the time scales involved.

  9. Effect of roasting time of buckwheat groats on the formation of Maillard reaction products and antioxidant capacity.

    Science.gov (United States)

    Małgorzata, Wronkowska; Konrad, Piskuła Mariusz; Zieliński, Henryk

    2016-04-01

    Changes in the formation of Maillard reaction products and antioxidant capacity of buckwheat, induced by roasting at 160 °C for 30, 40 and 50 min, were evaluated in the study. Furozine, was detected after roasting, in all buckwheat samples. Increase of FIC, the presence of significant amounts of CML and enhanced browning were observed, along with increasing times of roasting. The formation of acrylamide in the obtained buckwheat products was also significantly connected with the time of roasting. A significant degradation was observed in natural antioxidants, as affected by heat treatment time. The colour parameter changed significantly with the increasing of roasting time. Overall, 30min of roasting was beneficial from a nutritional point of view for the obtained buckwheat product.

  10. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  11. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    Science.gov (United States)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  12. EVIDENCE BASED PROGRESSIVE CORE STABILIZATION EXERCISE FORMATION FOR LOW CORE ENDURANCE INDIVIDUALS

    Directory of Open Access Journals (Sweden)

    Kulandaivelan.S

    2014-06-01

    Full Text Available Low back pain (LBP is the commonest pain among individuals affecting more than half of the population. Segmental stabilization exercises gaining popularity among many treatment choices available to the therapist. Transverses abdominis (TA and Multifidi (MF are the two core muscles that were affected by LBP. This descriptive partial review study examines how various exercises recruits TA and MF? Then how do one to prognoses them progressively over short period of time? And what is the dose, volume needed? This review put an attempt to solve the above questions based on recent evidence based practice. Finally we have given exercise schedule for physiotherapists to follow.

  13. The effect of reactions on the formation and readout of the gradient of Bicoid

    CERN Document Server

    Ipiña, Emiliano Perez

    2016-01-01

    During early development, the establishment of gradients of transcriptional factors determines the patterning of cell fates. The case of Bicoid (Bcd) in {\\it Drosophila melanogaster} embryos is well documented and studied. There are still controversies as to whether {\\it SDD} models in which Bcd is {\\it Synthesized} at one end, then {\\it Diffuses} and is {\\it Degraded} can explain the gradient formation within the timescale observed experimentally. The Bcd gradient is observed in embryos that express a Bicoid-eGFP fusion protein (Bcd-GFP) which cannot differentiate if Bcd is freely diffusing or bound to immobile sites. In this work we analyze an {\\it SDID} model that includes the {\\it Interaction} of Bcd with binding sites. Using previously determined biophysical parameters we find that this model can explain the gradient formation within the experimentally observed time. Analyzing the differences between the free and bound Bcd distributions we observe that the latter spans over a longer lengthscale. We concl...

  14. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, O-okayama Meguroku, Tokyo, 152-8550 (Japan)

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  15. Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

    Science.gov (United States)

    Frenklach, M.; Clary, D. W.; Gardiner, W. C., Jr.; Stein, S. E.

    1986-01-01

    The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

  16. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    Science.gov (United States)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  17. Progressive star formation in the young galactic super star cluster NGC 3603

    CERN Document Server

    Beccari, Giacomo; De Marchi, Guido; Paresce, Francesco; Young, Erick; Andersen, Morten; Panagia, Nino; Balick, Bruce; Bond, Howard; Calzetti, Daniela; Carollo, C Marcella; Disney, Michael J; Dopita, Michael A; Frogel, Jay A; Hall, Donald N B; Holtzman, Jon A; Kimble, Randy A; McCarthy, Patrick J; O'Connell, Robert W; Saha, Abhijit; Silk, Joseph I; Trauger, John T; Walker, Alistair R; Whitmore, Bradley C; Windhorst, Rogier A

    2010-01-01

    Early release science observations of the cluster NGC3603 with the WFC3 on the refurbished HST allow us to study its recent star formation history. Our analysis focuses on stars with Halpha excess emission, a robust indicator of their pre-main sequence (PMS) accreting status. The comparison with theoretical PMS isochrones shows that 2/3 of the objects with Halpha excess emission have ages from 1 to 10 Myr, with a median value of 3 Myr, while a surprising 1/3 of them are older than 10 Myr. The study of the spatial distribution of these PMS stars allows us to confirm their cluster membership and to statistically separate them from field stars. This result establishes unambiguously for the first time that star formation in and around the cluster has been ongoing for at least 10-20 Myr, at an apparently increasing rate.

  18. Acetonitrile and N-Chloroacetamide Formation from the Reaction of Acetaldehyde and Monochloramine.

    Science.gov (United States)

    Kimura, Susana Y; Vu, Trang Nha; Komaki, Yukako; Plewa, Michael J; Mariñas, Benito J

    2015-08-18

    Nitriles and amides are two classes of nitrogenous disinfection byproducts (DBPs) associated with chloramination that are more cytotoxic and genotoxic than regulated DBPs. Monochloramine reacts with acetaldehyde, a common ozone and free chlorine disinfection byproduct, to form 1-(chloroamino)ethanol. Equilibrium (K1) and forward and reverse rate (k1,k-1) constants for the reaction between initial reactants and 1-(chloroamino)ethanol were determined between 2 and 30 °C. Activation energies for k1 and k-1 were 3.04 and 45.2 kJ·mol(-1), respectively, and enthalpy change for K1 was -42.1 kJ·mol(-1). In parallel reactions, 1-(chloroamino)ethanol (1) slowly dehydrated (k2) to (chloroimino)ethane that further decomposed to acetonitrile and (2) was oxidized (k3) by monochloramine to produce N-chloroacetamide. Both reactions were acid/base catalyzed, and rate constants were characterized at 10, 18, and 25 °C. Modeling for drinking water distribution system conditions showed that N-chloroacetamide and acetonitrile concentrations were 5-9 times higher at pH 9.0 compared to 7.8. Furthermore, acetonitrile concentration was found to form 7-10 times higher than N-chloroacetamide under typical monochloramine and acetaldehyde concentrations. N-chloroacetamide cytotoxicity (LC50 = 1.78 × 10(-3) M) was comparable to dichloroacetamide and trichloroacetamide, but less potent than N,2-dichloroacetamide and chloroacetamide. While N-chloroacetamide was not found to be genotoxic, N,2-dichloroacetamide genotoxic potency (5.19 × 10(-3) M) was on the same order of magnitude as chloroacetamide and trichloroacetamide.

  19. Antioxidants Inhibit Formation of 3-Monochloropropane-1,2-diol Esters in Model Reactions.

    Science.gov (United States)

    Li, Chang; Jia, Hanbing; Shen, Mingyue; Wang, Yuting; Nie, Shaoping; Chen, Yi; Zhou, Yongqiang; Wang, Yuanxing; Xie, Mingyong

    2015-11-11

    The capacities of six antioxidants to inhibit the formation of 3-monochloropropane-1,2 diol (3-MCPD) esters were examined in this study. Inhibitory capacities of the antioxidants were investigated both in chemical models containing the precursors (tripalmitoyl glycerol, 1,2-dipalmitoyl-sn-glycerol, monopalmitoyl glycerol, and sodium chloride) of 3-MCPD esters and in oil models (rapeseed oil and sodium chloride). Six antioxidants, butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), L-ascorbyl palmitate (AP), and α-tocopherol (VE), were found to exhibit inhibiting capacities on 3-MCPD ester formation both in chemical models and in oil models. TBHQ provided the highest inhibitory capacity both in chemical models and in oil models; 44% of 3-MCPD ester formation was inhibited in the presence of TBHQ (66 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min, followed by PG and AP. BHT, BHA, and VE appeared to have weaker inhibitory abilities in both models. VE exhibited the lowest inhibition rate; 22% of 3-MCPD esters were inhibited in the presence of VE (172 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min. In addition, the inhibition rates of PG and VE decreased dramatically with an increase in temperature or heating time. The results suggested that some antioxidants, such as TBHQ, PG, and AP, could be the potential inhibitors of 3-MCPD esters in practice.

  20. The Wnt11 Signaling Pathway in Potential Cellular EMT and Osteochondral Differentiation Progression in Nephrolithiasis Formation

    OpenAIRE

    Deng He; Yuchao Lu; Henglong Hu; Jiaqiao Zhang; Baolong Qin; Yufeng Wang; Shuai Xing; Qilin Xi; Shaogang Wang

    2015-01-01

    The molecular events leading to nephrolithiasis are extremely complex. Previous studies demonstrated that calcium and transforming growth factor-β1 (TGF-β1) may participate in the pathogenesis of stone formation, but the explicit mechanism has not been defined. Using a self-created genetic hypercalciuric stone-forming (GHS) rat model, we observed that the increased level of serous/uric TGF-β1 and elevated intracellular calcium in primary renal tubular epithelial cells (PRECs) was associated...

  1. Formation and densification of SiAlON materials by reaction bonding and silicothermal reduction routes

    Science.gov (United States)

    Rouquié, Yann; Jones, Mark I.

    2011-05-01

    Samples of β and O-sialon with different levels of substitution (i.e. z = 1 and 4 for β-sialon and x = 0.05 and 0.2 for O-sialon) have been synthesized by both reaction bonding and silicothermal reduction techniques in a nitrogen atmosphere. The possibility of obtaining dense sialon materials by these lower cost production methods has been investigated using a statistical design methodology. The influence of different parameters (temperature, gas pressure and additive type) on the densification and decomposition has been studied and will be discussed in this presentation.

  2. Formation and densification of SiAlON materials by reaction bonding and silicothermal reduction routes

    Energy Technology Data Exchange (ETDEWEB)

    Rouquie, Yann; Jones, Mark I, E-mail: yrou002@aucklanduni.ac.nz [Department of Material and Chemicals Engineering, University of Auckland, New Zealand Private bag 92019, Auckland Mail Center, Auckland, 1142 (New Zealand)

    2011-05-15

    Samples of {beta} and O-sialon with different levels of substitution (i.e. z = 1 and 4 for {beta}-sialon and x = 0.05 and 0.2 for O-sialon) have been synthesized by both reaction bonding and silicothermal reduction techniques in a nitrogen atmosphere. The possibility of obtaining dense sialon materials by these lower cost production methods has been investigated using a statistical design methodology. The influence of different parameters (temperature, gas pressure and additive type) on the densification and decomposition has been studied and will be discussed in this presentation.

  3. Pattern formation in reaction-diffusion systems: From spiral waves to turbulence

    Science.gov (United States)

    Davidsen, Joern

    2009-05-01

    Almost all systems we encounter in nature possess some sort of form or structure. In many cases, the structures arise from an initially unstructured state without the action of an agent that predetermines the pattern. Such self-organized structures emerge from cooperative interactions among the constituents of the system and often exhibit properties that are distinct from those of their constituent elements or molecules. For example, chemical waves in reaction-diffusion systems are at the core of a huge variety of physical, chemical, and biological processes. In (quasi) two-dimensional situations, spiral wave patterns are especially prevalent and determine the characteristics of processes such as surface catalytic oxidation reactions, contraction of the heart muscle, and various signaling mechanisms in biological systems. In this talk, I will review and discuss recent theoretical and experimental results regarding the dynamics, properties and stability of spiral waves and their three-dimensional analog (scroll waves). Special emphasis will be given to synchronization defect lines which generically arise in complex-oscillatory media, and the phenomenon of defect-mediated turbulence or filament turbulence where the dynamics of a pattern is dominated by the rapid motion, nucleation, and annihilation of spirals or scroll waves, respectively. The latter is of direct relevance in the context of ventricular fibrillation - a turbulent electrical wave activity that destroys the coherent contraction of the ventricular muscle and its main pumping function leading to sudden cardiac death.

  4. Development of a reduced model of formation reactions in Zr-Al nanolaminates

    KAUST Repository

    Vohra, Manav

    2014-12-15

    A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

  5. Reaction kinetics of CuGaSe 2 formation from a GaSe/CuSe bilayer precursor film

    Science.gov (United States)

    Kim, W. K.; Payzant, E. A.; Kim, S.; Speakman, S. A.; Crisalle, O. D.; Anderson, T. J.

    2008-06-01

    The reaction pathway and kinetics of CuGaSe 2 formation were investigated by monitoring the phase evolution of temperature ramp annealed or isothermally soaked bilayer glass/GaSe/CuSe precursor film using time-resolved, in situ high-temperature X-ray diffraction. Bilayer GaSe/CuSe precursor films were deposited on alkali-free thin glass substrates in a migration-enhanced epitaxial deposition system. The initial CuSe phase begins to transform to β-Cu 2-xSe at around 230 °C, followed by CuGaSe 2 formation accompanied by a decrease in the β-Cu 2-xSe peak intensity at around 260 °C. Both the parabolic and Avrami diffusion-controlled reaction models represented the experimental data very well over the entire temperature range (280-370 °C) of the set of isothermal experiments with estimated activation energies of 115(±16) and 124(±19) kJ/mol, respectively. Transmission electron microscopy-energy-dispersive X-ray spectrometry (TEM-EDS) analysis suggests that CuGaSe 2 forms at the interface of the initial GaSe and CuSe layers.

  6. Relationship between Latent Aggression, Inflated Responsibility, Guilt Feeling and Reaction Formation with Severity of Obsessive-Compulsive Symptoms

    Directory of Open Access Journals (Sweden)

    Masoud Mohammadi

    2012-09-01

    Full Text Available Background: This research aims to study previous findings about interpersonal ambivalence in people with obsessive compulsive disorders that shows itself as hidden aggression, excessive responsibility, feelings of guilt, and reverse reaction formations. Materials and Methods: In this correlational study, 60 individuals (33 women and 27 men with obsessive-compulsive disorders who were referred to psychologists' offices and clinics of the city of Shiraz were selected through available sampling. Participants completed the Padua Inventory, Spielberger’s State-Trait Anger Inventory, the Responsibility Attitude Scale, the Guilt Inventory, and the Defense Mechanisms Inventory. SPSS-16 software was used to analyze the data.Results: The results showed that the Pearson correlation coefficient was significant between excessive responsibility, hidden aggression, feelings of guilt, and reverse reaction formations with the severity of obsessive-compulsive symptoms. Based on the results of the regression analysis, feelings of guilt were the strongest predictor of obsessive-compulsive symptoms (β=0.388. Also, the results of path analysis suggest that hidden aggression had predicted feelings of guilt (β=0.47, which was also a predictor of excessive responsibility (β=0.30.Conclusion: According to the results, it seems that a high interpersonal ambivalence exists among people with obsessive-compulsive disorders. Therefore, this structure has the eligibility to be considered in research, especially in the treatment.

  7. The gas phase reaction of ozone with 1,3-butadiene: formation yields of some toxic products

    Science.gov (United States)

    Kramp, Franz; Paulson, Suzanne E.

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separate experiments, small quantities of 1,3,5-trimethyl benzene were added as a tracer for OH. Formation yields of acrolein of (52±7)%, 1,2-epoxy-3-butene of (3.1±0.5)% and OH radicals of (13±3)% were observed. In addition, the rate coefficient of the gas-phase reaction of ozone with 1,2-epoxy-3-butene was measured both directly and relative to propene, finding an average of (1.6±0.4)×10 -18 cm 3 molecule -1 s -1, respectively, at 296±2 K. The results are briefly discussed in terms of the effect of atmospheric processing on the toxicity of 1,3-butadiene.

  8. Chloroacetonitrile and n,2-dichloroacetamide formation from the reaction of chloroacetaldehyde and monochloramine in water.

    Science.gov (United States)

    Kimura, Susana Y; Komaki, Yukako; Plewa, Michael J; Mariñas, Benito J

    2013-01-01

    Combined chlorine is increasingly being used as an alternative disinfectant to free chlorine to maintain a residual in drinking water distribution systems mainly because it would reduce the formation of regulated disinfection byproducts (DBPs) trihalomethanes and haloacetic acids. However, the use of combined chlorine could promote the formation of currently unregulated nitrogenous DBPs (N-DBPs) such as haloacetonitriles and haloacetamides that are found to be more cyto- and genotoxic than regulated DBPs. Monochloramine quickly reacts with chloroacetaldehyde, a DBP formed during primary disinfection with free chlorine, forming and reaching pseudoequilibrium (equilibrium constant K1 = 1.87 × 10(3) M(-1)) with the carbinolamine 2-chloro-1-(chloroamino)ethanol. 2-Chloro-1-(chloroamino)ethanol undergoes slow dehydration to form the imine 1-chloro-2-(chloroimino)ethane that decomposes at a faster rate to chloroacetonitrile. 2-Chloro-1-(chloroamino)ethanol is also oxidized by monochloramine to produce the previously unreported DBP N,2-dichloroacetamide. The carbinolamine dehydration step was found to be acid/base catalyzed (k2(0) = 3.30 × 10(-6) s(-1), k2(H) = 2.43 M(-1) s(-1), k2(OH) = 3.90 M(-1) s(-1)). In contrast, N,2-dichloroacetamide formation was observed to be only base catalyzed (k3(OH) = 3.03 × 10(4) M(-2) s(-1)). N,2-dichloroacetamide cytotoxicity (LC50 = 2.56 × 10(-4) M) was found to be slightly lower compared to that reported for chloroacetamide but higher than those of di- and trichloroacetamide.

  9. Formation of amorphous Ti-50at.%Pt by solid state reactions during mechanical alloying

    CSIR Research Space (South Africa)

    Mahlatji, ML

    2013-10-01

    Full Text Available , and the formation of a nanocrystalline parent austenite phase, which has been shown to have a weakening effect on the martensite transformation (Waitz and Karnthaler, 2004; Guimaraes, 2007). It is generally accepted that this is due to the increasing difficulty... nanocrystalline B2-austenite parent phase. Experimental methods Mechanical alloying Elemental powders of commercially pure Ti and Pt were mixed in a 1:1 atomic ratio. The Ti particles were spherical and the Pt particles were spongy and irregular (Figure 3). MA...

  10. Formation and reactions of free radicals in the radiolysis of organic materials by ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Koizumi, H. [Hokkaido Univ., Division of Molecular Chemistry, Sapporo, Hokkaido (Japan)

    2000-03-01

    High-energy heavy ions deposit energy along ion tracks with high density. Chemical effects of the heavy ions may hence differ from that of {gamma}-rays and fast electrons. We can utilize these effects for material modification and fabrication of microstructure. It is necessary to know the dependence of the effects on ion beams and the variation of the effects on materials for developing new application of ion beams. We then studied radical formation in organic solids of alanine and of adipic acid by ion beams irradiation. (author)

  11. [Research progress in biofilm formation and regulatory mechanism of Campylobacter jejuni].

    Science.gov (United States)

    Wu, Qingping; Zhong, Xian; Zhang, Jumei

    2016-02-04

    Biofilm of Campylobacter jejuni was formed by cross-linking its extracellular secretion, polysaccharides, various extracellular proteins, nucleic acids etc to enhance its survival in hostile environments, especially for detergents, antibiotics and disinfectants. This paper elaborated C. jejuni biofilm formation and regulation mechanisms in the surface properties of the media, temperatures, gas environment, the regulation of gene etc, also analysed and discussed a variety of biofilm removal practical applications. We hope it can provide a reference for studies on biofilm control of C. jejuni.

  12. Formation of PdHg by reaction of palladium thin film contacts deposited onto mercuric iodide ({alpha}-HgI{sub 2}) radiation detector crystals

    Energy Technology Data Exchange (ETDEWEB)

    Medlin, D.L. [Sandia National Labs., Livermore, CA (United States); Van Scyoc, J.M. [Carnegie-Mellon Univ., Pittsburgh, PA (United States). Dept. of Electrical and Computer Engineering; Gilbert, T.S. [Carnegie-Mellon Univ., Pittsburgh, PA (United States). Dept. of Electrical and Computer Engineering; Schlesinger, T.E. [Carnegie-Mellon Univ., Pittsburgh, PA (United States). Dept. of Electrical and Computer Engineering; Boehme, D. [Sandia National Labs., Livermore, CA (United States); Schieber, M. [Sandia National Labs., Livermore, CA (United States); Natarajan, M. [TN Technologies, Inc., Round Rock, TX (United States); James, R.B. [Sandia National Labs., Livermore, CA (United States)

    1996-10-01

    The microstructure and phase distribution of palladium thin films sputter deposited onto {alpha}-HgI{sub 2} for use as electrical contacts in radiation detectors are investigated using electron microscopy. Our results show a limited reaction to form palladium mercuride (PdHg). It is shown that the formation of PdHg via several reaction pathways is thermodynamically feasible. (orig.).

  13. Reaction of dimethyl ether with hydroxyl radicals: kinetic isotope effect and prereactive complex formation.

    Science.gov (United States)

    Bänsch, Cornelie; Kiecherer, Johannes; Szöri, Milan; Olzmann, Matthias

    2013-09-05

    The kinetic isotope effect of the reactions OH + CH3OCH3 (DME) and OH + CD3OCD3 (DME-d6) was experimentally and theoretically studied. Experiments were carried out in a slow-flow reactor at pressures between 5 and 21 bar (helium as bath gas) with production of OH by laser flash photolysis of HNO3 and time-resolved detection of OH by laser-induced fluorescence. The temperature dependences of the rate coefficients obtained can be described by the following modified Arrhenius expressions: k(OH+DME) = (4.5 ± 1.3) × 10(-16) (T/K)(1.48) exp(66.6 K/T) cm(3) s(-1) (T = 292-650 K, P = 5.9-20.9 bar) and k(OH+DME-d6) = (7.3 ± 2.2) × 10(-23) (T/K)(3.57) exp(759.8 K/T) cm(3) s(-1) (T = 387-554 K, P = 13.0-20.4 bar). A pressure dependence of the rate coefficients was not observed. The agreement of our experimental results for k(OH+DME) with values from other authors is very good, and from a fit to all available literature data, we derived the following modified Arrhenius expression, which reproduces the values obtained in the temperature range T = 230-1500 K at pressures between 30 mbar and 21 bar to better than within ±20%: k(OH+DME) = 8.45 × 10(-18) (T/K)(2.07) exp(262.2 K/T) cm(3) s(-1). For k(OH+DME-d6), to the best of our knowledge, this is the first experimental study. For the analysis of the reaction pathway and the kinetic isotope effect, potential energy diagrams were calculated by using three different quantum chemical methods: (I) CCSD(T)/cc-pV(T,Q)Z//MP2/6-311G(d,p), (II) CCSD(T)/cc-pV(T,Q)Z//CCSD/cc-pVDZ, and (III) CBS-QB3. In all three cases, the reaction is predicted to proceed via a prereaction OH-ether complex with subsequent intramolecular hydrogen abstraction and dissociation to give the methoxymethyl radical and water. Overall rate coefficients were calculated by assuming a thermal equilibrium between the reactants and the prereaction complex and by calculating the rate coefficients of the hydrogen abstraction step from canonical transition state theory

  14. Scenarios of domain pattern formation in a reaction-diffusion system

    CERN Document Server

    Muratov, C B

    1996-01-01

    We performed an extensive numerical study of a two-dimensional reaction-diffusion system of the activator-inhibitor type in which domain patterns can form. We showed that both multidomain and labyrinthine patterns may form spontaneously as a result of Turing instability. In the stable homogeneous system with the fast inhibitor one can excite both localized and extended patterns by applying a localized stimulus. Depending on the parameters and the excitation level of the system stripes, spots, wriggled stripes, or labyrinthine patterns form. The labyrinthine patterns may be both connected and disconnected. In the the stable homogeneous system with the slow inhibitor one can excite self-replicating spots, breathing patterns, autowaves and turbulence. The parameter regions in which different types of patterns are realized are explained on the basis of the asymptotic theory of instabilities for patterns with sharp interfaces developed by us in Phys. Rev. E. 53, 3101 (1996). The dynamics of the patterns observed i...

  15. The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NOx

    Directory of Open Access Journals (Sweden)

    M. Jaoui

    2009-04-01

    Full Text Available The reaction of isoprene (C5H8 with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔHvapeff, the organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols were found to form in the absence of acidic sulfate aerosol. A re-evaluation of field samples in Research Triangle Park, North Carolina, during the summers of 2000 and 2001 indicated in the presence of the methyl butenediols from gas-phase denuder samples taken at the time. SOA/SOC (i.e., OM/OC was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol−1, consistent with values that have previously been used in modeling studies. The yields in this work (using an independent technique than that previous are lower than those of Kroll et al. (2006 for similar aerosol masses. SOC yields reported in this work range from 0.5–1.4% for carbon masses between 17 and 49 μgC m−3.

  16. DNA damage and radical reactions: Mechanistic aspects, formation in cells and repair studies

    Energy Technology Data Exchange (ETDEWEB)

    Cadet, J.; Ravanat, J.L. [CEA Grenoble, Inst Nanosci and Cryogenie, SCIB-UMR-E 3, Lab Les Acides Nucl, UJF, F-38054 Grenoble 9 (France); Carell, T. [Univ Munich, Dept Chem and Biochem, Ctr Integrat Prot Sci, D-81377 Munich (Germany); Cellai, L. [CNR, Ist Cristalog, Monterotondo Stn, I-00016 Rome (Italy); Chatgilialoglu, Ch. [CNR, ISOF, I-40129 Bologna, (Italy); Gimisis, Th. [Univ Athens, Dept Chem, Organ Chem Lab, Athens 15784, (Greece); Miranda, M. [Univ Politecn Valencia, Inst Technol Quim, Dept Quim, Valencia 46022 (Spain); O' Neill, P. [Univ Oxford, Oxford OX3 7DQ (United Kingdom); Robert, M. [Univ Paris 07, CNRS, UMR 7591, Electrochim Mol Lab, F-75251 Paris 05 (France)

    2008-07-01

    Several examples of oxidative and reductive reactions of DNA components that lead to single and tandem modifications are discussed in this review. These include nucleophilic addition reactions of the one-electron oxidation-mediated guanine radical cation and the one-electron reduced intermediate of 8-bromo-purine 2'-de-oxy-ribo-nucleosides that give rise to either an oxidizing guanine radical or related 5',8-cyclo-purine nucleosides. In addition, mechanistic insights into the reductive pathways involved in the photolyase induced reversal of cyclo-buta-cli-pyrimidine and pyrimidine (6-4) pyrimidone photoproducts are provided. Evidence for the occurrence and validation in cellular DNA of (OH){sup {center_dot}} radical degradation pathways of guanine that have been established in model systems has been gained from the accurate measurement of degradation products. Relevant information on biochemical aspects of the repair of single and clustered oxidatively generated damage to DNA has been gained from detailed investigations that rely on the synthesis of suitable modified probes. Thus the preparation of stable carbocyclic derivatives of purine nucleoside containing defined sequence oligonucleotides has allowed detailed crystallographic studies of the recognition step of the base damage by enzymes implicated in the base excision repair (BER) pathway. Detailed insights are provided on the BER processing of non-double strand break bi-stranded clustered damage that may consist of base lesions, a single strand break or abasic sites and represent one of the main deleterious classes of radiation-induced DNA damage. (authors)

  17. Progressive mechanical indentation of large-format Li-ion cells

    Science.gov (United States)

    Wang, Hsin; Kumar, Abhishek; Simunovic, Srdjan; Allu, Srikanth; Kalnaus, Sergiy; Turner, John A.; Helmers, Jacob C.; Rules, Evan T.; Winchester, Clinton S.; Gorney, Philip

    2017-02-01

    Large format Li-ion cells were used to study the mechanical responses of single cells of thickness 6.5 mm and stacks of three cells under compressive loading. Various sequences of increasing depth indentations were carried out using a 1.0 inch (25.4 mm) diameter steel ball with steel plate as a rigid support surface. The indentation depths were between 0.025″ and 0.250″ with main indentation increments tests of 0.025″ steps. Increment steps of 0.100″ and 0.005″ were used to pinpoint the onset of internal-short that occurred between 0.245″ and 0.250″. The indented cells were disassembled and inspected for internal damage. Load vs. time curves were compared with the developed computer models. Separator thinning leading to the short circuit was simulated using both isotropic and anisotropic mechanical properties. Our study show that separators behave differently when tested as a single layer vs. a stack in a typical pouch cell. The collective responses of the multiple layers must be taken into account in failure analysis. A model that resolves the details of the individual internal cell components was able to simulate the internal deformation of the large format cells and the onset of failure assumed to coincide with the onset of internal short circuit.

  18. Casein Kinase Iγ2 Impairs Fibroblasts Actin Stress Fibers Formation and Delays Cell Cycle Progression in G1

    Directory of Open Access Journals (Sweden)

    Mathieu Latreille

    2012-01-01

    Full Text Available Actin cytoskeleton remodeling is under the regulation of multiple proteins with various activities. Here, we demonstrate that the γ2 isoform of Casein Kinase I (CKIγ2 is part of a novel molecular path regulating the formation of actin stress fibers. We show that overexpression of CKIγ2 in fibroblasts alters cell morphology by impairing actin stress fibers formation. We demonstrate that this is concomitant with increased phosphorylation of the CDK inhibitor p27Kip and lower levels of activated RhoA, and is dependent on CKIγ2 catalytic activity. Moreover, we report that roscovitine, a potent inhibitor of cyclin-dependent kinases, including Cdk5, decreases p27Kip protein levels and restores actin stress fibers formation in CKIγ2 overexpressing cells, suggesting the existence of a CKIγ2-Cdk5-p27Kip-RhoA pathway in regulating actin remodeling. On the other hand, we also show that in a manner independent of its catalytic activity, CKIγ2 delays cell cycle progression through G1. Collectively our findings reveal that CKIγ2 is a novel player in the control of actin cytoskeleton dynamics and cell proliferation.

  19. A Reaction Method for Estimating Gibbs Energy and Enthalpy of Formation of Complex Minerals

    Science.gov (United States)

    Li, Ruibing; Zhang, Tingan; Liu, Yan; Kuang, Shibo

    2017-04-01

    New and updated thermodynamic data for simple binary compounds are readily available from both experimental measurements and theoretical calculations. Based on these available data, an approach is proposed to predict Gibbs energies and enthalpies of formation for complex minerals of metallurgical, chemical, and other industrial importance. The approach assumes that complex minerals are formed from binary composite oxides, which in turn, are formed from individual pure oxides. The validity of this approach is examined by comparing the calculated values of Gibbs energies and enthalpies against the experimentally measured ones reported in literature. The results show that for typical complex minerals with available experimental data, the calculated results exhibit an average residual of 0.51 pct for Gibbs energies and 0.52 pct for enthalpies, compared to the experimental results. This new approach thus correlates well with experimental approaches and can be applied to most of the complex minerals.

  20. Pathways of arachidonic acid peroxyl radical reactions and product formation with guanine radicals.

    Science.gov (United States)

    Crean, Conor; Geacintov, Nicholas E; Shafirovich, Vladimir

    2008-02-01

    Peroxyl radicals were derived from the one-electron oxidation of polyunsaturated fatty acids by sulfate radicals that were generated by the photodissociation of peroxodisulfate anions in air-equilibrated aqueous solutions. Reactions of these peroxyl and neutral guanine radicals, also generated by oxidation with sulfate radicals, were investigated by laser kinetic spectroscopy, and the guanine oxidation products were identified by HPLC and mass spectrometry methods. Sulfate radicals rapidly oxidize arachidonic (ArAc), linoleic (LnAc), and palmitoleic (PmAc) acids with similar rate constants, (2-4) x 10 (9) M (-1) s (-1). The C-centered radicals derived from the oxidation of ArAc and LnAc include nonconjugated Rn(.) ( approximately 80%) and conjugated bis-allylic Rba(.) ( approximately 20%) radicals. The latter were detectable in the absence of oxygen by their prominent, narrow absorption band at 280 nm. The Rn(.) radicals of ArAc (containing three bis-allylic sites) transform to the Rba(.) radicals via an intramolecular H-atom abstraction [rate constant (7.5 +/- 0.7) x 10 (4) s (-1)]. In contrast, the Rn(.) radicals of LnAc that contain only one bis-allylic site do not transform intramolecularly to the Rba(.) radicals. In the case of PmAc, which contains only one double bond, the Rba(.) radicals are not observed. The Rn(.) radicals of PmAc rapidly combine with oxygen with a rate constant of (3.8 +/- 0.4) x 10(9) M(-1) s(-1). The Rba(.) radicals of ArAc are less reactive and react with oxygen with a rate constant of (2.2 +/- 0.2) x 10 (8) M (-1) s (-1). The ArAc peroxyl radicals formed spontaneously eliminate superoxide radical anions [rate constant = (3.4 +/- 0.3) x 10 (4) M (-1) s (-1)]. The stable oxidative lesions derived from the 2',3',5'-tri- O-acetylguanosine or 2',3',5'-tri- O-acetyl-8-oxo-7,8-dihydroguanosine radicals and their subsequent reactions with ArAc peroxyl radicals were also investigated. The major products found were the 2,5-diamino-4 H

  1. Reaction Rind Formation in Mèlange in the Catalina Schist, California

    Science.gov (United States)

    Penniston-Dorland, S. C.; Bebout, G. E.; Sorensen, S. S.; Piccoli, P. M.; Walker, R. J.

    2011-12-01

    Reaction rinds between differing lithologies are commonly considered the result of fluid-assisted metasomatic alteration, however, enrichments in relatively fluid-immobile elements such as Cr and Ni seemingly reflect other processes such as volume strain or tectonic mixing. Eleven samples along a 30 cm traverse of an amphibolite grade block and its reaction rind adjacent to ultramafic-rich matrix, show dramatic change in mineral abundance and whole-rock major and trace element and Li isotope composition. Samples of the rind are enriched in whole-rock SiO2, K2O, Rb, Ba, Li, MgO, Cr, Ni, and also Os, Ir and Ru relative to samples of the block core, and are depleted in FeO, Al2O3, TiO2, CaO, and Zr. δ7LiL-SVEC ranges from -3 to +1% and the distribution of Li concentrations and δ7Li is consistent with diffusion on the scale of nearly the entire profile. FeO content of garnets in the rind is lower than that of garnets in the block core, reflecting whole-rock FeO concentrations, and suggesting garnet growth after the depletion in whole-rock FeO. Garnets in the rind show extensive pseudomorphing by decussate chlorite, suggesting post-garnet growth infiltration by H2O-rich fluid. Rind concentrations of Cr, Ni, Zr, Al2O3, TiO2, FeO, and possibly CaO, MgO, Na2O, and Sr can be most simply explained by mechanical mixing of mafic block with mèlange matrix. Such mixing cannot explain the increases in SiO2, K2O, Li, and Ba, and we propose that the concentrations of these elements in the rind reflect element mobility during relatively late-stage fluid infiltration. We propose an early episode of mechanical mixing during which mixing of material derived from the mafic block and mèlange matrix produced rind-like material which then accreted onto the basaltic block. Garnet growth in both the block core and the rind occurred after this mechanical mixing. Fluid infiltration in the rind occurred after peak metamorphism of the block, causing alteration of garnet to chlorite and the

  2. Kinetics and Mechanism for Formation of Olefin Complexes in the Reaction between Palladium(II) and Maleic Acid.

    Science.gov (United States)

    Shi, Tiesheng; Elding, Lars I.

    1998-10-19

    Complex formation between Pd(H(2)O)(4)(2+) and maleic acid (H(2)A) has been studied at 25 degrees C and 2.00 M ionic strength in acidic aqueous solution. Reaction takes place with 1:1 stoichiometry. The kinetics has been followed by use of stopped-flow spectrophotometry under pseudo-first-order conditions with maleic acid in excess. In the concentration ranges 0.01 C where, in addition, both steps contain contributions from parallel reactions. The amplitude of the first phase increases with increasing [H(2)A](tot) and with decreasing [H(+)]. Multiwavelength global analysis of the kinetic traces and the UV-vis spectral changes suggest that a monodentate oxygen-bonded hydrogen maleate complex, [Pd(H(2)O)(3)OOCCH=CHCOOH](+), B, with stability constant K(2) = 205 +/- 40 M(-)(1) is formed as an intermediate in this first step via two parallel reversible reactions in which Pd(H(2)O)(4)(2+) reacts with maleic acid and hydrogen maleate, respectively. In the following step, B --> C, slow intramolecular ring closure with a rate constant of 0.8 +/- 0.1 s(-)(1) at 25 degrees C gives the reaction product C, which is concluded to be a 4.5-membered olefin-carboxylato chelate complex on the basis of stoichiometry and UV-vis/NMR spectra. Parallel and irreversible attack by maleic acid and hydrogen maleate acting as olefins on the intermediate B also leads to formation of C. C is stable for at least 20 h for concentrations of

  3. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

    Science.gov (United States)

    Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

    2011-12-21

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  4. Pattern formation in a reaction-advection model with delay: a continuum approach to myxobacterial rippling

    Science.gov (United States)

    Börner, U.; Bär, M.

    2004-07-01

    Standing wave oscillations of the cell density (rippling) are observed in premature aggregates of developing myxobacteria. Recently the underlying pattern formation mechanism was shown to be based on the interplay between active cell motion and local interactions triggering reversals in the cells' direction of motion. The propagation of information through the system is mediated by the internal state of moving cells rather than by diffusible chemical signals. Discrete cellular automata and coupled-map lattices have been investigated earlier and indicate the importance of a minimum refractory period between subsequent reversals of a cell. In this paper we consider the continuum limit of the process, that yields a set of hyperbolic partial differential equations with a a single discrete time delay. The time delay corresponds to the duration of the mentioned refractory period of the cells. According to linear stability analysis a minimal time delay is required for a wave instability to occur. The results of the continuum model are in reasonable agreement with the findings in the discrete models adding credibility to the earlier studies.

  5. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

    Science.gov (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B

    2016-05-01

    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  6. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2

    Science.gov (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B.

    2016-05-01

    The anilide anion ( m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion ( m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion ( m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  7. A cell-regulatory mechanism involving feedback between contraction and tissue formation guides wound healing progression.

    Directory of Open Access Journals (Sweden)

    Clara Valero

    Full Text Available Wound healing is a process driven by cells. The ability of cells to sense mechanical stimuli from the extracellular matrix that surrounds them is used to regulate the forces that cells exert on the tissue. Stresses exerted by cells play a central role in wound contraction and have been broadly modelled. Traditionally, these stresses are assumed to be dependent on variables such as the extracellular matrix and cell or collagen densities. However, we postulate that cells are able to regulate the healing process through a mechanosensing mechanism regulated by the contraction that they exert. We propose that cells adjust the contraction level to determine the tissue functions regulating all main activities, such as proliferation, differentiation and matrix production. Hence, a closed-regulatory feedback loop is proposed between contraction and tissue formation. The model consists of a system of partial differential equations that simulates the evolution of fibroblasts, myofibroblasts, collagen and a generic growth factor, as well as the deformation of the extracellular matrix. This model is able to predict the wound healing outcome without requiring the addition of phenomenological laws to describe the time-dependent contraction evolution. We have reproduced two in vivo experiments to evaluate the predictive capacity of the model, and we conclude that there is feedback between the level of cell contraction and the tissue regenerated in the wound.

  8. CCL2 accelerates microglia-mediated Abeta oligomer formation and progression of neurocognitive dysfunction.

    Directory of Open Access Journals (Sweden)

    Tomomi Kiyota

    Full Text Available BACKGROUND: The linkages between neuroinflammation and Alzheimer's disease (AD pathogenesis are well established. What is not, however, is how specific immune pathways and proteins affect the disease. To this end, we previously demonstrated that transgenic over-expression of CCL2 enhanced microgliosis and induced diffuse amyloid plaque deposition in Tg2576 mice. This rodent model of AD expresses a Swedish beta-amyloid (Abeta precursor protein mutant. METHODOLOGY/PRINCIPAL FINDINGS: We now report that CCL2 transgene expression accelerates deficits in spatial and working memory and hippocampal synaptic transmission in beta-amyloid precursor protein (APP mice as early as 2-3 months of age. This is followed by increased numbers of microglia that are seen surrounding Abeta oligomers. CCL2 does not suppress Abeta degradation. Rather, CCL2 and tumor necrosis factor-alpha directly facilitated Abeta uptake, intracellular Abeta oligomerization, and protein secretion. CONCLUSIONS/SIGNIFICANCE: We posit that CCL2 facilitates Abeta oligomer formation in microglia and propose that such events accelerate memory dysfunction by affecting Abeta seeding in the brain.

  9. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  10. Formation of lead-aluminate ceramics: Reaction mechanisms in immobilizing the simulated lead sludge.

    Science.gov (United States)

    Lu, Xingwen; Shih, Kaimin

    2015-11-01

    We investigated a strategy of blending lead-laden sludge and an aluminum-rich precursor to reduce the release of hazardous lead from the stabilized end products. To quantify lead transformation and determine its incorporation behavior, PbO was used to simulate the lead-laden sludge fired with γ-Al2O3 by Pb/Al molar ratios of 1/2 and 1/12 at 600-1000 °C for 0.25-10 h. The sintered products were identified and quantified using Rietveld refinement analysis of X-ray diffraction data from the products generated under different conditions. The results indicated that the different crystallochemical incorporations of hazardous lead occurred through the formation of PbAl2O4 and PbAl12O19 in systems with Pb/Al ratios of 1/2 and 1/12, respectively. PbAl2O4 was observed as the only product phase at temperature of 950 °C for 3h heating in Pb/Al of 1/2 system. For Pb/Al of 1/12 system, significant growth of the PbAl12O19 phase clearly occurred at 1000 °C for 3 h sintering. Different product microstructures were found in the sintered products between the systems with the Pb/Al ratios 1/2 and 1/12. The leaching performances of the PbO, Pb9Al8O21, PbAl2O4 and PbAl12O19 phases were compared using a constant pH 4.9 leaching test over 92 h. The leachability data indicated that the incorporation of lead into PbAl12O19 crystal is a preferred stabilization mechanism in aluminate-ceramics.

  11. A coumarin-specific prenyltransferase catalyzes the crucial biosynthetic reaction for furanocoumarin formation in parsley.

    Science.gov (United States)

    Karamat, Fazeelat; Olry, Alexandre; Munakata, Ryosuke; Koeduka, Takao; Sugiyama, Akifumi; Paris, Cedric; Hehn, Alain; Bourgaud, Frédéric; Yazaki, Kazufumi

    2014-02-01

    Furanocoumarins constitute a sub-family of coumarin compounds with important defense properties against pathogens and insects, as well as allelopathic functions in plants. Furanocoumarins are divided into two sub-groups according to the alignment of the furan ring with the lactone structure: linear psoralen and angular angelicin derivatives. Determination of furanocoumarin type is based on the prenylation position of the common precursor of all furanocoumarins, umbelliferone, at C6 or C8, which gives rise to the psoralen or angelicin derivatives, respectively. Here, we identified a membrane-bound prenyltransferase PcPT from parsley (Petroselinum crispum), and characterized the properties of the gene product. PcPT expression in various parsley tissues is increased by UV irradiation, with a concomitant increase in furanocoumarin production. This enzyme has strict substrate specificity towards umbelliferone and dimethylallyl diphosphate, and a strong preference for the C6 position of the prenylated product (demethylsuberosin), leading to linear furanocoumarins. The C8-prenylated derivative (osthenol) is also formed, but to a much lesser extent. The PcPT protein is targeted to the plastids in planta. Introduction of this PcPT into the coumarin-producing plant Ruta graveolens showed increased consumption of endogenous umbelliferone. Expression of PcPT and a 4-coumaroyl CoA 2'-hydroxylase gene in Nicotiana benthamiana, which does not produce furanocoumarins, resulted in formation of demethylsuberosin, indicating that furanocoumarin production may be reconstructed by a metabolic engineering approach. The results demonstrate that a single prenyltransferase, such as PcPT, opens the pathway to linear furanocoumarins in parsley, but may also catalyze the synthesis of osthenol, the first intermediate committed to the angular furanocoumarin pathway, in other plants.

  12. Cerimetric determination of simvastatin in pharmaceuticals based on redox and complex formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Basavaiah, K.; Devi, O.Z [University of Mysore, Manasagangotri, Mysore (India). Dept. of Chemistry]. E-mail: basavaiahk@yahoo.co.in

    2008-07-01

    Two sensitive spectrophotometric methods are described for the determination of simvastatin (SMT) in bulk drug and in tablets. The methods are based on the oxidation of SMT by a measured excess of cerium (IV) in acid medium followed by determination of unreacted oxidant by two different reaction schemes. In one procedure (method A), the residual cerium (IV) is reacted with a fixed concentration of ferroin and the increase in absorbance is measured at 510 nm. The second approach (method B) involves the reduction of the unreacted cerium (IV) with a fixed quantity of iron (II), and the resulting iron (III) is complexed with thiocyanate and the absorbance measured at 470 nm. In both methods, the amount of cerium (IV) reacted corresponds to SMT concentration. The experimental conditions for both methods were optimized. In method A, the absorbance is found to increase linearly with SMT concentration (r = 0.9995) whereas in method B, the same decreased (r = -0.9943). The systems obey Beer's law for 0.6-7.5 and 0.5-5.0 {mu}g mL{sup -1} for method A and method B, respectively. The calculated molar absorptivity values are 2.7 X 104 and 1.06 X 105 Lmol{sup -1} cm{sup -1}, respectively; and the corresponding sandel sensitivity values are 0.0153 and 0.0039 {mu}g cm{sup -2}, respectively. The limit of detection (LOD) and quantification (LOQ) are reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of SMT in tablets and the results were statistically compared with those of the reference method by applying the Student's t-test and F-test. No interference was observed from the common excipients added to tablets. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard addition procedure. (author)

  13. Progress in the study on the composition and formation mechanism of gallstone

    Institute of Scientific and Technical Information of China (English)

    SUN; Ying

    2001-01-01

    [1]Soloway, R. D., Trotman, B. W., Maddrey, W. C. et al., The influence of hemolysis, infection and stasis on the calcium salts in pigment gallstones, Dig. Dis. Sci., 1986, 31: 454-460.[2]Cheng, L. J., Zhang, Y., Ma, J. S. et al., Chemical preparation and properties of ditaurobilirubin disodium salt, Chemical Reagents, 2000, 22(2): 70-71.[3]Ma. J. S., Wang, C. Q., Yan F., Hypocrellin A-sensitized photooxidation of bilirubin in aprotic solvents, Photographic Science and Photochemistry, 1991, 9(1): 58-61.[4]Yang, Z. H., Wang, K., Liu, X. T., Studies of electron-spin-resonance on bilirubin free radicals, Science in China, Series B,1992, 35(9): 1093-1100.[5]Ostrow, J. D., Overview the bile pigment metabolism, in Bile Pigments and Jaundice: Molecular, Metabolic, and Medical Aspects (ed. Ostrow, J. D.), New York: Marcel Dekker, 1986, 1-6.[6]Ouyang, J. M., Li, C., Li, Y. Q. et al., Monolayer and Langmuir-Blodgett films of bilirubin dihexadecyl ester, Thin Solid Films, 1999, 348: 242-247.[7]Wu, J. G., Shen, G. R., Zhou, X, S. et al., Structure characteristics of bilirubin gallstone, Chinese Science Bulletin, 1979,24: 1054-1056.[8]Zhou, X. S., Wang, S. S., Wu, J. G. et al., Pigment gallstones study, Chinese Medical Journal, 1982, 95(12): 905-911.[9]Wu, J. G., Shen, G. R., Zhou, X. S. et al., Study on the composition, structure and mechanism of formation of bilirubin gallstone, Acta Scientiarum Naturalium Universitatis Pekinensis, 1980, 1: 34-43.[10]Zhou, X. S., Shen, G. R., Wu, J. G. et al., A spectroscopic study of pigment gallstone in China, Biospectroscopy, 1997,3(3): 371-380.[11]Soloway, R. D., Wu, J. G., Analysis of Gallstones, Boca Raton, Ann Arbor, London, Tokyo: CRC Press, 1995, 167-190.[12]Yang, Z. L., Weng, S. F., Wu, J. G., Study on the composition of pigment gallstones, Acta Scientiarum Naturalium Universitatis Pekinensis, 1998, 34(4): 429-434.[13]Soloway, R. D., Song, Y. Y., Wu, J. G. et al., Serial Fourier

  14. Formation Mechanism and Emission Spectrum of AlO Radicals in Reaction of Laser-ablated Al Atom and Oxygen

    Institute of Scientific and Technical Information of China (English)

    ZHANG Shu-dong; LI Hai-Yang

    2003-01-01

    The emission spectrum of AlO radicals was analyzed in 440-540 nm in the reaction of laser ablated Al beam and O2. The carrier of spectrum was assigned to Δν=0, ±1, ±2 vibrational sequences of B2Σ+-X2Σ+ transition of AlO radicals, the observed maximum vibrational quantum number was ν′=6. The rotational and vibrational temperatures of B state were estimated at 3000 and 7500 K by spectrally simulating the rovibronic population distribution. There is a strong evidence that the production of excited Al(2S) atoms is essential to the formation of excited AlO radicals.

  15. Compound nucleus formation probability PCN determined within the dynamical cluster-decay model for various "hot" fusion reactions

    Science.gov (United States)

    Kaur, Arshdeep; Chopra, Sahila; Gupta, Raj K.

    2014-08-01

    The compound nucleus (CN) fusion/formation probability PCN is defined and its detailed variations with the CN excitation energy E*, center-of-mass energy Ec .m., fissility parameter χ, CN mass number ACN, and Coulomb interaction parameter Z1Z2 are studied for the first time within the dynamical cluster-decay model (DCM). The model is a nonstatistical description of the decay of a CN to all possible processes. The (total) fusion cross section σfusion is the sum of the CN and noncompound nucleus (nCN) decay cross sections, each calculated as the dynamical fragmentation process. The CN cross section σCN is constituted of evaporation residues and fusion-fission, including intermediate-mass fragments, each calculated for all contributing decay fragments (A1, A2) in terms of their formation and barrier penetration probabilities P0 and P. The nCN cross section σnCN is determined as the quasi-fission (qf) process, where P0=1 and P is calculated for the entrance-channel nuclei. The DCM, with effects of deformations and orientations of nuclei included in it, is used to study the PCN for about a dozen "hot" fusion reactions forming a CN of mass number A ˜100 to superheavy nuclei and for various different nuclear interaction potentials. Interesting results are that PCN=1 for complete fusion, but PCNPCN≪1 due to the nCN contribution, depending strongly on different parameters of the entrance-channel reaction but found to be independent of the nuclear interaction potentials used.

  16. Ectopic runx2 expression in mammary epithelial cells disrupts formation of normal acini structure: implications for breast cancer progression.

    Science.gov (United States)

    Pratap, Jitesh; Imbalzano, Karen M; Underwood, Jean M; Cohet, Nathalie; Gokul, Karthiga; Akech, Jacqueline; van Wijnen, Andre J; Stein, Janet L; Imbalzano, Anthony N; Nickerson, Jeffrey A; Lian, Jane B; Stein, Gary S

    2009-09-01

    The transcription factor Runx2 is highly expressed in breast cancer cells compared with mammary epithelial cells and contributes to metastasis. Here we directly show that Runx2 expression promotes a tumor cell phenotype of mammary acini in three-dimensional culture. Human mammary epithelial cells (MCF-10A) form polarized, growth-arrested, acini-like structures with glandular architecture. The ectopic expression of Runx2 disrupts acini formation, and electron microscopic ultrastructural analysis revealed the absence of lumens. Characterization of the disrupted acini structures showed increased cell proliferation (Ki-67 positive cells), decreased apoptosis (Bcl-2 induction), and loss of basement membrane formation (absence of beta(4) integrin expression). In complementary experiments, inhibition of Runx2 function in metastatic MDA-MB-231 breast cancer cells by stable expression of either short hairpin RNA-Runx2 or a mutant Runx2 deficient in subnuclear targeting resulted in reversion of acini to more normal structures and reduced tumor growth in vivo. These novel findings provide direct mechanistic evidence for the biological activity of Runx2, dependent on its subnuclear localization, in promoting early events of breast cancer progression and suggest a molecular therapeutic target.

  17. An atypical cause of rapidly progressing breast lump with abscess formation: Pure squamous cell carcinoma of the breast.

    Science.gov (United States)

    Cilekar, Murat; Erkasap, Serdar; Oner, Ulku; Akici, Murat; Ciftci, Evrim; Dizen, Hayrettin; Turel, Serkan; Kavak, Ozgu I; Yilmaz, Sezgin

    2015-01-01

    Squamous cell carcinoma (SCC) is a rare type of breast malignancy and little is known about long-term outcome. In the present report, the clinical features, histopathologic findings and postoperative course of a patient with squamous cell carcinoma are described. We have treated a 47-years-old woman who admitted for right breast mass without any discharge, bleeding and pain. The tumor was, 3 × 2 × 1.5 cm in size with central abscess formation. The result of surgical biopsy revealed large cell keratinizing type of SCC. The metastatic work-up studies ruled out any other probable sources of primary tumor. The patient was performed modified radical mastectomy and axillary dissection and received two cycles of chemotherapy. Squamous cell carcinoma of the breast (SCCB) is a rare entity and should be considered in patients with rapidly progressing breast mass. It should also be considered in breast lesions with abscess formation. The initial therapeutic approach should be surgical excision after histopathological diagnosis.

  18. Pattern Formation in the Turing-Hopf Codimension-2 Phase Space in a Reaction-Diffusion System

    Institute of Scientific and Technical Information of China (English)

    YUAN Xu-Jin; SHAO Xin; LIAO Hui-Min; OUYANG Qi

    2009-01-01

    We systematically investigate the behaviour of pattern formation in a reaction-diffusion system when the system is located near the Turing-Hopf codimension-2 point in phase space. The chloride-iodide-malonic acid (CIMA) reaction is used in this study. A phase diagram is obtained using the concentration of polyvinyl alcohol (PVA) and malonic acid (MA) as control parameters. It is found that the Turing-Hopf mixed state appears only in a small vicinity near the codimension-2 point, and has the form of hexagonal pattern overlapped with anti-target wave; the boundary line separating the Thring state and the wave state is independent of the concentration of MA, only relies on the concentration of PVA. The corresponding numerical simulation using the Lengyel-Epstein (LE) model gives a similar phase diagram as the experiment; it reproduces most patterns observed in the experiment. However, the mixed state we obtain in simulation only appears in the anti-wave tip area, implying that the 3-D effect in the experiments may change the pattern forming behaviour in the codimension-2 regime.

  19. Nitrogen oxide formation from chemically-bound nitrogen during the combustion of fossil fuels. [Extended Zeldovich reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, R.E.

    1976-06-01

    One of the many problems associated with the firing of fossil fuels is the impact on the ambient levels of nitrogen oxides. Since the use of coals, oils and coal-derived fuels is expected to triple by 1985, it is urgent that the formation of nitrogen oxides from molecular nitrogen and organo-nitrogen species be fully characterized so that emission abatement strategies can be formulated. The thermal fixation of atmospheric nitrogen and the free radical reactions of nitrogenous species are the sources of NO/sub x/. The fixation reactions can be described by the extended Zeldovich mechanism, and techniques such as staged combustion and flue gas recirculation have been employed to reduce combustion temperatures and, hence, thermally formed NO. These techniques have had little effect, however, on the conversion of chemically-bound nitrogen to NO/sub x/. The fate of chemically-bound nitrogen depends upon such factors as the nitrogen content of the fuel and the equivalence ratio and upon the physical processes governing combustion. Research is proposed to establish the kinetic processes involved in the conversion of fuel nitrogen to NO and N/sub 2/ in environments characteristic of fossil fuel combustion and to identify those conditions which favor the reduction of NO to N/sub 2/.

  20. Enhanced reactivity of hydroxylated polycyclic aromatic hydrocarbons to birnessite in soil: reaction kinetics and nonextractable residue formation.

    Science.gov (United States)

    Jung, Jae-Woong; Lee, Seunghwan; Ryu, Hyerim; Nam, Kyoungphile; Kang, Ki-Hoon

    2008-05-01

    Phenanthrene and pyrene were not transformed by birnessite (delta-MnO2) in the presence of phenol. The phenoxy radicals generated from phenol by birnessite did not act as a mediator for polycyclic aromatic hydrocarbon radical reaction under the studied conditions. In contrast, 9-hydroxyphenanthrene and 1-hydroxypyrene were remarkably sensitive to birnessite. The disappearance patterns of the test compounds both in the aqueous phase and soil followed first-order kinetics, with a linear relationship found between the rate constants and the surface area of birnessite. Moreover, the data indicated that the reaction was faster in the presence of soil than in the aqueous phase probably because of the presence of hydroxyl groups in soil organic matter. Sequential solvent extraction was not successful in the recovery of 9-hydroxyphenanthrene from the birnessite-treated soil samples, and capillary electrophoresis data suggest the formation of nonextractable residues of the compound in soil. In addition, the acute toxicity determined by Microtox declined approximately 8.3 times in the soil samples treated with birnessite compared to untreated samples, demonstrating that the toxic compound was no longer present as its parent form.

  1. Formation of submicron magnesite during reaction of natural forsterite in H2O-saturated supercritical CO2

    Science.gov (United States)

    Qafoku, Odeta; Hu, Jianzhi; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in bulk liquid water saturated with supercritical CO2 (scCO2) and scCO2 saturated with water at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3·3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In liquid water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in scCO2 saturated with H2O magnesite formation was identified at all three temperatures: 35, 50, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 and 80 °C, but nesquehonite was dominant at 35 °C. The magnesite particles formed under scCO2 saturated with H2O conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with nucleation and growth on the forsterite surface.

  2. Formation of Submicron Magnesite during Reaction of Natural Forsterite in H2O-Saturated Supercritical CO2

    Energy Technology Data Exchange (ETDEWEB)

    Qafoku, Odeta; Hu, Jian Z.; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in a) liquid water saturated with supercritical CO2 (scCO2) and in b) H2O-saturated scCO2 at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3.3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in H2O-saturated scCO2 magnesite formation was identified at all three temperatures: 35 °, 50 °, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 ° and 80 °C; but nesquehonite was dominant at 35 °C. The magnesite particles formed under H2O-saturated scCO2 conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with epitaxial nucleation and growth on the forsterite surface.

  3. The formation of diethyl ether via the reaction of iodoethane with atomic oxygen on the Ag(110) surface

    Science.gov (United States)

    Jones, G. Scott; Barteau, Mark A.; Vohs, John M.

    1999-01-01

    The reactions of iodoethane (ICH 2CH 3) on clean and oxygen-covered Ag(110) surfaces were investigated using temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). Iodoethane adsorbs dissociatively at 150 K to produce surface ethyl groups on both clean and oxygen-covered Ag(110) surfaces. The ethyl species couple to form butane on both surfaces, with the desorption peak maximum located between 218 and 238 K, depending on the ethyl coverage. In addition to butane, a number of oxidation products including diethyl ether, ethanol, acetaldehyde, surface acetate, ethylene, carbon dioxide and water were formed on the oxygen-dosed Ag(110) surface. Diethyl ether was the major oxygenate produced at all ethyl:oxygen ratios, and the peak temperature for ether evolution varied from 220 to 266 K depending on the relative coverages of these reactants. The total combustion products, CO 2 and H 2O, were primarily formed at low ethyl coverages in the presence of excess oxygen. The formation of ethylene near 240 K probably involves an oxygen-assisted dehydrogenation pathway since ethylene is not formed from ethyl groups on the clean surface. Acetaldehyde and ethanol evolve coincidentally with a peak centered at 270-280 K, and are attributed to the reactions of surface ethoxide species. The surface acetate which decomposes near 620 K is formed from subsequent reactions of acetaldehyde with oxygen atoms. The addition of ethyl to oxygen to form surface ethoxides was verified by HREELS results. The yields of all products exhibited a strong dependence on the relative coverages of ethyl and oxygen.

  4. Laser kinetic spectroscopic studies of (a) the unimolecular reactions of nitroalkanes and, (b) elementary reactions important in combustion. Annual progress report 1 Jan-31 Aug 81

    Energy Technology Data Exchange (ETDEWEB)

    Estler, R.C.; Reisler, H.; Wittig, C.

    1981-08-31

    The multiphoton ionization (MPI) of NO is used to probe the dynamics of the photodissociation of NO2 in a one-color experiment. The resulting MPI spectra clearly indicate the high internal rotational energy in the NO fragment. MPI shows promise as a highly-sensitive, information-rich diagnostic for internal state determinations of nitric oxide. We report that the 300 K reaction of C2H with O2 has as one of its product channels CH + CO2. By monitoring time resolved CH chemiluminescence following laser photolysis production of C2H in the presence of O2, we have measured rate coefficients for reactions of C2H with O2, H2, and CH4.

  5. Formation and Migration of Oxygen Vacancies in SrCoO3 and their effect on Oxygen Evolution Reactions

    KAUST Repository

    Tahini, Hassan A.

    2016-07-18

    Perovskite SrCoO3 is a potentially useful material for promoting the electrocatalytic oxygen evolution reaction, with high activities predicted theoretically and observed experimentally for closely related doped perovskite materials. However, complete stoichiometric oxidation is very difficult to realize experimentally – in almost all cases there are significant fractions of oxygen vacancies present. Here, using first principles calculations we study oxygen vacancies in perovskite SrCoO3 from thermodynamic, electronic and kinetic points of view. We find that an oxygen vacancy donates two electrons to neighboring Co sites in the form of localized charge. The formation energy of a single vacancy is very low and estimated to be 1.26 eV in the dilute limit. We find that a vacancy is quite mobile with a migration energy of ~0.5 eV. Moreover, we predict that oxygen vacancies exhibit a tendency towards clustering which is in accordance with the material’s ability to form a variety of oxygen-deficient structures. These vacancies have a profound effect on the material’s ability to facilitate OER, increasing the overpotential from ~0.3 V for the perfect material to ~0.7 for defective surfaces. A moderate compressive biaxial strain (2%) is predicted here to increase the surface oxygen vacancy formation energy by ca. 30%, thus reducing the concentration of surface vacancies and thereby preserving the OER activity of the material.

  6. Nanograin formation and reaction-induced fracturing due to decarbonation: Implications for the microstructures of fault mirrors

    Science.gov (United States)

    Pluymakers, A.; Røyne, A.

    2017-10-01

    Principal slip zones often contain highly reflective surfaces referred to as fault mirrors, shown to consist of a nanogranular coating. There is currently no consensus on how the nanograins form, or why they survive weathering on a geological time-scale. To simplify the complex system of a natural fault zone, where slip and heat generation are inherently coupled, we investigated the effect of elevated temperatures on carbonate rock surfaces, as well as their resistance to water exposure. This allows us to isolate the role of the decarbonation process in the formation of nanograins. We used cleaved crystals of Iceland spar calcite, manually polished dolomite protolith, as well as natural dolomite fault mirror surfaces. The samples were heated to 200-800 °C in a ∼5 h heating cycle, followed by slow cooling (∼12 h) to room temperature. Subsequently, we imaged the samples using scanning electron microscopy and atomic force microscopy. Nanograin formation on all sample surfaces was pervasive at and above 600 °C. The Foiana fault mirror samples were initially coated with aligned naturally-formed nanograins, but display a non-directional nanogranular coating after heating. The nanograins that were formed by heating rapidly recrystallized to bladed hydroxides upon exposure to deionized water, whereas the nanograins on unheated fault mirror samples remained unchanged in water. This shows that the nanograins formed by heating alone are different from those formed in fault zones, and calls for a better characterization of nanograins and their formation mechanisms. Furthermore, we find a characteristic star-shaped crack pattern associated with reacted regions of the carbonate surfaces. The existence of this pattern implies that the mechanical stresses set up by the decarbonation reaction can be sufficiently large to drive fracturing in these systems. We propose that this mechanism may contribute to grain size reduction in fault zones.

  7. Formation of nitrogen-containing polycyclic cations by gas-phase and intracluster reactions of acetylene with the pyridinium and pyrimidinium ions.

    Science.gov (United States)

    Soliman, Abdel-Rahman; Hamid, Ahmed M; Attah, Isaac; Momoh, Paul; El-Shall, M Samy

    2013-01-09

    Here, we present evidence from laboratory experiments for the formation of nitrogen-containing complex organic ions by sequential reactions of acetylene with the pyridinium and pyrimidinium ions in the gas phase and within ionized pyridine-acetylene binary clusters. Additions of five and two acetylene molecules onto the pyridinium and pyrimidinium ions, respectively, at room temperature are observed. Second-order rate coefficients of the overall reaction of acetylene with the pyridinium and pyrimidinium ions are measured as 9.0 × 10(-11) and 1.4 × 10(-9) cm(3) s(-1), respectively, indicating reaction efficiencies of about 6% and 100%, respectively, at room temperature. At high temperatures, only two acetylene molecules are added to the pyridinium and pyrimidinium ions, suggesting covalent bond formation. A combination of ion dissociation and ion mobility experiments with DFT calculations reveals that the addition of acetylene into the pyridinium ion occurs through the N-atom of the pyridinium ion. The relatively high reaction efficiency is consistent with the absence of a barrier in the exothermic N-C bond forming reaction leading to the formation of the C(7)H(7)N(•+) covalent adduct. An exothermic addition/H-elimination reaction of acetylene with the C(7)H(7)N(•+) adduct is observed leading to the formation of a bicyclic quinolizinium cation (C(9)H(8)N(+)). Similar chemistry is observed in the sequential reactions of acetylene with the pyrimidinium ion. The second acetylene addition onto the pyrimidinium ion involves an exclusive addition/H-elimination reaction at room temperature leading to the formation of a bicyclic pyrimidinium cation (C(8)H(7)N(2)(+)). The high reactivity of the pyridinium and pyrimidinium ions toward acetylene is in sharp contrast to the very low reactivity of the benzene cation, which has a reaction efficiency of 10(-4)-10(-5). This indicates that the presence of a nitrogen atom within the aromatic ring enhances the ring growth

  8. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    Science.gov (United States)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  9. Effect of Ag additions on the β phase formation reaction in the Cu–9 wt.%Al–6 wt.%Mn alloy

    Energy Technology Data Exchange (ETDEWEB)

    Adorno, A.T., E-mail: atadorno@iq.unesp.br [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil); Carvalho, T.M. [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil); Silva, R.A.G. [Departamento de Ciências Exatas e da Terra, UNIFESP, 09972-270 Diadema, SP (Brazil); Santos, C.M.A.; Magdalena, A.G. [Departamento de Físico-Química, Instituto de Química, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP (Brazil)

    2015-09-15

    Highlights: • The results suggest a multi-step process involving reversible reactions. • Ag solubilizes preferably at the Cu matrix. • Ag additions decrease the activation energy for the process. - Abstract: The influence of 4 and 5 wt.%Ag additions on the kinetics of β [T{sub 7}-(CuMn){sub 3}Al] phase formation reaction in the Cu–9 wt.%Al–6 wt.%Mn alloy was studied using differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The results indicate that the conversion dependence of the activation energy has a descending shape, suggesting a multi-step process involving reversible reactions. The presence of Ag facilitates the formation of the β phase. The results also showed that the Ag precipitates formation includes the dissolution of Mn and Al atoms, thus decreasing the partial fraction of these elements available to react.

  10. Formats

    Directory of Open Access Journals (Sweden)

    Gehmann, Ulrich

    2012-03-01

    Full Text Available In the following, a new conceptual framework for investigating nowadays’ “technical” phenomena shall be introduced, that of formats. The thesis is that processes of formatting account for our recent conditions of life, and will do so in the very next future. It are processes whose foundations have been laid in modernity and which will further unfold for the time being. These processes are embedded in the format of the value chain, a circumstance making them resilient to change. In addition, they are resilient in themselves since forming interconnected systems of reciprocal causal circuits.Which leads to an overall situation that our entire “Lebenswelt” became formatted to an extent we don’t fully realize, even influencing our very percep-tion of it.

  11. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    Science.gov (United States)

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  12. Transition metal-promoted synthesis of 2-aryl/heteroaryl-thioquinazoline: C-S Bond formation by “Chan-Lam Cross-Coupling” Reaction

    Indian Academy of Sciences (India)

    SATYA KARUNA PULAKHANDAM; NARESH KUMAR KATARI; RAVI PRAKASH REDDY MANDA

    2017-02-01

    An efficient method for the synthesis of S-aryl/heteroaryl-quinazoline has been developed through the cross-coupling of 1,4-dihydroquinazoline with a variety of aryl and heteroaryl boronic acids assisted by [Cu(OAc)₂] as the catalyst for the formation of carbon-sulfur bonds. This newly developed method demonstratesthat the conditions of the traditional copper-catalyzed Chan-Lam reaction can be improved. Optimized reaction involves base, solvent and catalyst.

  13. Palladium(II)-Catalyzed C-H Bond Activation/C-C and C-O Bond Formation Reaction Cascade: Direct Synthesis of Coumestans.

    Science.gov (United States)

    Neog, Kashmiri; Borah, Ashwini; Gogoi, Pranjal

    2016-12-02

    A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

  14. DFT study of the formation mechanism of anthraquinone from the reaction of NO2 and anthracene on NaCl clusters: the role of NaNO3.

    Science.gov (United States)

    Luo, Chao; Yu, Qiming; Wang, Hongming

    2016-12-08

    Polycyclic aromatic hydrocarbons (PAHs) and oxygenated-PAHs are globally worrisome air pollutants because of their highly direct-acting mutagenicity and carcinogenicity. The formation of oxygenated-PAHs is of crucial importance for the prevention of their atmospheric pollution successfully. In this paper, the formation mechanism of oxygenated-PAHs from the heterogeneous reaction of NO2 with anthracene on the surface of NaCl was studied by density functional theory (DFT) calculations. At first, the various adsorption configurations of NO2 and N2O4 on NaCl were investigated. The chemical conversion mechanisms among these configurations were also investigated. It is found that these structures can easily interconvert due to their low energy barriers. NaNO3 was found to be the main product of the reaction of NO2/N2O4 on NaCl. Then the oxidation mechanism of anthracene by NO2 on the NaCl surface showed that NaNO3 is able to oxidize anthracene and plays a catalytic role in the reaction process. This means that the formation of NaNO3 is very important to promote the formation of 9,10-anthraquinone from the heterogeneous reaction of NO2 with anthracene. Our calculations also showed that the introduction of water can greatly accelerate this reaction process.

  15. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

    Science.gov (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  16. Development of a competency-based formative progress test with student-generated MCQs: Results from a multi-centre pilot study

    Directory of Open Access Journals (Sweden)

    Wagener, Stefan

    2015-10-01

    Full Text Available Introduction: Progress tests provide students feedback on their level of proficiency over the course of their medical studies. Peer-assisted learning and competency-based education have become increasingly important in medical education. Although progress tests have been proven to be useful as a longitudinal feedback instrument, there are currently no progress tests that have been created in cooperation with students or that focus on competency in medical education.In this study, we investigated the extent to which students can be included in the development of a progress test and demonstrated that aspects of knowledge related to competency can be represented on a competency-based progress test.Methods: A two-dimensional blueprint for 144 multiple-choice questions (MCQs covering groups of medical subjects and groups of competency areas was generated by three expert groups for developing the competency-based progress test. A total of 31 students from seven medical schools in Germany actively participated in this exercise. After completing an intensive and comprehensive training programme, the students generated and reviewed the test questions for the competency-based progress test using a separate platform of the ItemManagementSystem (IMS. This test was administered as a formative test to 469 students in a pilot study in November 2013 at eight medical schools in Germany. The scores were analysed for the overall test and differentiated according to the subject groups and competency areas.Results: A pool of more than 200 MCQs was compiled by the students for pilot use, of which 118 student-generated MCQs were used in the progress test. University instructors supplemented this pool with 26 MCQs, which primarily addressed the area of scientific skills. The post-review showed that student-generated MCQs were of high quality with regard to test statistic criteria and content. Overall, the progress test displayed a very high reliability. When the

  17. Studies of heavy-ion reactions and transuranic nuclei. Progress report, September 1, 1992--August 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, W.U.

    1993-08-01

    This report contain papers on the following topics: The Cold-Fusion Saga; Decay Patterns of Dysprosium Nuclei Produced in {sup 32}S + {sup 118,124}Sn Fusion Reactions; Unexpected Features of Reactions Between Very Heavy Ions at Intermediate Bombarding Energies; Correlations Between Neutrons and Charged Products from the Dissipative Reaction {sup 197}Au+{sup 208}Pb at E/A = 29 MeV; Dissipative Dynamics of Projectile-Like Fragment Production in the Reaction {sup 209}Bi+{sup 136}Xe at E/A = 28.2 MeV; Dynamical Production of Intermediate-Mass Fragments in Peripheral {sup 209}Bi+{sup 136}Xe Collisions at E{sub lab}/A = 28.2 MeV; The Rochester 960-Liter Neutron Multiplicity Meter; A Simple Pulse Processing Concept for a Low-Cost Pulse-Shape-Based Particle Identification; A One-Transistor Preamplifier for PMT Anode Signals; A Five-Channel Multistop TDC/Event Handler for the SuperBall Neutron Multiplicity Meter; Construction of the SuperBall -- a 16,000-Liter Neutron Detector for Calorimetric Studies of Intermediate-Energy Heavy-Ion Reactions; A Computer Code for Light Detection Efficiency Calculations for Photo-multipliers of a Neutron Detector; Evaluation of Gd-Loaded Liquid Scintillators for the SuperBall Neutron Calorimeter; and Measurement of the Interaction of Cosmic-Ray {mu}{sup {minus}} with a Muon Telescope.

  18. Studies of complex fragment emission in heavy ion reactions. Progress report, January 1, 1990--August 5, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Charity, R.J.; Sobotka, L.G.

    1992-09-01

    Our work involves the study of intermediate energy heavy-ion nuclear reactions. This work has two foci. On the one hand, we desire to learn about the properties of nuclear matter under abnormal conditions, in this energy domain, predominately low densities. This purpose runs abreast of the second, which is the study of the relevant reaction mechanisms. The two objectives are inexorably linked because our experimental laboratory for studying nuclear matter properties is a dynamic one. We are forced to ask how nuclear matter properties, such as phase transitions, are reflected in the dynamics of the reactions. It may be that irrefutable information about nuclear matter will not be extracted from the reaction work. Nevertheless, we are compelled to undertake this effort not only because it is the only game in town and as yet we do not know that information cannot be extracted, but also because of our second objective. The process leads to an understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. Our program has been: To study energy, mass, and angular momentum deposition by studying incomplete fusion reactions. To gain confidence that we understand how highly excited systems decompose by studying all emissions from the highly excited systems. To push these kinds of studies into the intermediate energy domain, with excitation function studies. And attempt to learn about the dynamics of the decays using particle-particle correlations. In the last effort, we have decided to focus on simple systems, where we believe, definitive statements are possible. These avenues of research share a common theme, large complex fragment production.

  19. [Endothelial dysfunction and nonspecific immune reactions in development and progression of osteoarthrosis in women engaged into manual work].

    Science.gov (United States)

    Maliutina, N N; Nevzorova, M S

    2015-01-01

    The article considers mechanisms of development and progression of osteoarthrosis as an occupationally conditioned disease in women of manual work. Women working in physical overstrain conditions are under occupational risk with dysfunction of many body systems. The authors set a hypothesis on association of endothelial dysfunction markers dysbalance and structural remodelling of cartilage matrix as a proof of degenerative changes.

  20. Using Formal Embedded Formative Assessments Aligned with a Short-Term Learning Progression to Promote Conceptual Change and Achievement in Science

    Science.gov (United States)

    Yin, Yue; Tomita, Miki K.; Shavelson, Richard J.

    2014-01-01

    This study examined the effect of learning progression-aligned formal embedded formative assessment on conceptual change and achievement in middle-school science. Fifty-two sixth graders were randomly assigned to either an experimental group or a control group. Both groups were taught about sinking and floating by the same teacher with identical…

  1. Study on Sensory Quality, Antioxidant Properties, and Maillard Reaction Products Formation in Rye-Buckwheat Cakes Enhanced with Selected Spices

    Directory of Open Access Journals (Sweden)

    Małgorzata Przygodzka

    2015-01-01

    Full Text Available The effect of selected spices included in the recipe of rye-buckwheat cakes on sensory quality, nutritional value, and Maillard reaction (MR products formation was addressed in this study. The cakes with cloves, nutmeg, allspice, cinnamon, vanilla, and spice mix addition revealed the highest overall quality values. Cakes enriched with cloves, allspice, and spice mix showed the highest rutin content and almost threefold higher available lysine contents whereas cakes enhanced with mix, cloves, and cinnamon were the richest source of phenolic compounds. The highest antioxidant capacity showed cakes with cloves and spice mix. The furosine, a marker of early stage of MR, was decreased in cakes with cloves, allspice, spice mix, and vanilla whereas fluorescent intermediatory compounds were reduced in cakes enhanced with cloves, allspice, and cinnamon. In contrast, browning index was increased as compared to cakes without spices. The FAST index was significantly lowered in all cakes enriched with spices, especially with cloves, allspice, and mix addition. The presence of cloves, allspice, and vanilla in cake formula was the most efficient in acrylamide strategy. It can be suggested that cloves, allspice, and vanilla might be used for production of safety and good quality cakes.

  2. Excitation functions for the formation of some short-lived products in proton-induced reactions on silver

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, M.S.; Latif, S.K.A. [Inst. of Nuclear Science and Technology, Atomic Energy Research Establishment, Savar, Dhaka (Bangladesh); Baba, M.; Hagiwara, M. [Cyclotron and Radioisotope Center, Tohoku Univ., Sendai (Japan); Qaim, S.M. [Inst. fuer Nuklearchemie, Forschungszentrum Juelich GmbH, Juelich (Germany)

    2008-07-01

    Excitation functions of the {sup nat}Ag(p, xn){sup 104,} {sup 105}Cd and {sup nat}Ag(p, pxn){sup 103,} {sup 104m,g,} {sup 104g}Ag reactions were measured for the first time over the proton energy range of 32 to about 60 MeV. The data were compared with the results of precompound-hybrid model calculations, whereby only partial agreement was obtained. The contribution of the {sup 103}Ag precursor decay to the total formation of the therapeutic radionuclide {sup 103}Pd in proton activation of silver was estimated: it amounted to about 70%. The various possible routes for the production of {sup 103}Pd were also considered: the {sup nat}Ag(p, x){sup 103}Pd and {sup 103}Rh(p, n){sup 103}Pd processes were found to be most interesting. Despite its somewhat lower yield, the latter process is preferred because it can be applied at a low-energy cyclotron. (orig.)

  3. Ambiguities of the Rate of Oxygen Formation During Stellar Helium Burning in the 12C(a,g) Reaction

    CERN Document Server

    Gai, Moshe

    2013-01-01

    The rate of oxygen formation determines the C/O ratio during stellar helium burning. It is the single most important nuclear input of stellar evolution theory including the evolution of Type II and Type Ia supernova. Yet the low energy cross section of the fusion of 4He + 12C denoted as the 12C(a,g)16O reaction still remains uncertain after forty years of extensive work. We analyze and critically review the most recent measurements of complete angular distributions of the outgoing gamma-rays at very low energies (Ecm > 1.0 MeV). Our analysis of the angular distribution measured with the EUROGAM/GANDI arrays lead us to conclude considerably larger error bars than published hence they are excluded from the current sample of "world data". We show that the current sample of "world data" of the measured E2 cross section factors below 1.7 MeV cluster to two distinct groups that lead to two distinct extrapolations of SE2(300) ~ 60 or ~ 154 keVb. We point to a much neglected discrepancy between the measured E1-E2 pha...

  4. Anhydride formation is not a valid mechanism for peptide cleavage by carboxypeptidase-A: a semiempirical reaction pathway study

    Science.gov (United States)

    Vardi-Kilshtain, Alexandra; Shoham, Gil; Goldblum, Amiram

    The mechanism of action of zinc metalloproteinases has been studied by following the direct nucleophilic pathway, which has been frequently suggested but not yet examined by computational methods, and comparing it to other pathways. We computed the reaction enthalpies for the direct nucleophilic attack by Glu270 in the active site model of carboxypeptidase-A on a model substrate's peptide carbonyl and followed this pathway through mixed anhydride formation and subsequent anhydride cleavage by water. The starting molecular coordinates originate in our own high-resolution crystal structure and the computations have been conducted with the minimal neglect of differential overlap (MNDO) Hamiltonian, modified to include the d-orbitals of zinc and the effects of multiple hydrogen bonding, thus labelled MNDO/d/H. Compared to our recent results for two other candidate pathways for this mechanism, both of the General-Acid-General-Base type, we conclude that the direct nucleophilic or 'anhydride' pathway has a much higher energy barrier at the rate determining step, which is a proton transfer, than previously calculated paths. We argue that the 'anhydride' pathway is thus not a valid one for the cleavage of peptides by carboxypeptidase-A.

  5. Recent Progress in Copper-Catalyzed C-S Coupling Reactions%铜催化C-S偶联反应的研究新进展

    Institute of Scientific and Technical Information of China (English)

    秦元成; 彭强

    2011-01-01

    Copper-catalyzed C-S coupling reaction is an important method for the synthesis of sulphur-containing compounds and also a hightlight on organic and catalyst chemistry. In this paper, the recent progress in copper-catalyzed C-S coupling reactions is reviewed according to the different ligands.%铜催化C-S偶联反应是有机合成中的重要手段,近年来一直是有机化学和催化化学的研究热点之一.按照反应中所使用的配体的不同对铜催化C-S偶联反应的研究新进展进行了综述.

  6. 异丙苯催化氧化的研究进展%PROGRESS IN THE RESEARCH OF CUMENE OXIDATION REACTION

    Institute of Scientific and Technical Information of China (English)

    郭建维; 王乐夫; 纪红兵; 黄仲涛; 崔英德

    2001-01-01

    对传统的异丙苯氧化工艺及反应流程进行了简单评述,指出了该工艺存在的缺陷,并对近年来异丙苯氧化的反应工艺、催化体系等研究成果进行了总结归纳和综合评述,在此基础上对这一领域今后的研究方向和发展趋势进行了预测。%The traditional technology and the typical industrial process of cumene oxidation reaction were introduced and commented in this paper, including shortages of this intraditional technology and process. The progresses on reaction conditions, catalytic systems for cumene oxidition were summarized and reviewed. Finally, the possible directions for future research in this area were forcasted.

  7. 芳烃硝化反应机理的研究的进展%Research Progress on Aromatic Nitration Reaction Mechanism

    Institute of Scientific and Technical Information of China (English)

    柏葳

    2016-01-01

    Nitro compounds are important intermediates, but progress for nitration reaction mechanism is relatively slow. In research of the traditional theory of the experiment, researchers have proved that nitroxyl cation in the reaction mechanism is an intermediate state. In terms of the theory of quantum chemistry, researchers have proved that there is no isotope effect in the electrophilic substitution during the experimental facts. It should focus on the traditional optimal experimental conditions, and should also pay more attention to new technologies and new applications. The research progress on aromatic nitration reaction mechanism was described, help to find the nitration reaction transition state and contribute to the development of industrial nitration.%硝基化合物作为重要的中间体,但对于硝化反应机理的研究进展较为缓慢。在传统实验理论研究方面,证明了硝酰阳离子作为中间态的反应机理;在量子化学的理论方面,业已阐明了在亲电取代过程中无同位素效应的实验事实。研究工作者应在注重传统实验条件优化的同时,应多关注新技术与新应用。本文通过对硝化反应机理研究进展的介绍,希望能够为研究者找硝化反应过渡态提供帮助,为硝化工业的发展做出贡献。

  8. A label-free fluorescence DNA probe based on ligation reaction with quadruplex formation for highly sensitive and selective detection of nicotinamide adenine dinucleotide.

    Science.gov (United States)

    Zhao, Jingjin; Zhang, Liangliang; Jiang, Jianhui; Shen, Guoli; Yu, Ruqin

    2012-05-11

    A simple label-free fluorescent sensing scheme for sensitive and selective detection of nicotinamide adenine dinucleotide (NAD(+)) has been developed based on DNA ligation reaction with ligand-responsive quadruplex formation. This approach can detect 0.5 nM NAD(+) with high selectivity against other NAD(+) analogs.

  9. Differential effects of mindful breathing, progressive muscle relaxation, and loving kindness meditation on decentering and negative reactions to repetitive thoughts

    OpenAIRE

    Feldman, Greg; Greeson, Jeff; Senville, Joanna

    2010-01-01

    Decentering has been proposed as a potential mechanism of mindfulness-based interventions but has received limited empirical examination to date in experimental studies comparing mindfulness meditation to active comparison conditions. In the present study, we compared the immediate effects of mindful breathing (MB) to two alternative stress management techniques: progressive muscle relaxation (PMR) and loving kindness meditation (LKM) to test whether decentering is unique to mindfulness medit...

  10. Caffeic acid inhibits the formation of 1-hydroxyethyl radical in the reaction mixture of rat liver microsomes with ethanol partly through its metal chelating activity.

    Science.gov (United States)

    Ikeda, Hideyuki; Kimura, Yuka; Masaki, Miho; Iwahashi, Hideo

    2011-05-01

    Effect of caffeic acid on the formation of 1-hydroxyethyl radicals via the microsomal ethanol-oxidizing system pathway was examined. The electron spin resonance spin trapping showed that 1-hydroxyethyl radicals form in the control reaction mixture which contained 0.17 M ethanol, 1 mg protein/ml rat river microsomes, 0.1 M α-(4-pyridyl-1-oxide)-N-tert-butylnitrone, 5 mM nicotinamide adenine dinucleotide phosphate and 30 mM phosphate buffer (pH 7.4). When the electron spin resonance spectra of the control reaction mixtures with caffeic acid were measured, caffeic acid inhibited the formation of 1-hydroxyethyl radicals in a concentration dependent manner. Gallic acid, dopamine, l-dopa, chlorogenic acid and catechin also inhibited the formation of 1-hydroxyethyl radicals. Above results indicated that the catechol moiety is essential to the inhibitory effect. Caffeic acid seems to chelate of iron ion at the catechol moiety. Indeed, the inhibitory effect by caffeic acid was greatly diminished in the presence of desferrioxamine, a potent iron chelator which removes iron ion in the Fe (III)-caffeic acid complex. Since Fe (III)-desferrioxamine complex is active for the 1-hydroxyethyl radicals formation, caffeic acid inhibits the formation of 1-hydroxyethyl radicals in the reaction mixture partly through its metal chelating activity.

  11. Investigations of nuclear structure and nuclear reactions induced by complex projectiles. Progress report, September 1, 1991--August 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Sarantites, D.G.

    1992-12-01

    The research program described touches five areas of nuclear physics: nuclear structure studies at high spin (hyperdeformation in the mass A {approx_equal} 182 region, structure of {sup 182}Hg and {sup 182}Au at high spin, a highly deformed band in {sup 136}Pm and the anomalous h{sub 11/2} proton crossing in the A{approximately}135 superdeformed region), studies at the interface between structure and reactions (population of entry states in heavy-ion fusion reactions, nuclear structure effects in proton evaporation spectra, nuclear structure- dependent entry state population by total spectroscopy, entrance channel effects in fusion near the barrier, lifetimes of subbarrier {alpha} particles by the atomic clock method), production and study of hot nuclei (the statistical model evaporation code EVAP, statistical emission of deuterons and tritons from highly excited compound nuclei, heavy-fragment emission as a probe of the thermal properties of highly excited compound nuclei, use of incoming-wave boundary condition transmission coefficients in the statistical model: implications in the particle evaporation spectra, study of transparency in the optical model), reaction mechanism studies (binary character of highly dissipative {sup 209}Bi + {sup 136}Xe collisions at E/A=28.2 MeV), and development and use of novel techniques and instrumentation in these areas of research (including a 4{pi} channel selection device, a novel x-ray detector, and a simple channel-selecting detector).

  12. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    Science.gov (United States)

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-06

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Photochemical Reaction of 7,12-Dimethylbenz[a]anthracene (DMBA and Formation of DNA Covalent Adducts

    Directory of Open Access Journals (Sweden)

    Peter P. Fu

    2005-04-01

    Full Text Available DMBA, 7,12-dimethylbenz[a]anthracene, is a widely studied polycyclic aromatic hydrocarbon that has long been recognized as a probable human carcinogen. It has been found that DMBA is phototoxic in bacteria as well as in animal or human cells and photomutagenic in Salmonella typhimurium strain TA102. This article tempts to explain the photochemistry and photomutagenicity mechanism. Light irradiation converts DMBA into several photoproducts including benz[a]anthracene-7,12-dione, 7-hydroxy-12-keto-7-methylbenz[a]anthracene, 7,12-epidioxy-7,12-dihydro-DMBA, 7-hydroxymethyl-12-methylbenz[a]anthracene and 12-hydroxymethyl-7-methylbenz[a]anthracene. Structures of these photoproducts have been identified by either comparison with authentic samples or by NMR/MS. At least four other photoproducts need to be assigned. Photo-irradiation of DMBA in the presence of calf thymus DNA was similarly conducted and light-induced DMBA-DNA adducts were analyzed by 32P-postlabeling/TLC, which indicates that multiple DNA adducts were formed. This indicates that formation of DNA adducts might be the source of photomutagenicity of DMBA. Metabolites obtained from the metabolism of DMBA by rat liver microsomes were reacted with calf thymus DNA and the resulting DNA adducts were analyzed by 32P-postlabeling/TLC under identical conditions. Comparison of the DNA adduct profiles indicates that the DNA adducts formed from photo-irradiation are different from the DNA adducts formed due to the reaction of DMBA metabolites with DNA. These results suggest that photo-irradiation of DMBA can lead to genotoxicity through activation pathways different from those by microsomal metabolism of DMBA.

  14. The catalytic effect of water, water dimers and water trimers on H2S + (3)O2 formation by the HO2 + HS reaction under tropospheric conditions.

    Science.gov (United States)

    Zhang, Tianlei; Yang, Chen; Feng, Xukai; Kang, Jiaxin; Song, Liang; Lu, Yousong; Wang, Zhiyin; Xu, Qiong; Wang, Wenliang; Wang, Zhuqing

    2016-06-29

    In this article, the reaction mechanisms of H2S + (3)O2 formation by the HO2 + HS reaction without and with catalyst X (X = H2O, (H2O)2 and (H2O)3) have been investigated theoretically at the CCSD(T)/6-311++G(3df,2pd)//B3LYP/6-311+G(2df,2p) level of theory, coupled with rate constant calculations by using conventional transition state theory. Our results show that in the presence of catalyst X (X = H2O, (H2O)2 and (H2O)3) into the channel of H2S + (3)O2 formation, the reactions between the SH radical and HO2(H2O)n (n = 1-3) complexes are more favorable than the corresponding reactions of the HO2 radical with HS(H2O)n (n = 1-3) complexes due to the lower barrier of the former reactions and the higher concentrations of HO2(H2O)n (n = 1-3) complexes. Meanwhile, the catalytic effect of water, water dimers and water trimers is mainly taken from the contribution of a single water vapor molecule, since the total effective rate constant of HO2H2O + HS and H2OHO2 + HS reactions was, respectively, larger by 7-9 and 9-12 orders of magnitude than that of SH + HO2(H2O)2 and SH + HO2(H2O)3 reactions. Besides, the enhancement factor of water vapor is only 0.37% at 240 K, while at high temperatures, such as 425 K, the positive water vapor effect is enhanced up to 38.00%, indicating that at high temperatures the positive water effect is obvious under atmospheric conditions. Overall, these results show how water and water clusters catalyze the gas phase reactions under atmospheric conditions.

  15. Products and Mechanisms of Aerosol Formation from Reactions of OH Radicals with Linear and Branched Alkenes in the Presence of NOx (Invited)

    Science.gov (United States)

    Ziemann, P. J.; Matsunaga, A.

    2009-12-01

    The chemical and physical processes involved in the formation of secondary organic aerosol (SOA) are complex and can include reactions of volatile organic compounds with a number of atmospheric oxidants (the major ones are O3, and OH and NO3 radicals), as well as surface and condensed-phase reactions, homogeneous nucleation, and gas-particle partitioning. It should come as no surprise that understanding and accurately modeling these processes is a major challenge that has not yet been fully addressed. Alkenes emitted from vegetation are the largest source of non-methane hydrocarbons to the global atmosphere and consist mostly of isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24), compounds with a large range of sizes and molecular structures. Their atmospheric oxidation is initiated primarily by reactions with hydroxyl radicals and can lead to a variety of products, some of which can form SOA. Because of the complexity of terpene reactions and the large numbers of products that are formed, there are advantages to studying the chemistry of simpler alkenes in order to gain insights that can be applied to more complex reaction systems. This is the approach we have taken, and in this talk I will report results of studies of the products, SOA yields, and mechanisms of SOA formation from reactions of a variety of linear and branched alkenes with hydroxyl radicals in the presence of nitrogen oxides. Products consist of a large array of multifunctional compounds, including oligomers, containing carbonyl, hydroxy, carboxyl, and nitrate groups. I will demonstrate some of the ways in which changes in molecular structure can alter both gas and SOA products, including those formed through condensed-phase reactions, and also SOA yields, and suggest explanations for these effects based on current understanding of chemical reaction mechanisms.

  16. 催化水煤气变换反应的计算模拟进展%Progress of theoretical simulation of catalytic water-gas-shift reaction

    Institute of Scientific and Technical Information of China (English)

    陈玉; 张福丽; 姚辉超; 刘植昌; 崔佳; 徐春明

    2012-01-01

    The progress of theoretical simulation of catalytic water-gas-shift(WGS) reaction is reviewed,by focusing on the reaction mechanism.As to traditional Cu-Zn-,Fe-Cr-,and Co-Mo-based heterogeneous catalysts,carboxyl and redox mechanisms dominate.Promoters and supports also affect the entire reaction process,and may take part in the reaction process directly.Improved or novel catalysts,such as gold or gold-loaded catalyst have also been explored theoretically,and there is also no end to apprehending respective catalytic reaction mechanism.For those homogeneous catalytic reactions like WGS catalyzed by carbonyls of iron group,the understanding of the reaction mechanism is getting deeper.Theoretical studies are expected to expand from those simple model systems to more complex and real WGS model systems.Theoretical studies will show their advantages,such as convenience and low cost,in comparison with experimental investigation,and also provide successful examples for the design of catalysts.%综述了对具有广泛工业应用的水煤气变换(WGS)反应进行理论模拟所取得的进展,重点讨论反应机理方面获得的成果。对于传统的铜锌、铁铬和钴钼等非均相催化剂而言,羧基机理和氧化还原机理占统治地位,而助剂和载体对反应机理也有影响,有时甚至直接参与反应过程。对改进型、新型催化剂如金或负载金等催化WGS反应机理的认识过程尚未结束。对铁族羰基络合均相催化WGS反应机理的理解逐步深入。理论模拟研究将从少数简单的WGS模型体系扩展到更多复杂的真实体系;在预言新的催化体系反应机理上,与实验研究相比,有望体现出费用低和非常便利的优势,并能为催化剂的设计提供理论依据和成功案例。

  17. Direct measurements of the total rate constant of the reaction NCN + H and implications for the product branching ratio and the enthalpy of formation of NCN.

    Science.gov (United States)

    Fassheber, Nancy; Dammeier, Johannes; Friedrichs, Gernot

    2014-06-21

    The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K reaction channel (2a) yielding CH + N2 and channel (2b) yielding HCN + N as the products. A more refined analysis taking into account experimental and theoretical literature data provided a consistent rate constant set for k2a, its reverse reaction k1a (CH + N2 → NCN + H), k2b as well as a value for the controversial enthalpy of formation of NCN, ΔfH = 450 kJ mol(-1). The analysis verifies the expected strong temperature dependence of the branching fraction ϕ = k2b/k2 with reaction channel (2b) dominating at the experimental high-temperature limit. In contrast, reaction (2a) dominates at the low-temperature limit with a possible minor contribution of the HNCN forming recombination channel (2d) at T < 1150 K.

  18. THE C({sup 3}P) + NH{sub 3} REACTION IN INTERSTELLAR CHEMISTRY. I. INVESTIGATION OF THE PRODUCT FORMATION CHANNELS

    Energy Technology Data Exchange (ETDEWEB)

    Bourgalais, Jérémy; Capron, Michael; Picard, Sébastien D. Le [Institut de Physique de Rennes, Astrophysique de Laboratoire, UMR CNRS 6251, Université de Rennes 1, Bât. 11C, Campus de Beaulieu, F-35042 Rennes Cedex (France); Kailasanathan, Ranjith Kumar Abhinavam; Goulay, Fabien [Department of Chemistry, West Virginia University, Morgantown, WV 26506 (United States); Osborn, David L. [Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, CA 94551 (United States); Hickson, Kevin M.; Loison, Jean-Christophe [Université de Bordeaux, Institut des Sciences Moléculaires, UMR 5255, F-33400 Talence (France); Wakelam, Valentine, E-mail: sebastien.lepicard@univ-rennes1.fr, E-mail: fabien.goulay@mail.wvu.edu, E-mail: jean-christophe.loison@u-bordeaux.fr [Univ. Bordeaux, LAB, UMR 5804, F-33270 Floirac (France)

    2015-10-20

    The product formation channels of ground state carbon atoms, C({sup 3}P), reacting with ammonia, NH{sub 3}, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH{sub 3} reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by the Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H{sub 2}CN production channel represents 100% of the product yield for this reaction. Kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.

  19. Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et2dtc)3(phen)

    Institute of Scientific and Technical Information of China (English)

    Song Weiming; Hu Qilin; Chang Xuan; Chen Sanping; Xie Gang; Gao Shengli

    2006-01-01

    A ternary solid complex Yb(Et2dtc)3(phen) was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1, 10-phenanthroline (o-phen·H2O) in absolute ethanol.The bonding characteristics of the complex were characterized by IR.The result shows Yb3+ bands with two sulfur atoms in the Na(Et2dtc)3 and two nitrogen atoms in the o-phen.The enthalpy change of liquid-phase reaction of formation of the complex ΔrHθm (l), was determined as being (-24.838±0.114) kJ·mol-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter.The enthalpy change of the solid-phase reaction of formation of the complex ΔrHθm (s), was calculated as being (108.015±0.479) kJ·mol-1 on the basis of an appropriate thermochemistry cycle.The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction.Fundamental parameters, the activation enthalpy, ΔHθ≠, the activation entropy, ΔSθ≠, the activation free energy, ΔGθ≠, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic experiments.At the same time, the molar heat capacity of the complex cm, p, was determined to be (86.34±1.74) J·mol-1·K-1 by the same microcalormeter.The constant-volume combustion energy of the complex, ΔcU, was determined to be (-17954.08±8.11) kJ·mol-1 by an RBC-Ⅱ type rotating-bomb calorimeter at 298.15 K.Its standard enthalpy of combustion, ΔcHθm, and standard enthalpy of formation, ΔfHθm, were calculated to be (-17973.29±8.11) kJ·mol-1 and (-770.36±9.02) kJ·mol-1, respectively.

  20. Research progress on adverse reactions of pravastatin-associated myopathy%普伐他汀相关肌病不良反应的研究进展

    Institute of Scientific and Technical Information of China (English)

    刘海霞; 李全斌

    2015-01-01

    目的:对普伐他汀导致相关肌病不良反应的最新研究进展进行简要综述,探讨普伐他汀在临床上的合理应用及肌病不良反应的防治措施。方法检索EMbase、万方数据库、中国生物医学文献数据库中相关文献,结合临床,进行综合分析。结果普伐他汀可致相关性肌病、疲倦和劳力性疲劳等不良反应。结论制定普伐他汀的合理用药方案,最大限度地发挥其降脂疗效,减少肌病等不良反应的发生。%Objective To briefly review the latest research progress about adverse reactions of pravastatin re-lated myopathy,investigate the reasonable application of pravastatin in the clinical and prevention measures of myopa-thy adverse reactions. Methods The EMbase,Wanfang database,China biomedical literature database of relevant liter-atures were retrieved,and the results were comprehensively analyzed combined with clinical. Results Pravastatin can cause related myopathy,tired and exertional fatigue and other adverse reactions. Conclusion Rational use of pravasta-tin can maximize its lipid-lowering effect,reduce the occurrence of adverse reactions such as myopathy.

  1. Crossed beam investigation of elementary reactions relevant to the formation of polycyclic aromatic hydrocarbon (PAH)-like molecules in extraterrestrial environments

    Science.gov (United States)

    Kaiser, R. I.; Asvany, O.; Lee, Y. T.

    2000-04-01

    The reactions of ground state carbon atoms, C( 3P j), with benzene, C 6H 6, and phenyl radicals, C 6H 5, with methylacetylene, CH 3CCH, were investigated in crossed beam experiments at collision energies of 21.8 and 140 kJ mol -1 to investigate elementary reactions relevant to the formation and chemistry of polycyclic aromatic hydrocarbons (PAHs) in extraterrestrial environments. The C( 3P j) reaction proceeds via complex formation and gives a cyclic, seven-membered C 7H 5 doublet radical plus atomic hydrogen. This pathway has neither an entrance nor exit barrier, and is exothermic. Together with the experimental verification of the carbon versus hydrogen exchange under single collision conditions, the findings have an important impact on the chemistry of aromatic molecules in interstellar clouds and outflow of carbon stars. Even in the coldest molecular clouds ( T=10 K), the benzene molecule can be destroyed upon reaction with carbon atoms, whereas they are resistant toward an attack of oxygen and nitrogen atoms. Since the aromatic benzene unit is ubiquitous in extraterrestrial, PAH-like material, our results suggest that PAHs might react with carbon atoms as well. On the other side, the reaction of C 6H 5 radicals with methylacetylene to form phenylmethylacetylene is direct. Since an entrance barrier inhibits the reaction in cold molecular clouds and in the atmospheres of hydrocarbon rich planets like Jupiter and Saturn and satellites such as Titan, this reaction is expected to play a role in PAH synthesis only in high temperature interstellar environments, such as circumstellar outflows of carbon stars.

  2. On the formation of cyclopentadiene in the C3H5˙ + C2H2 reaction

    NARCIS (Netherlands)

    Bouwman, J.; Bodi, A.; Oomens, J.; Hemberger, P.

    2015-01-01

    The reaction between the allyl radical (C3H5˙) and acetylene (C2H2) in a heated microtubular reactor has been studied at the VUV beamline of the Swiss Light Source. The reaction products are sampled from the reactor and identified by their photoion mass-selected threshold photoelectron spectra

  3. Reaction Kinetics of Acetone Peroxide Formation and Structure Investigations Using Raman Spectroscopy and X-ray Diffraction

    DEFF Research Database (Denmark)

    Jensen, Lars; Mortensen, Peter Mølgaard; Trane, Rasmus

    2009-01-01

    Triacetone triperoxide (TATP) has been prepared in order to study the effect of pH and temperature on the reaction kinetics. Raman spectra of liquid mixtures of acetone and hydrogen peroxide were recorded versus time throughout the experiments. The spectral data of the liquid phases indicate...... that at 25 degrees C the reaction between acetone and hydrogen peroxide proceeds to form intermediates within one day. Based on the assumption that a likely reaction path involves a sequence of reaction steps between acetone and hydrogen peroxide, calculations of Raman spectra were performed using a density...... functional theory (DFT)/Hartree-Fock approach. It was not possible from this to assess with certainty which intermediate products formed most extensively in an acetone/hydrogen peroxide mixture. However, it was concluded that the most likely reaction mixture is a mixture of the different intermediate...

  4. Effect of some naturally occurring iron ion chelators on the formation of radicals in the reaction mixtures of rat liver microsomes with ADP, Fe3+ and NADPH

    Science.gov (United States)

    Minakata, Katsuyuki; Fukushima, Kazuaki; Nakamura, Masayuki; Iwahashi, Hideo

    2011-01-01

    In order to clarify the mechanism by polyphenols of protective effects against oxidative damage or by quinolinic acid of its neurotoxic and inflammatory actions, effects of polyphenols or quinolinic acid on the radical formation were examined. The ESR measurements showed that some polyphenols such as caffeic acid, catechol, gallic acid, D-(+)-catechin, L-dopa, chlorogenic acid and L-noradrenaline inhibited the formation of radicals in the reaction mixture of rat liver microsomes with ADP, Fe3+ and NADPH. The ESR measurements showed that α-picolinic acid, 2,6-pyridinedicarboxylic acid and quinolinic acid (2,3-pyridinedicarboxylic acid) enhanced the formation of radicals in the reaction mixture of rat liver microsomes with Fe3+ and NADPH. Caffeic acid and α-picolinic acid had no effects on the formation of radicals in the presence of EDTA, suggesting that the chelation of iron ion seems to be related to the inhibitory and enhanced effects. The polyphenols may exert protective effects against oxidative damage of erythrocyte membrane, ethanol-induced fatty livers, cardiovascular diseases, inflammatory and cancer through the mechanism. On the other hand, quinolinic acid may exert its neurotoxic and inflammatory effects because of the enhanced effect on the radical formation. PMID:22128221

  5. Effect of some naturally occurring iron ion chelators on the formation of radicals in the reaction mixtures of rat liver microsomes with ADP, Fe and NADPH.

    Science.gov (United States)

    Minakata, Katsuyuki; Fukushima, Kazuaki; Nakamura, Masayuki; Iwahashi, Hideo

    2011-11-01

    In order to clarify the mechanism by polyphenols of protective effects against oxidative damage or by quinolinic acid of its neurotoxic and inflammatory actions, effects of polyphenols or quinolinic acid on the radical formation were examined. The ESR measurements showed that some polyphenols such as caffeic acid, catechol, gallic acid, D-(+)-catechin, L-dopa, chlorogenic acid and L-noradrenaline inhibited the formation of radicals in the reaction mixture of rat liver microsomes with ADP, Fe(3+) and NADPH. The ESR measurements showed that α-picolinic acid, 2,6-pyridinedicarboxylic acid and quinolinic acid (2,3-pyridinedicarboxylic acid) enhanced the formation of radicals in the reaction mixture of rat liver microsomes with Fe(3+) and NADPH. Caffeic acid and α-picolinic acid had no effects on the formation of radicals in the presence of EDTA, suggesting that the chelation of iron ion seems to be related to the inhibitory and enhanced effects. The polyphenols may exert protective effects against oxidative damage of erythrocyte membrane, ethanol-induced fatty livers, cardiovascular diseases, inflammatory and cancer through the mechanism. On the other hand, quinolinic acid may exert its neurotoxic and inflammatory effects because of the enhanced effect on the radical formation.

  6. Formation of high-molecular-weight angiotensinogen during pregnancy is a result of competing redox reactions with the proform of eosinophil major basic protein

    DEFF Research Database (Denmark)

    Kløverpris, Søren; Skov, Louise Lind; Glerup, Simon

    2013-01-01

    compared to monomeric AGT and the proMBP-AGT complex. Furthermore, we have used recombinant proteins to analyse the formation of the proMBP-PAPP-A and the proMBP-AGT complexes, and we demonstrate that they are competing reactions, depending on the same cysteine residue of proMBP, but differentially...... on the redox potential, potentially important for the relative amounts of the complexes in vivo. These findings may be important physiologically, since the biochemical properties of the proteins change as a consequence of complex formation....

  7. Hydrogen atom abstraction reactions from tertiary amines by benzyloxyl and cumyloxyl radicals: influence of structure on the rate-determining formation of a hydrogen-bonded prereaction complex.

    Science.gov (United States)

    Salamone, Michela; DiLabio, Gino A; Bietti, Massimo

    2011-08-05

    A time-resolved kinetic study on the hydrogen atom abstraction reactions from a series of tertiary amines by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. With the sterically hindered triisobutylamine, comparable hydrogen atom abstraction rate constants (k(H)) were measured for the two radicals (k(H)(BnO(•))/k(H)(CumO(•)) = 2.8), and the reactions were described as direct hydrogen atom abstractions. With the other amines, increases in k(H)(BnO(•))/k(H)(CumO(•)) ratios of 13 to 2027 times were observed. k(H) approaches the diffusion limit in the reactions between BnO(•) and unhindered cyclic and bicyiclic amines, whereas a decrease in reactivity is observed with acyclic amines and with the hindered cyclic amine 1,2,2,6,6-pentamethylpiperidine. These results provide additional support to our hypothesis that the reaction proceeds through the rate-determining formation of a C-H/N hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the nitrogen lone pair wherein hydrogen atom abstraction occurs, and demonstrate the important role of amine structure on the overall reaction mechanism. Additional mechanistic information in support of this picture is obtained from the study of the reactions of the amines with a deuterated benzyloxyl radical (PhCD(2)O(•), BnO(•)-d(2)) and the 3,5-di-tert-butylbenzyloxyl radical.

  8. Theoretical study of reactions at the electrode-electrolyte interface. Progress report, February 1, 1993--March 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J.W.

    1994-04-01

    Electron transfer rates are predicted by numerical methods, in collaboration with ANL. Emphasis is on electron transfer involving ions known to be important in enhancing stress corrosion cracking in light water reactors and on electron transfer at oxide surfaces. We have completed studies of the ferrous-ferric electron transfer rate in which effects of electric field, entropic effects in the free energy and quantum effects are included for the first time in the calculation of the rate of an electrochemical (heterogeneous) reaction rate. These new results confirm assumptions made in earlier calculations. The ferric ion has been modelled in a dissociable polarizable model showing the six-fold coordination of this ion in aqueous solution is stabilized by the three body interactions arising from the polarizability of water. In our studies of oxides, we have completed a Hartree self consistent calculation of the electronic structure of fayalite. The calculation utilizes a new method which takes phenomenological account of local electron correlations which have plagued electronic structure calculations of oxides for a long time. No electronic structure calculation of fayalite has been previously reported to our knowledge. Similar methods have been used to calculate the electronic structure of a vacancy in rutile (TiO{sub 2}). Results show that the screening donor electrons are anisotropically distributed around the vacancy.

  9. Asymmetric Synthesis of Bicyclic Nitrocyclopropanes from Primary Nitro Compounds and Stereoselective Formation of Tetrahydro-2H-cyclopenta[b]furans via Ring Expansion/Cyclization Reaction.

    Science.gov (United States)

    Kamimura, Akio; Moriyama, Takaaki; Ito, Yuji; Kawamoto, Takuji; Uno, Hidemitsu

    2016-06-03

    Optically active bicyclic nitrocyclopropanes are readily prepared from primary chiral nitro compounds, prepared by the conjugate addition of propionaldehyde to a nitro alkene in the presence of proline-derived organocatalysts. The one-step cyclopropanation took place smoothly in a highly stereoselective manner regardless of the stereogenic center adjacent to the allylic unit. Although the allylation reaction catalyzed by BF3·OEt2 provides a mixture of two possible diastereomers, subsequent oxidation of the alcoholic carbon after the formation of nitrocyclopropanes gave diastereomerically pure single products. As a result, separation of the diastereomers during the reaction sequence is unnecessary. Baeyer-Villiger oxidation of the bicyclic nitrocyclopropane ketones followed by enolization resulted in stereoselective formation of a novel cyclopenta[b]furan ring in good yield via ring expansion followed by transannular nucleophilic cyclization.

  10. An elementary reaction kinetic model of the gas-phase formation of polychlorinated dibenzofurans from chlorinated phenols

    Energy Technology Data Exchange (ETDEWEB)

    Dellinger, B.; Khachatryan, L. [Louisiana State Univ., Baton Rouge, LA (United States); Asatryan, R. [State Medical Univ., Yerevan (Armenia)

    2004-09-15

    Combustion and thermal processes are generally recognized as the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F or simply ''dioxins'') in the environment. A previously developed, simple mechanism of gas-phase formation of PCDD from chlorinated phenols suggested that the gas-phase formation pathway was too slow to account for concentrations of PCDD observed in full-scale combustors. As a result, most research on formation of PCDD/F in combustion sources focused on surface-mediated formation. In this manuscript, we report the development of a modified model for the purely gas-phase formation of polychlorinated dibenzofurans (PCDFs) that is based on the experimentally observed formation of PCDF from the oxidation of 2,4,6-trichlorophenol (TCP) in the presence of hexane.

  11. Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

    Science.gov (United States)

    Im, Y.; Jang, M.; Beardsley, R. L.

    2014-04-01

    The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. The model was evaluated with aromatic SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene (135-TMB) under various concentrations of NOx and SO2 using an outdoor reactor (University of Florida Atmospheric PHotochemical Outdoor Reactor (UF-APHOR) chamber). When inorganic species (sulfate, ammonium and water) are present in aerosol, the prediction of both toluene SOA and 135-TMB SOA, in which the oxygen-to-carbon (O : C) ratio is lower than 0.62, are approached under the assumption of a complete organic/electrolyte-phase separation below a certain relative humidity. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on their volatility (6 levels) and reactivity (5 levels) and exploited to construct the stoichiometric coefficient (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on aromatic SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. The OMAR module predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fractions in the SOA predicted by the model were in good agreement with the experimentally measured OS fractions.

  12. TBAI-Catalyzed/Water-Assisted Double C-S Bond Formations: An Efficient Approach to Sulfides through Metal-Free Three-Component Reactions.

    Science.gov (United States)

    Chu, Xue-Qiang; Xu, Xiao-Ping; Ji, Shun-Jun

    2016-09-26

    An aqueous catalytic method for double C-S bond formations that involves alcohol derivatives, organic halides, and sodium thiosulfate has been developed. A diverse range of functionalized sulfides, including pharmaceutical and biological derivatives, can be obtained in an efficient and eco-friendly manner under air. The mechanistic studies revealed that this tetrabutylammonium-iodide-catalyzed/water-assisted reaction generated a mercaptan species as the key intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Efficient CN Formation for Preparingα-Branched Primary Amines by Recycled Intramolecular Reactions of 1,8-Naphthosultone Using Ammonia as Nitrogen Source

    Institute of Scientific and Technical Information of China (English)

    周新锐; 陈洁; 曾小萍; 刘季红; Istvan E.Mark

    2014-01-01

    Amination of tertiary and secondary alcohols using aqueous ammonia as nitrogen source was carried out by a process with recyclable intramolecular reaction of 1,8-naphthosultone, which lead to α-branched primary amines. Sulfonic resin serves as the heterogeneous catalyst for CN bond formation and protects the neighboring hydroxyl group until the required hydrolysis starts in the alkaline solution. The process can be conducted under mild conditions, no additional solvent is needed and no overreaction to secondary or tertiary amines occurs.

  14. Formation of noble-gas hydrides and decay of solvated protons revisited: diffusion-controlled reactions and hydrogen atom losses in solid noble gases.

    Science.gov (United States)

    Tanskanen, Hanna; Khriachtchev, Leonid; Lignell, Antti; Räsänen, Markku; Johansson, Susanna; Khyzhniy, Ivan; Savchenko, Elena

    2008-02-07

    UV photolysis and annealing of C2H2/Xe, C2H2/Xe/Kr, and HBr/Xe matrices lead to complicated photochemical processes and reactions. The dominating products in these experiments are noble-gas hydrides with general formula HNgY (Ng = noble-gas atom, Y = electronegative fragment). We concentrate on distinguishing the local and global mobility and losses of H atoms, barriers of the reactions, and the decay of solvated protons. Different deposition temperatures change the amount of lattice imperfections and thus the amount of traps for H atoms. The averaged distance between reacting species influencing the reaction kinetics is controlled by varying the precursor concentration. A number of solid-state processes connected to the formation of noble-gas hydrides and decay of solvated protons are discussed using a simple kinetic model. The most efficient formation of noble-gas hydrides is connected with global (long-range) mobility of H atoms leading to the H + Xe + Y reaction. The highest concentration of noble-gas hydrides was obtained in matrices of highest optical quality, which probably have the lowest concentration of defects and H-atom losses. In matrices with high amount of geometrical imperfections, the product formation is inefficient and dominated by a local (short-range) process. The decay of solvated protons is rather local than a global process, which is different from the formation of noble-gas molecules. However, the present data do not allow distinguishing local proton and electron mobilities. Our previous results indicate that these are electrons which move to positively-charged centers and neutralize them. It is believed that the image obtained here for solid xenon is applicable to solid krypton whereas the case of argon deserves special attention.

  15. Cross sections for the formation of 69Znm,g and 71Znm,g in neutron induced reactions near their thresholds: Effect of reaction channel on the isomeric cross-section ratio

    Science.gov (United States)

    Nesaraja, C. D.; Sudár, S.; Qaim, S. M.

    2003-08-01

    Excitation functions were measured for the reactions 72Ge(n,α)69Znm,g, 69Ga(n,p)69Znm,g, 70Zn(n,2n)69Znm,g, 74Ge(n,α)71Znm,g, and 71Ga(n,p)71Znm,g over the neutron energy range of 6.3 12.4 MeV. Quasimonoenergetic neutrons in this energy range were produced via the 2H(d,n)3He reaction using a deuterium gas target at the Jülich variable energy compact cyclotron. Use was made of the activation technique in combination with high-resolution HPGe-detector γ-ray spectroscopy. In a few cases low-level β-counting was also applied. In order to decrease the interfering activities in those cases, either radiochemical separations were performed or isotopically enriched targets were used. For most of the reactions, the present measurements provide the first consistent sets of data near their thresholds. From the available experimental data, isomeric cross-section ratios were determined for the isomeric pair 69Znm,g in (n,α), (n,p), and (n,2n) reactions, and for the pair 71Znm,g in (n,α) and (n,p) reactions. Nuclear model calculations using the code STAPRE, which employs the Hauser-Feshbach (statistical model) and exciton model (precompound effects) formalisms, were undertaken to describe the formation of both isomeric and ground states of the products. The calculational results on the total (n,α), (n,p), and (n,2n) cross sections agree fairly well with the experimental data. The experimental isomeric cross-section ratios, however, are reproduced only approximately by the calculation. For both the isomeric pairs investigated, the isomeric cross-section ratio in the (n,p) reaction is higher than in other reactions.

  16. Carbon-carbon bond formation involving reactions of alkynes with group 9 metals (Ir, Rh, Co): preparation of conjugated olefins.

    Science.gov (United States)

    Chin, Chong Shik; Won, Gyongshik; Chong, Daesung; Kim, Mieock; Lee, Hyungeui

    2002-04-01

    Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.

  17. Development of a new molecular dynamics method for tribochemical reaction and its application to formation dynamics of MoS 2 tribofilm

    Science.gov (United States)

    Morita, Yusuke; Onodera, Tasuku; Suzuki, Ai; Sahnoun, Riadh; Koyama, Michihisa; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A.; Shin-yoshi, Takatoshi; Nishino, Noriaki; Suzuki, Atsushi; Miyamoto, Akira

    2008-09-01

    Recently we have developed a novel molecular dynamics program NEW-RYUDO-CR, which can deal with chemical reactions. The developed method has been applied to the study of tribochemical reaction dynamics of MoS 2 tribofilm on iron surface. The initially amorphous MoS 2 layer self-organized its structure as result of the tribochemical reactions and formed layered MoS 2 tribofilm. The friction coefficient significantly decreased as the MoS 2 tribofilm was formed. Besides, sliding was observed between sulfur layers of MoS 2 tribofilms which occurred due to repulsive Coulombic interaction forces between sulfur atoms. This indicates that the formation of the layered MoS 2 tribofilm is important to achieve better lubrication properties.

  18. The influence of pH and reaction time on the formation of FeSe{sub 2} upon selenite reduction by nano-sized pyrite-greigite

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Mingliang [Sun Yat-sen Univ., Zhuhai (China). Sino-French Institute of Nuclear Engineering and Technology; Bardelli, Fabrizio; Ma, Bin; Charlet, Laurent [Grenoble Univ. (France). Environmental Geochemistry Group; Chen, Fanrong; Yang, Yongqiang [Chinese Academy of Sciences, Guangzhou (China). Key Laboratory of Mineralogy and Metallogeny; Chinese Academy of Sciences, Guangzhou (China). Guangdong Provincial Key Laboratory of Mineral Physics and Materials

    2016-11-01

    The influence of pH and reaction time on the formation of FeSe{sub 2} by reductive precipitation of Se(IV) with nano-sized pyrite-greigite was investigated. Reductive precipitation is an effective method of attenuating the mobility of {sup 79}Se, which is foreseen to be a dangerous radioisotope for the geological disposal of high-level radioactive waste (HLW). The results indicated that Se(0)was formed at pH <4.05, whereas, at pH > 6.07, considerable amount of FeSe{sub 2} was formed along with Se(0). These observations are in agreement with the thermodynamic predictions reported in this work. Furthermore, the formation of FeSe{sub 2} was found to continue by increasing the reaction time, indicating that the Se(0) formed in the early reaction stage is gradually transformed to FeSe{sub 2} upon the depletion of aqueous Se(IV). Since FeSe{sub 2} has a stronger reactivity than pyrite, it was proposed that greigite, rather than pyrite, was responsible for the formation of FeSe{sub 2}. The findings in this study are of interest for key geochemical processes governing the mobility of toxic {sup 79}Se in the environment in presence of iron sulfides.

  19. Uniform Free-Energy Profiles of the P-O Bond Formation and Cleavage Reactions Catalyzed by DNA Polymerases β and λ.

    Science.gov (United States)

    Klvaňa, Martin; Bren, Urban; Florián, Jan

    2016-12-29

    Human X-family DNA polymerases β (Polβ) and λ (Polλ) catalyze the nucleotidyl-transfer reaction in the base excision repair pathway of the cellular DNA damage response. Using empirical valence bond and free-energy perturbation simulations, we explore the feasibility of various mechanisms for the deprotonation of the 3'-OH group of the primer DNA strand, and the subsequent formation and cleavage of P-O bonds in four Polβ, two truncated Polλ (tPolλ), and two tPolλ Loop1 mutant (tPolλΔL1) systems differing in the initial X-ray crystal structure and nascent base pair. The average calculated activation free energies of 14, 18, and 22 kcal mol(-1) for Polβ, tPolλ, and tPolλΔL1, respectively, reproduce the trend in the observed catalytic rate constants. The most feasible reaction pathway consists of two successive steps: specific base (SB) proton transfer followed by rate-limiting concerted formation and cleavage of the P-O bonds. We identify linear free-energy relationships (LFERs) which show that the differences in the overall activation and reaction free energies among the eight studied systems are determined by the reaction free energy of the SB proton transfer. We discuss the implications of the LFERs and suggest pKa of the 3'-OH group as a predictor of the catalytic rate of X-family DNA polymerases.

  20. Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Liu, Junzhi; Narita, Akimitsu; Osella, Silvio; Zhang, Wen; Schollmeyer, Dieter; Beljonne, David; Feng, Xinliang; Müllen, Klaus

    2016-03-02

    Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction.

  1. Effects of o-phenylenediamine on methylglyoxal generation from monosaccharide: Comment on "correlation of methylglyoxal with acrylamide formation in fructose/asparagine Maillard reaction model system".

    Science.gov (United States)

    Wang, Yu; Ho, Chi-Tang

    2008-07-01

    Methylglyoxal (MG), a reactive carbonyl compound, has recently garnered much attention because of its ability to modify proteins over time and yield advanced glycation end products (AGEs) that are thought to contribute to the development of diabetes mellitus and its complications. In a recent paper published in Food Chemistry by Yuan et al. [Yuan, Y., Zhao, G. H., Hu, X. S., Wu, J. H., Liu, J., & Chen, F. (2007a). Correlation of methylglyoxal with acrylamide formation in fructose/asparagines Maillard reaction model system. Food Chemistry, 108(3), 885-890] authors showed a high correlation between methylglyoxal formation and acrylamide formation. However, in their study, model systems of aqueous fructose/asparagines (Fru/Asn) and fructose/asparagines/o-phenylenediamine (Fru/Asn/OPD) heating at 150°C were used. The validity of these models relies on the assumption that OPD will only serve the role of a trapping agent for MG. In this short communication, we would like to call to attention that MG can also have a strong catalytic effect in the generation of MG from fructose. Therefore, it is concluded that the concentration of MG obtained in Fru/Asn/OPD model system cannot correspond to the total amount of MG formed by Maillard reaction of Fru and Asn as claimed by Yuan et al. [Yuan, Y., Zhao, G. H., Hu, X. S., Wu, J. H., Liu, J., & Chen, F. (2007a). Correlation of methylglyoxal with acrylamide formation in fructose/asparagines Maillard reaction model system. Food Chemistry, 108(3), 885-890, Yuan, Y., Zhao, G. H., Hu X. S., Wu, J. H., Liu, J., & Chen. F. (2007b). High correlation of methylglyoxal with acrylamide formation in glucose/asparagine Maillardreaction model. European Food Research and Technology. doi:10.1007/s00217-007-0658-0].

  2. Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

    Science.gov (United States)

    Kawamura, K.; Ferris, J. P.

    1999-01-01

    The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

  3. Insights into the formation of carlactone from in-depth analysis of the CCD8-catalyzed reactions

    KAUST Repository

    Bruno, Mark

    2017-02-10

    Strigolactones (SLs) are a new class of phytohormones synthesized from carotenoids via carlactone. The complex structure of carlactone is not easily deducible from its precursor, a cis-configured β-carotene cleavage product, and is thus formed via a poorly understood series of reactions and molecular rearrangements, all catalyzed by only one enzyme, the carotenoid cleavage dioxygenase 8 (CCD8). Moreover, the reactions leading to carlactone are expected to form a second, yet unidentified product. In this study, we used (13) C and (18) O-labelling to shed light on the reactions catalyzed by CCD8. The characterization of the resulting carlactone by LC-MS and NMR, and the identification of the assumed, less accessible second product allowed us to formulate a minimal reaction mechanism for carlactone generation. This article is protected by copyright. All rights reserved.

  4. Differential effects of mindful breathing, progressive muscle relaxation, and loving-kindness meditation on decentering and negative reactions to repetitive thoughts.

    Science.gov (United States)

    Feldman, Greg; Greeson, Jeff; Senville, Joanna

    2010-10-01

    Decentering has been proposed as a potential mechanism of mindfulness-based interventions but has received limited empirical examination to date in experimental studies comparing mindfulness meditation to active comparison conditions. In the present study, we compared the immediate effects of mindful breathing (MB) to two alternative stress-management techniques: progressive muscle relaxation (PMR) and loving-kindness meditation (LKM) to test whether decentering is unique to mindfulness meditation or common across approaches. Novice meditators (190 female undergraduates) were randomly assigned to complete one of three 15-min stress-management exercises (MB, PMR, or LKM) presented by audio recording. Immediately after the exercise, participants completed measures of decentering, frequency of repetitive thoughts during the exercise, and degree of negative reaction to thoughts. As predicted, participants in the MB condition reported greater decentering relative to the other two conditions. The association between frequency of repetitive thought and negative reactions to thoughts was relatively weaker in the MB condition than in the PMR and LKM conditions, in which these two variables were strongly and positively correlated. Consistent with the construct of decentering, the relative independence between these two variables in the MB condition suggests that mindful breathing may help to reduce reactivity to repetitive thoughts. Taken together, results help to provide further evidence of decentering as a potential mechanism that distinguishes mindfulness practice from other credible stress-management approaches. Copyright 2010 Elsevier Ltd. All rights reserved.

  5. IN-VITRO FORMATION OF PYROMORPHITE VIA REACTION OF PB SOURCES WITH SOFT-DRINK PHOSPHORIC ACID

    Science.gov (United States)

    Similar results were observed Pyromorphite (Pb5(PO4)3C1) is a Pb mineral whose rapid kinetic formation and thermodynamic stability (Nriagu, 1973, 1974) has gained much attention in recent years as a mechanism to diminish Pb toxicity. Our research examined the in-vitro formation o...

  6. In situ TEM observation of the Boudouard reaction: multi-layered graphene formation from CO on cobalt nanoparticles at atmospheric pressure.

    Science.gov (United States)

    Bremmer, G Marien; Zacharaki, Eirini; Sjåstad, Anja O; Navarro, Violeta; Frenken, Joost W M; Kooyman, Patricia J

    2017-02-09

    Using a MEMS nanoreactor in combination with a specially designed in situ Transmission Electron Microscope (TEM) holder and gas supply system, we imaged the formation of multiple layers of graphene encapsulating a cobalt nanoparticle, at 1 bar CO : N2 (1 : 1) and 500 °C. The cobalt nanoparticle was imaged live in a TEM during the Boudouard reaction. The in situ/operando TEM studies give insight into the behaviour of the catalyst at the nanometer-scale, under industrially relevant conditions. When switching from Fischer-Tropsch syngas conditions (CO : H2 : N2 1 : 2 : 3 at 1 bar) to CO-rich conditions (CO : N2 1 : 1 at 1 bar), we observed the formation of multi-layered graphene on Co nanoparticles at 500 °C. Due to the high temperature, the surface of the Co nanoparticles facilitated the Boudouard reaction, causing CO dissociation and the formation of layers of graphene. After the formation of the first patches of graphene at the surface of the nanoparticle, more and more layers grew over the course of about 40 minutes. In its final state, around 10 layers of carbon capped the nanoparticle. During this process, the carbon shell caused mechanical stress in the nanoparticle, inducing permanent deformation.

  7. SISGR - In situ characterization and modeling of formation reactions under extreme heating rates in nanostructured multilayer foils

    Energy Technology Data Exchange (ETDEWEB)

    Hufnagel, Todd C.

    2014-06-09

    Materials subjected to extreme conditions, such as very rapid heating, behave differently than materials under more ordinary conditions. In this program we examined the effect of rapid heating on solid-state chemical reactions in metallic materials. One primary goal was to develop experimental techniques capable of observing these reactions, which can occur at heating rates in excess of one million degrees Celsius per second. One approach that we used is x-ray diffraction performed using microfocused x-ray beams and very fast x-ray detectors. A second approach is the use of a pulsed electron source for dynamic transmission electron microscopy. With these techniques we were able to observe how the heating rate affects the chemical reaction, from which we were able to discern general principles about how these reactions proceed. A second thrust of this program was to develop computational tools to help us understand and predict the reactions. From atomic-scale simulations were learned about the interdiffusion between different metals at high heating rates, and about how new crystalline phases form. A second class of computational models allow us to predict the shape of the reaction front that occurs in these materials, and to connect our understanding of interdiffusion from the atomistic simulations to measurements made in the laboratory. Both the experimental and computational techniques developed in this program are expected to be broadly applicable to a wider range of scientific problems than the intermetallic solid-state reactions studied here. For example, we have already begun using the x-ray techniques to study how materials respond to mechanical deformation at very high rates.

  8. Thermokinetics on the Reaction of Formation of the Ternary Complex Nd[(C5H8NS2)3(C12H8N2)

    Institute of Scientific and Technical Information of China (English)

    FAN,Xue-Zhong(樊学忠); MENG,Xiang-Xin(孟祥鑫); CHEN,San-Ping(陈三平); JIAO,Bao-Juan(焦宝娟); REN,Yi-Xia(任宜霞); GAO,Sheng-Li(高胜利); SHI,Qi-Zhen(史启祯)

    2004-01-01

    The title ternary complex Nd[(C5H8NS2)3(C12H8N2)] has been synthesized in absolute ethanol by the reaction of atmosphere without any cautions against moisture. The bonding characteristics of the complex were characterized by IR, showing that Nd3+ is bonded with sulfur atom in the APDC and coordinated with nitrogen atom in the phen.TG-DTG investigation indicates that the title complex was decomposed into Nd2S3 and deposited carbon in one step where Nd2S3 predominated in the final products. The enthalpy change of formation of the reaction on the title complex in liquid-phase has been determined by a microcalorimeter. Thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy) and kinetics parameters (the rate constant, the apparent activation energy, the pre-exponential constant and the reaction order) of the title reaction have been calculated. The enthalpy change of the solid-phase reaction has been obtained by a thermochemistry cycle.

  9. Adduct Formation, B-H Activation and Ring Expansion at Room Temperature from Reactions of HBcat with NHCs.

    Science.gov (United States)

    Würtemberger-Pietsch, Sabrina; Schneider, Heidi; Marder, Todd B; Radius, Udo

    2016-09-05

    We report the reactions of catecholborane (HBcat; 1) with unsaturated and saturated NHCs as well as CAAC(Me) . Mono-NHC adducts of the type HBcat⋅NHC (NHC=nPr2 Im, iPr2 Im, iPr2 Im(Me) , and Dipp2 Im) were obtained by stoichiometric reactions of HBcat with the unsaturated NHCs. The reaction of CAAC(Me) with HBcat yielded the B-H activated product CAAC(Me) (H)Bcat via insertion of the carbine-carbon atom into the B-H bond. The saturated NHC Dipp2 SIm reacted in a 2:2 ratio yielding an NHC ring-expanded product at room temperature forming a six-membered -B-C=N-C=C-N- ring via C-N bond cleavage and further migration of the hydrides from two HBcat molecules to the former carbene-carbon atom.

  10. Pressure dependent low temperature kinetics for CN + CH3CN: competition between chemical reaction and van der Waals complex formation.

    Science.gov (United States)

    Sleiman, Chantal; González, Sergio; Klippenstein, Stephen J; Talbi, Dahbia; El Dib, Gisèle; Canosa, André

    2016-06-01

    The gas phase reaction between the CN radical and acetonitrile CH3CN was investigated experimentally, at low temperatures, with the CRESU apparatus and a slow flow reactor to explore the temperature dependence of its rate coefficient from 354 K down to 23 K. Whereas a standard Arrhenius behavior was found at T > 200 K, indicating the presence of an activation barrier, a dramatic increase in the rate coefficient by a factor of 130 was observed when the temperature was decreased from 168 to 123 K. The reaction was found to be pressure independent at 297 K unlike the experiments carried out at 52 and 132 K. The work was complemented by ab initio transition state theory based master equation calculations using reaction pathways investigated with highly accurate thermochemical protocols. The role of collisional stabilization of a CNCH3CN van der Waals complex and of tunneling induced H atom abstractions were also considered. The experimental pressure dependence at 52 and 132 K is well reproduced by the theoretical calculations provided that an anharmonic state density is considered for the van der Waals complex CH3CNCN and its Lennard-Jones radius is adjusted. Furthermore, these calculations indicate that the experimental observations correspond to the fall-off regime and that tunneling remains small in the low-pressure regime. Hence, the studied reaction is essentially an association process at very low temperature. Implications for the chemistry of interstellar clouds and Titan are discussed.

  11. Accelerated formation of strontium silicate by solid-state reaction in NaCl-H2O(v) system at lower temperature

    Science.gov (United States)

    Zhang, Junhao; Qiu, Yushi; Huang, Man; Zheng, Hongjuan; Yanagisawa, Kazumichi

    2015-08-01

    An environmentally friendly NaCl-H2O system was developed to prepare SrSiO3 nanostructures from commercially available raw materials, SrCO3 and amorphous SiO2 (α-SiO2), by a one-step solid state reaction at 600 °C for 2 h. The formation of SrSiO3 was accelerated by NaCl-H2O(v) system. The results demonstrate that both NaCl and H2O played vital roles to accelerate the formation of SrSiO3 nanostructures at lower temperature. NaCl was considered to enhance the diffusivity of starting materials and the rate of solid state reactions, and promote the crystallization of products at lower temperature. Additionally, two different phases of SrSiO3 (JPDS 00-032-1257) and SrSiO3 (JPDS 00-006-0415) were abtained without or with the addition of NaCl. Water vapor accelerated the decomposition of SrCO3, and absorbed water on the surface of solid materials dissolved NaCl to form an aqueous ionic liquid composed of Na and Cl ions, which was similar to a hydrothermal process, and further increased the diffusivity of components and reduced the reaction temperature.

  12. Study of DNA adduct 8 hydroxy-2’-deoxyguanosine (8-OHdG) formation through fenton reaction with tert-butylhydroquinone (TBHQ) and butyl hydroxy toluene (BHT)

    Science.gov (United States)

    Handayani, S.; Dani, I. C.; Budiawan; Pakuanisa, D.

    2017-05-01

    The research of DNA adduct formation 8-hydroxy-2’-Deoxyguanosine (8-OHdG) as a biomarker of DNA damage due to oxidative stress was carried out by reacting the DNA base 2’-deoxyguanosine-5’-monophosphate with TBHQ and BHT. The formationof 8-OHdG was carried out in various conditions, at temperature of 37° C and 60° C, pH 7.4 and pH 8.4, within 5 hours of incubation time and in the addition of FeSO4. The formation of DNA adducts profile were analyzed using reversed phase HPLC with UV detector at a wavelength of 254 nm. The results of the study showed that TBHQ and BHT can trigger the formation of 8-OHdG from the reaction of 2’-hydroxy Deoxyguanosine-5’-monophosphate in the presence of Fe (II). Meanwhile, in the addition of hydrogen peroxide, the formation of DNA adducts only occur in the test substance TBHQ. The results showed that the condition of higher temperature at 60°C and pH 8,4 affects the higher formation of DNA adducts.

  13. Microwave-assisted reaction of peptide formation by amino acid with phosphate: Exploration of the most possible channels for the origin of life

    Institute of Scientific and Technical Information of China (English)

    HU Rong; TIAN Jinping; YIN Yingwu

    2006-01-01

    Microwave-assisted reaction of peptide formation by amino acids with phosphate was studied. The results showed that the products were a mixture of peptides containing dipeptide, octapeptides and cyclic peptides, which could be obtained in a short time. Polyphosphate was also produced synchronously by the intermolecular condensation of phosphate. The polymerization degree reached 99% (pyrophosphate 64%, trimetaphosphate 35%) after 2 h at 200℃ under microwave irradiation. The intermediates of the mixed anhydrides formed by the intermolecular condensation of phosphates and glycin were determined by ESI-MS. Peptides were also produced by the reaction of amino acids with trimetaphosphate in aqueous solution. The conversion degree of valine reached 46.5% even at room temperature. The cyclic process of peptide formation and phosphate polymerization, regeneration and utilization in amino acids-phosphate system under microwave irradiation was detected and proved. Peptides could be continually formed only by inputting energy into this system. The above recycle may be the most possible process for primitive peptide formation in the origin of life.

  14. Dynamics of the reaction of C₃(a³Πu) radicals with C₂H₂: a new source for the formation of C₅H.

    Science.gov (United States)

    Huang, Wen-Jian; Sun, Yi-Lun; Chin, Chih-Hao; Lee, Shih-Huang

    2014-09-28

    The reaction C3(a(3)Πu) + C2H2 → C5H + H was investigated at collision energy 10.9 kcal mol(-1) that is less than the enthalpy of ground-state reaction C3(X(1)Σg (+)) + C2H2 → C5H + H. C3(a(3)Πu) radicals were synthesized from 1% C4F6/He by pulsed high-voltage discharge. The title reaction was conducted in a crossed molecular-beam apparatus equipped with a quadrupole-mass filter. Product C5H was interrogated with time-of-flight spectroscopy and synchrotron vacuum-ultraviolet ionization. Reactant C3(a(3)Πu) and product C5H were identified using photoionization spectroscopy. The ionization thresholds of C3(X(1)Σg(+)) and C3(a(3)Πu) are determined as 11.6 ± 0.2 eV and 10.0 ± 0.2 eV, respectively. The C5H product is identified as linear pentynylidyne that has an ionization energy 8.4 ± 0.2 eV. The title reaction releases translational energy 10.6 kcal mol(-1) in average and has an isotropic product angular distribution. The quantum-chemical calculation indicates that the C3(a(3)Πu) radical attacks one of the carbon atoms of C2H2 and subsequently a hydrogen atom is ejected to form C5H + H, in good agreement with the experimental observation. As far as we are aware, the C3(a(3)Πu) + C2H2 reaction is investigated for the first time. This work gives an implication for the formation of C5H from the C3(a(3)Πu) + C2H2 reaction occurring in a combustion or discharge process of C2H2.

  15. PROBLEM OF FORMATION OF EMOTIONAL REACTION IN PRE-SCHOOL CHILDREN WITH MULTIPLE DEVELOPMENTAL DISORDERS IN SUBJECT-COMMUNICATIVE ACTIVITY IN THE CONDITIONS OF KINDERGARTEN

    Directory of Open Access Journals (Sweden)

    Ольга Валентиновна Шохова

    2013-11-01

    Full Text Available The article is devoted to the problem of emotional response in children with developmental disorders in subject-communicative activity . The characteristic of the particularities of emotional reaction in children with divelopmental disorders is given. The author proves that it is necessary to develop emotional response as the base for further social adaptation of children with multiple disorders in development; mechanisms of formation of emotional reaction in communicative activity are described: contents, methods used for multiple diorders. Experimental data has proved the effectiveness of pedagogical thechnology on forming of emotional reaction in subject-communicative activity. Corrective and development work used in this technology is based on principles of integrity, complexness; the interralated series of thematical studies is organized intended for develoment of motor, sensor, communicative and emotional sphere in different activities of children. All this facilitate gradual interiorization of emotional reactions, their automatization in communicative activity.DOI: http://dx.doi.org/10.12731/2218-7405-2013-10-7

  16. Quantum tunneling during interstellar surface-catalyzed formation of water: the reaction H + H$_2$O$_2$ $\\rightarrow$ H$_2$O + OH

    CERN Document Server

    Lamberts, Thanja; Köhn, Andreas; Kästner, Johannes

    2016-01-01

    The final step of the water formation network on interstellar grain surfaces starting from the H + O$_2$ route is the reaction between H and H$_2$O$_2$. This reaction is known to have a high activation energy and therefore at low temperatures it can only proceed via tunneling. To date, however, no rate constants are available at temperatures below 200 K. In this work, we use instanton theory to compute rate constants for the title reaction with and without isotopic substitutions down to temperatures of 50 K. The calculations are based on density functional theory, with additional benchmarks for the activation energy using unrestricted single-reference and multireference coupled-cluster single-point energies. Gas-phase bimolecular rate constants are calculated and compared with available experimental data not only for H + H$_2$O$_2$ $\\rightarrow$ H$_2$O + OH, but also for H + H$_2$O$_2$ $\\rightarrow$ H$_2$ + HO$_2$. We find a branching ratio where the title reaction is favored by at least two orders of magnitu...

  17. [Reaction of 3-aryl-2-nitroacrylates with titanium tetrachloride. Formation of 4H-1,2-oxazines and hydroxy-arylaldehydes].

    Science.gov (United States)

    Hirotani, S; Zen, S

    1994-04-01

    The reaction of ethyl 3-aryl-2-nitroacrylate (1a: aryl = 3-methoxyphenyl) with toluene in the presence of titanium tetrachloride gave 4-(4'-methyl-phenyl)-4H-1,2-benzoxazine (3) in a 44.2% yield. The acrylate 1a reacted with dichloromethane in the presence of titanium tetrachloride to give 5-methoxy-salicylaldehyde (2a) in a 61.8% yield. Therefore, 2a was presumed to be formed via an intermediate 4H-1,2-benzoxazine (3'), followed by ring opening to quinone methide and cyano formate. In a similar reaction using both toluene and dichloromethane, 1 bearing a 2-naphthyl group gave a dimer of quinone methide and 1-hydroxy-2-naphthaldehyde via 4H-naphth[2,1-e]-1,2-oxazine, respectively.

  18. Successive hydrogen-elimination reactions with low activation energies in the a-Si:H formation process: An ab initio molecular-orbital study

    Science.gov (United States)

    Sato, Kota; Sugiyama, Yoko; Uchiyama, Akihiko; Iwabuchi, Susumu; Hirano, Tsuneo; Koinuma, Hideomi

    1992-07-01

    Successive hydrogen elimination reactions with low activation energies during the formation of a-Si:H by silane plasma chemical vapor deposition are proposed on the basis of an ab initio molecular-orbital method. The activation energy of the first step, the reaction of a dangling-bond site with an adjacent tetrahedrally coordinated silicon atom, was found to be 25.2 kcal/mol at 0 K when the zero-point vibrational energy was taken into account. The subsequent step was an exothermic process with a lower activation energy. The total process was thermodynamically much more favorable than the molecular processes by which a hydrogen atom or molecule is eliminated.

  19. Theoretical insights into the cycloaddition reaction mechanism between ketenimine and methyleneimine: An alternative approach to the formation of pyrazole and imidazole

    Indian Academy of Sciences (India)

    Nana Wang; Xiaojun Tan; Weihua Wang; Fangfang Wang; Ping Li

    2016-02-01

    The cycloaddition reaction mechanism between interstellar molecules, ketenimine and methyleneimine, has been systematically investigated employing the second-order Møller-Plesset perturbation theory (MP2) method in order to better understand the reactivity of nitrogenous cumulene ketenimine with the C=N double bond compound methyleneimine. Geometry optimizations and vibrational analyses have been performed for the stationary points on the potential energy surfaces of the system. Calculations show that five-membered cyclic carbene intermediates could be produced through pericyclic reaction processes between ketenimine and methyleneimine. Through the subsequent hydrogen transfer processes, carbene intermediates can be isomerized to the pyrazole and imidazole compounds, respectively. The present study is helpful to understand the formation of prebiotic species in interstellar space.

  20. Theoretical studies on atmospheric chemistry of HFE-245mc and perfluoro-ethyl formate: Reaction with OH radicals, atmospheric fate of alkoxy radical and global warming potential

    Science.gov (United States)

    Lily, Makroni; Baidya, Bidisha; Chandra, Asit K.

    2017-02-01

    Theoretical studies have been performed on the kinetics, mechanism and thermochemistry of the hydrogen abstraction reactions of CF3CF2OCH3 (HFE-245mc) and CF3CF2OCHO with OH radical using DFT based M06-2X method. IRC calculation shows that both hydrogen abstraction reactions proceed via weakly bound hydrogen-bonded complex preceding to the formation of transition state. The rate coefficients calculated by canonical transition state theory along with Eckart's tunnelling correction at 298 K: k1(CF3CF2OCH3 + OH) = 1.09 × 10-14 and k2(CF3CF2OCHO + OH) = 1.03 × 10-14 cm3 molecule-1 s-1 are in very good agreement with the experimental values. The atmospheric implications of CF3CF2OCH3 and CF3CF2OCHO are also discussed.

  1. Formation of a covalent Nepsilon2-guanylylhistidyl reaction intermediate by the GTP:GTP guanylyltransferase from the brine shrimp Artemia.

    Science.gov (United States)

    Cartwright, J L; McLennan, A G

    1999-01-01

    The chemical nature of the enzyme-nucleotide phosphoramidate reaction intermediate employed by the unique GTP:GTP guanylyltransferase from yolk platelets of Artemia franciscana cysts to synthesize diguanosine tetraphosphate (Gp4G) has been investigated. Labeling of the enzyme with [alpha-32P]GTP followed by isolation of the labeled phosphoamino acid by periodate treatment and alkaline hydrolysis and comparison of the product with phosphoamino acid standards by thin-layer and ion-exchange chromatography showed that the linkage involves the Nepsilon2 ring nitrogen of an enzyme histidyl residue. Thus, this enzyme is distinct from the mRNA capping enzymes which can also synthesize Gp4G but which employ a lysyl-nucleotide intermediate. Based on its reaction mechanism and substrate specificity, GTP:GTP guanylyltransferase may belong to the GAFH superfamily which includes the histidine triad proteins, Ap4A phosphorylases, and galactose-1-phosphate uridylyltransferase.

  2. Shielding effects in polymer-polymer reactions. V. Concentration dependence of contact formation between star-branched and linear chains.

    Science.gov (United States)

    Nardai, Michael M; Zifferer, Gerhard

    2013-07-19

    By use of the Dissipative Particle Dynamics (DPD) simulation technique mixtures of star-branched (arm number F = 4) and linear chains in athermal (good) solvent are analyzed regarding probabilities for intermolecular contacts of various reactive sites within different polymer coils. The accompanying sterical hindrances are described in the framework of shielding factors in order to investigate reactions and side reactions in radical polymerization and other techniques that involve polymer-polymer coupling. The shielding factors are studied as a function of total concentration from high dilution up to the bulk for different chain lengths of star-shaped and linear chains. Results indicate that their concentration dependence can be described by a power law for systems above the overlap concentration, whereas the chain length dependence vanishes when extrapolating to infinite chain lengths in that concentration range. Also the influence of the ratio of star chains and linear chains is studied for various concentrations.

  3. A STUDY OF FUNDAMENTAL REACTION PATHWAYS FOR TRANSITION METAL ALKYL COMPLEXES. I. THE REACTION OF A NICKEL METHYL COMPLEX WITH ALKYNES. II. THE MECHANISM OF ALDEHYDE FORMATION IN THE REACTION OF A MOLYBDENUM HYDRIDE WITH MOLYBDENUM ALKYLS

    Energy Technology Data Exchange (ETDEWEB)

    Huggins, John Mitchell

    1980-06-01

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO){sub 3}H (1a) with CpMo(CO){sub 3}R (2, R= CH{sub 3}, C{sub 2}H{sub 5}) at 50{degrees} C in THF gives the aldehyde RCHO and the dimers [CpMo(CO){sub 3}]{sub 2} (3a) and [CpMo(CO){sub 2}]{sub 2} (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the

  4. Formation of novel spiro, spiroansa and dispiroansa derivatives of cyclotetraphosphazene from the reactions of polyfunctional amines with octachlorocyclotetraphosphazatetraene

    Indian Academy of Sciences (India)

    Hani̇fe Ii̇bi̇şoğlu; Gönül Yeni̇lmez Çi̇ftçi̇; Adem Kiliç; Esra Tanriverdi̇; İlker Ün; Hakan Dal; Tuncer Hökelek

    2009-03-01

    Nucleophilic substitution reactions of N4P4Cl8, with di-, tri-, and tetra-functional reagents such as N-methyl-1,3-propanediamine, N,N'-methyl-1,3-propanediamine, spermidine and spermine were investigated in this study. Six novel products were isolated whose structures have been characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy. The structure of (11) was investigated by X-ray crystallography.

  5. Initial formation behaviour of polypyrrole on single crystal TiO2 through photo-electrochemical reaction.

    Science.gov (United States)

    Kawakita, Jin; Weitzel, Matthias

    2011-04-01

    Hybrid materials of the organic and inorganic semiconductors have a potential to show the better performance in the charge separation at the junction upon the photovoltaic action by the presence of the space charge layer in the inorganic semiconductor. In this study, the photo-anodic polymerization was selected as a fabrication method for the hybrid materials composed of TiO2 and polypyrrole on the basis of some advantages of this method. For the process control of the photo-anodic polymerization, it is important to elucidate the formation and growth mechanisms of the organic polymer. In this study, a flat sheet of single-crystal TiO2 was used as a well-defined surface for preparation of the organic polymer of pyrrole. Photo-anodic polarization behaviour was clarified and polypyrrole was prepared on TiO2. The formation process, especially the initial step was revealed by observation of polypyrrole with atomic force microscope (AFM) and statistical interpretation of the morphology of polypyrrole in the nano-scopic level. The formation process of polypyrrole on the TiO2 surface was summarized; (1) adsorption of precursors, (2) localized formation and growth of polypyrrole under the photo-illumination, and (3) homogenous growth of polypyrrole with the external current application under the photo-illumination.

  6. Kinetics of reaction of roasting of soda ash and ilmenite ore concentrate for formation of sodium titanates

    Directory of Open Access Journals (Sweden)

    Nafeaa I.A.

    2015-01-01

    Full Text Available Alkaline metals and hydrogen titanates are of great interest for possible applications. The soda ash and Rosetta ilmenite ore concentrate briquette were investigated. The kinetic of formation of sodium titanate was studied in the temperature range 700°C to 900°C.

  7. Zinc Oxide Nanoparticles Catalyzed Condensation Reaction of Isocoumarins and 1,7-Heptadiamine in the Formation of Bis-Isoquinolinones

    OpenAIRE

    Varadhan Krishnakumar; Kesarla Mohan Kumar; Badal Kumar Mandal; Fazlur-Rahman Nawaz Khan

    2012-01-01

    The diversified bis-isoquinolinones were obtained in two steps, utilizing homophthalic acid and various acid chlorides providing 3-substituted isocoumarins in the first step which on further condensation with 1,7-heptadiamine involving C–N bond formation from the lactone in the presence of 10 mol% zinc oxide nanoparticles (ZnO NPs) (

  8. Features of formation spirituality pictures of the world in youth in in the era of information-highlytechnological scientific and technical progress

    Directory of Open Access Journals (Sweden)

    N. V. Polishchuk

    2016-06-01

    Full Text Available In clause necessity of formation of a spiritual picture of the world, anthropocosmos at young generation at the present stage of development much crisis world and, including, the Ukrainian society is proved. In the article the necessity of formation of anthropocosmos-spiritual picture of the world at young generation at the present stage of development bagalicious the world and, in particular, of the Ukrainian society. The proposed definition of new terms: anthropocosmos is a spiritual picture of the world, anthropocosmic spirituality, anthropocosmic worldview and other anthropocentric concepts and definitions in contemporary philosophical and pedagogical discourse. The presented model of the formation of anthropocosmos-spiritual worldview of the young generation in the information and high-tech scientific and technical progress and the author’s interpretation of its philosophical, educational, pedagogical and spiritual essence. It is proved, that having generated in consciousness of the young man a anthropocosmos-spiritual picture of the world, will allow it in conditions of inevitable crash in the near future of a human civilization, if it will not solve present global-civilizational crises and will not avoid geocosmic accidents, to understand sense space-ekzoplanete lives which will be esclusivi, and, therefore, crisis-free, conflict-free, comprehensive and meaningful, anthropocosmos-highly spiritual (divine M. Berdyaev, and, therefore, progressive and virtually eternal as the life of society, which is composed of such anthropocosmos educated individuals. Solved zagalnoosvitnioi sense anthropocosmos spiritual world picture, which is to solve the problem of the choice of life strategies of mankind, the search for new ways of civilization development, in particular, resettlement anthropocosmos-conscious part of humanity for exoplanets space with the aim of preserving the gene pool of humanity and creation of human cosmically

  9. Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint.

    Science.gov (United States)

    Bartolomei, Vincent; Sörgel, Matthias; Gligorovski, Sasho; Alvarez, Elena Gómez; Gandolfo, Adrien; Strekowski, Rafal; Quivet, Etienne; Held, Andreas; Zetzsch, Cornelius; Wortham, Henri

    2014-01-01

    Gaseous nitrogen dioxide (NO2) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO2 levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO2 with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO2 with selected indoor paint surfaces in the presence of light (300 nmlight (5.5 W m(-2)), an increase of HONO production rate of up to 8.6·10(9) molecules cm(-2) s(-1) was observed at [NO2]=60 ppb and 50% relative humidity (RH). At higher light intensity of 10.6 (W m(-2)), the HONO production rate increased to 2.1·10(10) molecules cm(-2) s(-1). A high NO2 to HONO conversion yield of up to 84% was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO2 heterogeneous reactions.

  10. Formation and reaction of allylic species on silver surfaces: bond-order conservation Morse-potential analysis

    Science.gov (United States)

    Shustorovich, Evgeny

    1992-12-01

    The reaction energetics, particularly the intrinsic activation barriers for possible reactions involving allylic species C 3H 5X, X = H, OH, O, Cl on clean and oxygen-preadsorbed Ag surfaces, have been calculated by using the bond-order conservation Morse-potential (BOC-MP) method. The calculations were made for low coverages of C 3H 5X with qualitative corrections for higher coverages. On clean Ag surfaces, propylene C 3H 6 and allyl alcohol C 3H 5OH are projected to desorb without dissociation, in contrast to allyl chloride C 3H 5C1, which is projected to desorb only at high coverages but to dissociate at low coverages forming a stable π-allyl (and atomic chlorine). It is found that the intrinsic activation barrier for dimerization of π-allyl into 1,5-hexadiene is very small and the apparent barrier should be mainly of diffusional character. In the presence of preadsorbed hydroxyl OH s, π-allyl is projected to undergo various transformations producing allyl alcohol, allyl alkoxide, acrolein, and propylene, when most recombination and disproportionation reactions have low intrinsic activation barriers. The BOC-MP model projections are in good agreement with experiment, particularly with the recent HREEL and TPD studies of C 3H 5C1.

  11. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    Science.gov (United States)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  12. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    Science.gov (United States)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  13. Evaluation of the geological relationships to gas hydrate formation and stability. Progress report, June 16--September 30, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Krason, J.; Finley, P.

    1988-12-31

    The summaries of regional basin analyses document that potentially economic accumulations of gas hydrates can be formed in both active and passive margin settings. The principal requirement for gas hydrate formation in either setting is abundant methane. Passive margin sediments with high sedimentation rates and sufficient sedimentary organic carbon can generate large quantities of biogenic methane for hydrate formation. Similarly, active margin locations near a terrigenous sediment source can also have high methane generation potential due to rapid burial of adequate amounts of sedimentary organic matter. Many active margins with evidence of gas hydrate presence correspond to areas subject to upwelling. Upwelling currents can enhance methane generation by increasing primary productivity and thus sedimentary organic carbon. Structural deformation of the marginal sediments at both active and passive sites can enhance gas hydrate formation by providing pathways for migration of both biogenic and thermogenic gas to the shallow gas hydrate stability zone. Additionally, conventional hydrocarbon traps may initially concentrate sufficient amounts of hydrocarbons for subsequent gas hydrate formation.

  14. A reaction–diffusion mechanism influences cell lineage progression as a basis for formation, regeneration, and stability of intestinal crypts

    Directory of Open Access Journals (Sweden)

    Zhang Lei

    2012-07-01

    Full Text Available Abstract Background Colon crypts, a single sheet of epithelia cells, consist of a periodic pattern of stem cells, transit-amplifying cells, and terminally differentiated cells that constantly renew and turnover. Experimental evidence suggests that Wnt signaling promotes and regulates stem cell division, differentiation, and possible cell migrations while intestinal BMP signaling inhibits stem cell self-renewal and repression in crypt formation. As more molecular details on Wnt and BMP in crypts are being discovered, little is still known about how complex interactions among Wnt, BMP, and different types of cells, and surrounding environments may lead to de novo formation of multiple crypts or how such interactions affect regeneration and stability of crypts. Results We present a mathematical model that contains Wnt and BMP, a cell lineage, and their feedback regulations to study formation, regeneration, and stability of multiple crypts. The computational explorations and linear stability analysis of the model suggest a reaction–diffusion mechanism, which exhibits a short-range activation of Wnt plus a long-range inhibition with modulation of BMP signals in a growing tissue of cell lineage, can account for spontaneous formation of multiple crypts with the spatial and temporal pattern observed in experiments. Through this mechanism, the model can recapitulate some distinctive and important experimental findings such as crypt regeneration and crypt multiplication. BMP is important in maintaining stability of crypts and loss of BMP usually leads to crypt multiplication with a fingering pattern. Conclusions The study provides a mechanism for de novo formation of multiple intestinal crypts and demonstrates a synergetic role of Wnt and BMP in regeneration and stability of intestinal crypts. The proposed model presents a robust framework for studying spatial and temporal dynamics of cell lineages in growing tissues driven by multiple signaling

  15. Co-formation of hydroperoxides and ultra-fine particles during the reactions of ozone with a complex VOC mixture under simulated indoor conditions

    DEFF Research Database (Denmark)

    Fan, Z.H.; Weschler, Charles J.; Han, IK

    2005-01-01

    in the O-3/23 VOCs system. The present study confirmed the findings of a previous study carried out in a real-world office and generated new findings regarding co-formation of UFP. Through a comparative analysis of H2O2* yields under different reaction conditions, this study demonstrates that VOCs co......) under simulated indoor conditions. The VOC mixture contained 23 compounds, including two terpenes (d-limonene and alpha-pinene), two unsaturated alkenes (1-decene and 1-octene), and 19 other saturated organic compounds. These compounds are commonly found in indoor air but their concentrations were...

  16. The new C-C bond formation in the reaction of o-amidophenolate indium(III) complex with alkyl iodides.

    Science.gov (United States)

    Piskunov, Alexandr V; Meshcheryakova, Irina N; Fukin, Georgy K; Shavyrin, Andrei S; Cherkasov, Vladimir K; Abakumov, Gleb A

    2013-08-07

    The reaction of bis(4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-amidophenolato)indium(III) anion with alkyl iodides is reported. This process includes oxidative addition of two RI (R = Me, Et) molecules to the non-transition metal complex and results in an alkyl transfer to ring carbon atoms with the formation of two new C-C bonds. The interaction proceeds at mild conditions and gives new indium(III) derivatives containing iminocyclohexa-1,4-dienolate type ligands.

  17. Investigations on the effect of antioxidant type and concentration and model system matrix on acrylamide formation in model Maillard reaction systems.

    Science.gov (United States)

    Constantinou, Costas; Koutsidis, Georgios

    2016-04-15

    The formation of acrylamide in model Maillard reaction systems containing phenolic compounds was examined, with regards to phenolic type, concentration, and model system matrix. In dry glyoxal/asparagine waxy maize starch (WMS) systems, 9 out of 10 examined phenolics demonstrated an inhibiting effect, with the most significant reductions (55-60%) observed for caffeoylquinic acids. In WMS glucose/asparagine systems, examination of three different concentrations (0.1, 0.5 and 1 μmol/g WMS) suggested a 'minimum effective concentration' for epicatechin and caffeic acid, whilst addition of caffeoylquinic acids resulted in dose-dependent acrylamide reduction (25-75%). The discordant results of further studies utilising different matrices (dry and wet-to-dry) indicated that, apart from the nature and chemical reactivity, the matrix and the physical state of the reactants might be important for acrylamide formation.

  18. Formation of a necklike structure in {sup 35}Cl+{sup 12}C and {sup 197}Au reactions at 43 MeV/nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Larochelle, Y.; Gingras, L.; Beaulieu, L.; Qian, X.; Saddiki, Z.; Djerroud, B.; Dore, D.; Laforest, R.; Roy, R.; Samri, M.; St-Pierre, C. [Laboratoire de Physique Nucleaire, Departement de Physique, Universite Laval, Quebec, G1K 7P4 (CANADA); Ball, G.C.; Bowman, D.R.; Galindo-Uribarri, A.; Hagberg, E.; Horn, D. [AECL, Chalk River Laboratories, Ontario, K0J 1J0 (CANADA); Lopez, J.A.; Robinson, T. [Department of Physics, University of Texas at El Paso, El Paso, Texas 79968-0515 (United States)

    1997-04-01

    The experimental signature of the formation of a necklike structure, with a velocity between that of the projectilelike emitter and that of the targetlike emitter, is investigated with the same beam and experimental setup for targets lighter and heavier than the projectile. The reactions are {sup 35}Cl on {sup 12}C and on {sup 197}Au at 43 MeV/nucleon. Particle velocity distributions are compared with two-source statistical simulations and the presence of a necklike structure is inferred from the data. In the second part of the paper, dynamical model simulations with the formation of a necklike structure are presented for the {sup 35}Cl+{sup 12}C system at 43 MeV/nucleon. {copyright} {ital 1997} {ital The American Physical Society}

  19. Nuclear excitations and reaction mechanisms. Report of progress, February 1, 1975--October 31, 1975. [Summaries of research activities at Brown Univ

    Energy Technology Data Exchange (ETDEWEB)

    1975-11-01

    Progress in the following areas of research is reported: Energies of giant isoscalar monopole and quadrupole excitations, energy-weighted sum rules, the random-phase approximation, Hartree-Fock calculations, spreading widths, physical consequences of the locality of current-density commutators and current-current sum rules. Electron-hydrogen scattering using the inhomogenous equation method; variational calculation of e/sup -/ + H scattering using the symmetrized channel coupling array equation; K operators and unitary approximations for the 3-body problem; approximate calculation of model (d-p) and (dd) amplitudes and cross sections; multi-step processes in direct reactions; bound state calculations using the channel coupling array theory. Methods for determining nuclear charge distributions, relativistic effects in nuclei, dispersion corrections and recoil corrections to elastic electron scattering; unitarity of elastic scattering amplitudes; low energy theorems for two-photon processes; pion-exchange contributions to the charge density; recoil effects and energy-dependent Hamiltonians; pion-exchange contributions to two-photon processes; hypervirial theorems for the Dirac equation; Coulomb energies of nuclei. Pion-nucleus scattering, diagonalization of the ..delta..-(nucleon-hole) configurations, doorway states and doorway dominance, calculations for /sup 4/He, discussion of experimental results.

  20. Thermodynamics of formation reactions of intermetallides Ni/sub 3/Ta and Ni/sub 2/Ta

    Energy Technology Data Exchange (ETDEWEB)

    Lyakishev, N.P.; Snitko, Yu.P.; Alekseev, V.I.; Levshin, G.A. (Tsentral' nyj Nauchno-Issledovatel' skij Inst. Chernoj Metallurgii, Moscow (USSR))

    1981-01-01

    Thermodynamical functions of the formation of Ni/sub 3/Ta and Ni/sub 2/Ta intermetallides are studied when investigating the electromotive force of the cell MoVertical BarTa/sub 2/O/sub 5/, Nisub(x)Tasub(y)Vertical Bar0.99ThOsub(2)i0.01 CaOVertical Bar Fe, Fesub(0.95)OVertical BarMo in the temperature range of 1173-1323 K. Thermodynamical functions of Ni/sub 3/Ta and Ni/sub 2/Ta formation are equal to: ..delta..Gsub(f)sup(0) (1273 K) 31.70 and 28.86; ..delta..Hsub(f)sup(0) (1173-1323 K) 27.88, 07.9 kcal/mol; ..delta..Ssub(f)sup(0) (1173-1323 K) 3,U and 0.75 cal/molxdegree, respectively.

  1. Inhibition of mixed-lineage kinase (MLK) activity during G2-phase disrupts microtubule formation and mitotic progression in HeLa cells.

    Science.gov (United States)

    Cha, Hyukjin; Dangi, Surabhi; Machamer, Carolyn E; Shapiro, Paul

    2006-01-01

    The mixed-lineage kinases (MLK) are serine/threonine protein kinases that regulate mitogen-activated protein (MAP) kinase signaling pathways in response to extracellular signals. Recent studies indicate that MLK activity may promote neuronal cell death through activation of the c-Jun NH2-terminal kinase (JNK) family of MAP kinases. Thus, inhibitors of MLK activity may be clinically useful for delaying the progression of neurodegenerative diseases, such as Parkinson's. In proliferating non-neuronal cells, MLK may have the opposite effect of promoting cell proliferation. In the current studies we examined the requirement for MLK proteins in regulating cell proliferation by examining MLK function during G2 and M-phase of the cell cycle. The MLK inhibitor CEP-11004 prevented HeLa cell proliferation by delaying mitotic progression. Closer examination revealed that HeLa cells treated with CEP-11004 during G2-phase entered mitosis similar to untreated G2-phase cells. However, CEP-11004 treated cells failed to properly exit mitosis and arrested in a pro-metaphase state. Partial reversal of the CEP-11004 induced mitotic arrest could be achieved by overexpression of exogenous MLK3. The effects of CEP-11004 treatment on mitotic events included the inhibition of histone H3 phosphorylation during prophase and prior to nuclear envelope breakdown and the formation of aberrant mitotic spindles. These data indicate that MLK3 might be a unique target to selectively inhibit transformed cell proliferation by disrupting mitotic spindle formation resulting in mitotic arrest.

  2. Olmesartan, an angiotensin II receptor blocker inhibits the progression of cataract formation in cadmium chloride induced hypertensive albino rats.

    Science.gov (United States)

    Choudhary, Rajesh; Bodakhe, Surendra H

    2016-12-15

    Previously we found that cadmium chloride (CdCl2) exposure substantially elevates hypertension and potentiates cataract formation. In the present study, we investigated the protective effects of olmesartan, an angiotensin II receptor blocker against cataractogenesis in the CdCl2-induced hypertensive animal model. Male Sprague-Dawley albino rats (150-180g) were randomly selected and assigned to four groups (n=6). Among the four groups, one group (normal) received 0.3% carboxymethyl cellulose (10ml/kg/day, p.o.), another group (CdCl2 control) received CdCl2 (0.5mg/kg/day, i.p.), and remaining two groups received olmesartan at two doses level (2 and 4mg/kg/day, p.o.) concurrently with CdCl2 for six consecutive weeks. Blood pressure and cataract formation were examined biweekly, and pathophysiological parameters in serum and eye lenses were evaluated after six weeks of the experimental protocol. The olmesartan treatment significantly restored the blood pressure, lenticular opacity, serum and lens antioxidants (catalase, superoxide dismutase, glutathione peroxidase, and glutathione reduced), and malondialdehyde level. Additionally, it significantly restored the proteins, ions (Na(+), K(+), and Ca(2+)), and ATPase pumps activity (Na(+)K(+) ATPase and Ca(2+) ATPase) in the lens as compared to CdCl2 control group. The findings demonstrate that olmesartan potentially inhibits the risk of cataract formation in the hypertensive state via restoration of lenticular oxidative stress, ATPase function, and ionic contents in the eye lenses. The results suggest that angiotensin II receptor blockers play an important role to prevent cataract formation in several pathogenic conditions like hypertension, diabetes, and oxidative stress. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. A novel route for the synthesis of mesoporous and low-thermal stability materials by coupled dissolution-reprecipitation reactions: mimicking hydrothermal mineral formation.

    Science.gov (United States)

    Brugger, Joël; Mcfadden, Aoife; Lenehan, Claire E; Etschmann, Barbara; Xia, Fang; Zhao, Jing; Pring, Allan

    2010-01-01

    Replacement reactions ('pseudomorphism') commonly occur in Nature under a large range of conditions (T 25 to >600 degrees C; P 1 to >5 kbar). Whilst mineral replacement reactions are often assumed to proceed by solid-state diffusion of the metal ions through the mineral, many actually proceed via a coupled dissolution and reprecipitation (CDR) mechanism. In such cases, a starting mineral is dissolved into a fluid and this dissolution is coupled with the precipitation of a replacement phase across the reaction front. In cases where there are close relationships between the crystal structures of the parent and newly formed minerals, the replacement can be topotactic (interface-coupled dissolution and reprecipitation). The kinetics and chemistry of the CDR route are fundamentally different from solid-state diffusion and can be exploited i) for the synthesis of materials that are often difficult to synthesise via traditional methods and ii) to obtain materials with unique properties. This review highlights recent research into the use of CDR for such synthetic challenges. Emphasis has been given to i) the use of CDR to synthesise compounds with relatively low thermal stability such as the thiospinel mineral violarite ((Ni,Fe)(3)S(4)), ii) preliminary work into use of CDR for the production of roquesite (CulnS(2)), a potentially important photovoltaic component and, iii) examples where the textures resulting from CDR reactions are controlled by the nature and texture of the parent phase and the reaction conditions; these being the formation of micro-porous gold and three-dimensional ordered arrays of nanozeolite of uniform size and crystallographic orientation.

  4. Unexpected Formation of Highly Functionalized Dihydropyrans via Addition-Cyclization Reactions Between Dimethyl Oxoglutaconate and α,β-Unsaturated Hydrazones.

    Science.gov (United States)

    Mullins, Jason E; Etoga, Jean-Louis G; Gajewski, Mariusz; Degraw, Joseph I; Thompson, Charles M

    2009-05-20

    The condensation between dienophiles and α,β-unsaturated hydrazone azadienes was previously reported to afford piperidines. During an attempt to adapt this reaction to the preparation of piperidine-based conformationally-restricted analogs of glutamate, it was discovered that the electrophile, dimethyl oxoglutaconate (DOG) led to highly substituted dihydropyrans in 20-50% yield. The unexpected pyran product likely results from an initial 1,4-addition of the hydrazone to the oxoglutaconate followed by intramolecular cyclization of the resultant enolate oxygen to the α,β-unsaturated iminium ion. Further manipulations afford substituted tetrahydropyran 6-methamino-2,4-dicarboxylic acids.

  5. The citric acid-Mn III,IVO 2(birnessite) reaction. Electron transfer, complex formation, and autocatalytic feedback

    Science.gov (United States)

    Wang, Yun; Stone, Alan T.

    2006-09-01

    Citrate released by plants, bacteria, and fungi into soils is subject to abiotic oxidation by MnO 2(birnessite), yielding 3-ketoglutarate, acetoacetate, and Mn II. Citrate loss and generation of products as a function of time all yield S-shaped curves, indicating autocatalysis. Increasing the citrate concentration decreases the induction period. The maximum rate ( rmax) along the reaction coordinate follows a Langmuir-Hinshelwood dependence on citrate concentration. Increases in pH decrease rmax and increase the induction time. Adding Mn II, Zn II, orthophosphate, or pyrophosphate at the onset of reaction decreases rmax. Mn II addition eliminates the induction period, while orthophosphate and pyrophosphate addition increase the induction period. These findings indicate that two parallel processes are responsible. The first, relatively slow process involves the oxidation of free citrate by surface-bound Mn III,IV, yielding Mn II and citrate oxidation products. The second process, which is subject to strong positive feedback, involves electron transfer from Mn II-citrate complexes to surface-bound Mn III,IV, generating Mn III-citrate and Mn II. Subsequent intramolecular electron transfer converts Mn III-citrate into Mn II and citrate oxidation products.

  6. Measurement of Large Spiral and Target Waves in Chemical Reaction-Diffusion-Advection Systems: Turbulent Diffusion Enhances Pattern Formation

    Science.gov (United States)

    von Kameke, A.; Huhn, F.; Muñuzuri, A. P.; Pérez-Muñuzuri, V.

    2013-02-01

    In the absence of advection, reaction-diffusion systems are able to organize into spatiotemporal patterns, in particular spiral and target waves. Whenever advection is present that can be parametrized in terms of effective or turbulent diffusion D*, these patterns should be attainable on a much greater, boosted length scale. However, so far, experimental evidence of these boosted patterns in a turbulent flow was lacking. Here, we report the first experimental observation of boosted target and spiral patterns in an excitable chemical reaction in a quasi-two-dimensional turbulent flow. The wave patterns observed are ˜50 times larger than in the case of molecular diffusion only. We vary the turbulent diffusion coefficient D* of the flow and find that the fundamental Fisher-Kolmogorov-Petrovsky-Piskunov equation, vf∝D*, for the asymptotic speed of a reactive wave remains valid. However, not all measures of the boosted wave scale with D* as expected from molecular diffusion, since the wave fronts turn out to be highly filamentous.

  7. Hydrophilic group formation and cell culturing on polystyrene Petri-dish modified by ion-assisted reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ki-Hwan E-mail: hama@kist.re.kr; Cho, Jun-Sik; Choi, Doo-Jin; Koh, Seok-Keun

    2001-04-01

    Polystyrene (PS) Petri-dishes were modified by an ion-assisted reaction (IAR) to improve wettability and to supply a suitable surface for cell culturing. Low energy Ar{sup +} ions with 1000 eV were irradiated on the surface of PS in oxygen gas environment. Water contact angles of PS were not reduced much by ion irradiation without oxygen gas and had a value of 40 deg. In the case of ion irradiation with flowing oxygen gas, however, the water contact angles were dropped significantly from 73 deg. to 19 deg. X-ray photoelectron spectroscopy analysis showed that the hydrophilic groups were formed on the surface of PS by a chemical reaction between unstable chains induced by ion irradiation and the oxygen gas. Newly formed hydrophilic groups were identified as -(C-O)-, -(C=O)- and -(C=O)-O- bonds. The influence of the surface modification on growth of the rat pheochromocytoma (PC12) cells was investigated. The IAR-treated PS surfaces showed enhanced attachment and growth in PC12 cell culture test.

  8. On the relevance of the H2 + O reaction pathway for the surface formation of interstellar water - A combined experimental and modeling study

    CERN Document Server

    Lamberts, Thanja; Fedoseev, Gleb; Ioppolo, Sergio; Chuang, Ko-Ju; Linnartz, Harold

    2014-01-01

    The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to o...

  9. Correlation between the inhibition of positronium formation by scavenger molecules, and chemical reaction rate of electrons with these molecules in nonpolar liquids

    Energy Technology Data Exchange (ETDEWEB)

    Levay, B.; Mogensen, O.E.

    1977-03-10

    o-Ps yields were determined in various liquid hydrocarbons, tetramethylsilane, and mixtures thereof as a function of C/sub 2/H/sub 5/Br and CCl/sub 4/ concentration. These molecules are known to be good electron scavengers and positronium inhibitors as well. The spur reaction model of Ps formation predicts a correlation between the inhibition coefficient and the chemical rate constant of electrons with scavenger molecules. We found that the dependence of the inhibition coefficient on the work function (V/sub 0/) of electrons in different liquids shows a very unusual behavior, similar to that recently found for the chemical rate constants of quasifree electrons with the same scavenger molecules. The inhibition coefficient as a function of V/sub 0/ had a maximum for C/sub 2/H/sub 5/Br, while it increased monotonously with decreasing V/sub 0/ for CCl/sub 4/. The inhibition coefficient for C/sub 2/H/sub 5/Br in a 1 : 1 molar tetramethylsilane-n-tetradecane mixture was found to be greater than in both of the pure components. The clear correlation found between electron scavenging rate constants and positronium inhibition constitutes the severest test to date of the spur reaction model of positronium formation. The importance of the positron annihilation method from the point of view of radiation chemistry is also emphasized.

  10. Zinc Oxide Nanoparticles Catalyzed Condensation Reaction of Isocoumarins and 1,7-Heptadiamine in the Formation of Bis-Isoquinolinones

    Directory of Open Access Journals (Sweden)

    Varadhan Krishnakumar

    2012-01-01

    Full Text Available The diversified bis-isoquinolinones were obtained in two steps, utilizing homophthalic acid and various acid chlorides providing 3-substituted isocoumarins in the first step which on further condensation with 1,7-heptadiamine involving C–N bond formation from the lactone in the presence of 10 mol% zinc oxide nanoparticles (ZnO NPs (<150 nm afforded the desired bis-isoquinolinones in high yield and purity. The synthesized compounds were then characterized using FTIR, 1H NMR, 13C NMR, and HRMS techniques.

  11. Zinc Oxide Nanoparticles Catalyzed Condensation Reaction of Isocoumarins and 1,7-Heptadiamine in the Formation of Bis-Isoquinolinones

    Science.gov (United States)

    Krishnakumar, Varadhan; Mohan Kumar, Kesarla; Mandal, Badal Kumar; Khan, Fazlur-Rahman Nawaz

    2012-01-01

    The diversified bis-isoquinolinones were obtained in two steps, utilizing homophthalic acid and various acid chlorides providing 3-substituted isocoumarins in the first step which on further condensation with 1,7-heptadiamine involving C–N bond formation from the lactone in the presence of 10 mol% zinc oxide nanoparticles (ZnO NPs) (<150 nm) afforded the desired bis-isoquinolinones in high yield and purity. The synthesized compounds were then characterized using FTIR, 1H NMR, 13C NMR, and HRMS techniques. PMID:22536149

  12. Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure, phosphate activation and montmorillonite composition on phosphodiester bond formation

    Science.gov (United States)

    Ferris, James P.; KAMALUDDIN; Ertem, Gozen

    1990-01-01

    The 2(prime)-d-5(prime)-GMP and 2(prime)-d-5(prime)-AMP bind 2 times more strongly to montmorillonite 22A than do 2(prime)-d-5(prime)-CMP and 5(prime)-TMP. The dinucleotide d(pG)2 forms in 9.2 percent yield and the cyclic dinucleotide c(dpG)2 in 5.4 percent yield in the reaction of 2(prime)-d-5(prime)-GMP with EDAC in the presence of montmorillonite 22A. The yield of dimers which contain the phosphodiester bond decreases as the reaction medium is changed from 0.2 M NaCl to a mixture of 0.2 M NaCl and 0.075 M MgCl2. A low yield of d(pA)2 was observed in the condensation reaction of 5(prime)-ImdpA on montmorillonite 22A. The yield of d(pA)2 obtained when EDAC is used as the condensing agent increases with increasing iron content of the Na(+)-montmorillonite used as catalyst. Evidence is presented which shows that the acidity of the Na(+)-montmorillonite is a necessary but not sufficient factor for the montmorillonite catalysis of phosphodiester bond formation.

  13. Reaction between atomic N(4S) and molecular CO at very low temperature: possible formation of HNCO in the Oort cloud

    Science.gov (United States)

    Nourry, Sendres; Zins, Emilie-Laure; Krim, Lahouari

    2015-07-01

    Beyond the Kuiper belt, the Oort cloud is characterized by particularly cold temperatures and the absence of energetic particles. Specific chemical processes involving cold radicals may occur in this reservoir of comets. A microwave-driven atomic source can be used to generate cold atomic nitrogen (N (4S)) for reactivity study of ices relevant to the Oort cloud. Without any additional source of energy, atomic nitrogen does not react with CO molecules to form NCO. This is consistent with a previous theoretical investigation carried out by Yazidi et al., who have shown that the potential energy surface for the CO (X1Σ+) + N (4S) system is purely dissociative. On the other hand, a very small amount of water is sufficient to induce a reaction between these two species. This three-body reaction leads to the formation of the HNCO monomer, the (HNCO)(H2O) complex, and the hydroxyl radical. Such reactions, leading to prebiotic molecules, may take place in the Oort cloud and in the Kuiper belt, from which most of the comets come.

  14. Reaction Time and Film Thickness Effects on Phase Formation and Optical Properties of Solution Processed Cu2ZnSnS4 Thin Films

    Science.gov (United States)

    Safdar, Amna; Islam, Mohammad; Akram, Muhammad Aftab; Mujahid, Mohammad; Khalid, Yasir; Shah, S. Ismat

    2016-02-01

    Copper-zinc-tin-sulfide (Cu2ZnSnS4 or CZTS) is a promising p-type semiconductor material as absorber layer in thin film solar cells. The sulfides of copper and tin as well as zinc and sulfur powders were dissolved in hydrazine. The effect of chemical reaction between precursor species, at room temperature, was assessed for 6 to 22 h. For 22 h reaction time, the effect of spin coated film thickness on the resulting composition, after annealing under N2 flow at 500 °C for 1 h, was investigated. The morphology, composition, and optical properties of the annealed films were determined by means of x-ray diffraction, scanning electron microscope, and spectrophotometer studies. It was found that, for less than optimal reaction time of 22 h or film thickness below 1.2 µm, other ternary phases namely Cu4SnS4, Cu5Sn2S7, and ZnS co-exist in different proportions besides CZTS. Formation of phase-pure CZTS films also exhibited a tendency to minimize film cracking during annealing. Depending on the processing conditions, the band gap ( E g) values were determined to be in the range of 1.55 to 1.97 eV. For phase-pure annealed CZTS film, an increase in the E g value may be attributed to quantum confinement effect due to small crystallite size.

  15. Structures and reaction mechanisms of cumene formation via benzene alkylation with propylene in a newly synthesized ITQ-24 zeolite: an embedded ONIOM study.

    Science.gov (United States)

    Jansang, Bavornpon; Nanok, Tanin; Limtrakul, Jumras

    2006-06-29

    The cumene formation via benzene alkylation with propylene on the new three-dimensional nanoporous catalyst, ITQ-24 zeolite, has been investigated by using the ONIOM2(B3LYP/6-31G(d,p):UFF) method. Both consecutive and associative reaction pathways are examined. The contributions of the short-range van der Waals interactions, which are explicitly included in the ONIOM2 model, and an additional long-range electrostatic potential from the extended zeolite framework to the energy profile are taken into consideration. It is found that benzene alkylation with propylene in the ITQ-24 zeolite prefers to occur through the consecutive reaction mechanism. The benzene alkylation step is the reaction rate-determining step with an estimated activation energy of 35.70 kcal/mol, comparable with an experimental report in beta-zeolite of 34.9 kcal/mol. The electrostatic potential from the extended zeolite framework shows a much more significant contribution to the transition state selectivity than the van der Waals interactions.

  16. Development of protein biomarkers in cerebrospinal fluid for secondary progressive multiple sclerosis using selected reaction monitoring mass spectrometry (SRM-MS

    Directory of Open Access Journals (Sweden)

    Jia Yan

    2012-07-01

    Full Text Available Abstract Background Multiple sclerosis (MS is a chronic inflammatory disorder of the central nervous system (CNS. It involves damage to the myelin sheath surrounding axons and to the axons themselves. MS most often presents with a series of relapses and remissions but then evolves over a variable period of time into a slowly progressive form of neurological dysfunction termed secondary progressive MS (SPMS. The reasons for this change in clinical presentation are unclear. The absence of a diagnostic marker means that there is a lag time of several years before the diagnosis of SPMS can be established. At the same time, understanding the mechanisms that underlie SPMS is critical to the development of rational therapies for this untreatable stage of the disease. Results Using high performance liquid chromatography-coupled mass spectrometry (HPLC; we have established a highly specific and sensitive selected reaction monitoring (SRM assay. Our multiplexed SRM assay has facilitated the simultaneous detection of surrogate peptides originating from 26 proteins present in cerebrospinal fluid (CSF. Protein levels in CSF were generally ~200-fold lower than that in human sera. A limit of detection (LOD was determined to be as low as one femtomol. We processed and analysed CSF samples from a total of 22 patients with SPMS, 7 patients with SPMS treated with lamotrigine, 12 patients with non-inflammatory neurological disorders (NIND and 10 healthy controls (HC for the levels of these 26 selected potential protein biomarkers. Our SRM data found one protein showing significant difference between SPMS and HC, three proteins differing between SPMS and NIND, two proteins between NIND and HC, and 11 protein biomarkers showing significant difference between a lamotrigine-treated and untreated SPMS group. Principal component analysis (PCA revealed that these 26 proteins were correlated, and could be represented by four principal components. Overall, we established an

  17. Reactions between water-soluble organic acids and nitrates in atmospheric aerosols: Recycling of nitric acid and formation of organic salts

    Science.gov (United States)

    Wang, Bingbing; Laskin, Alexander

    2014-03-01

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate (Ca(NO3)2) occurs when nitrogen oxides and nitric acid (HNO3) react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here we present a systematic microanalysis study on chemical composition of laboratory-generated particles composed of water-soluble organic acids and nitrates (i.e., NaNO3 and Ca(NO3)2) using computer-controlled scanning electron microscopy with energy-dispersive X-ray microanalysis and Fourier transform infrared microspectroscopy. The results show that water-soluble organic acids can react with nitrates and release gaseous HNO3 during the dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase because of its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that, in turn, may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling that may further affect concentrations of gas and condensed phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  18. Pattern formation in a two-component reaction-diffusion system with delayed processes on a network

    Science.gov (United States)

    Petit, Julien; Asllani, Malbor; Fanelli, Duccio; Lauwens, Ben; Carletti, Timoteo

    2016-11-01

    Reaction-diffusion systems with time-delay defined on complex networks have been studied in the framework of the emergence of Turing instabilities. The use of the Lambert W-function allowed us to get explicit analytic conditions for the onset of patterns as a function of the main involved parameters, the time-delay, the network topology and the diffusion coefficients. Depending on these parameters, the analysis predicts whether the system will evolve towards a stationary Turing pattern or rather to a wave pattern associated to a Hopf bifurcation. The possible outcomes of the linear analysis overcome the respective limitations of the single-species case with delay, and that of the classical activator-inhibitor variant without delay. Numerical results gained from the Mimura-Murray model support the theoretical approach.

  19. Formation of a new copper(II) dimer through heterocyclic ligand ring opening reaction: Supramolecular features and magnetic properties

    Science.gov (United States)

    Gonçalves, Bruna Lisboa; Gervini, Vanessa Carratu; Flores, Alex Fabiani Claro; Junior, Jorge Luiz Pimentel; Bortoluzzi, Adailton João; Burrow, Robert Alan; Duarte, Rafael; da Silva, Robson Ricardo; Vicenti, Juliano Rosa de Menezes

    2017-01-01

    Two new compounds were synthesized and characterized in this work: the heterocycle (Z)-1-(4-(hydroxyimino)-3,5-dimethyl-1-(methylcarbamothioyl)-4,5-dihydro-1H-pyrazol-5-yl)-4-methylthiosemicarbazide and a copper(II) thiosemicarbazonato dimeric complex. Green prismatic single crystals of the dimer were obtained by the reaction of the heterocycle with copper(II) chloride dihydrate. Both compounds were essentially characterized by spectroscopic methods and X-ray diffraction crystallography. The crystal structures revealed molecules connected through supramolecular hydrogen bond interactions and copper(II) centers in a slightly distorted square-pyramidal environment. SQUID magnetometry performed for the dimer revealed both ferromagnetic and antiferromagnetic interactions in the studied complex, presenting a critical temperature of 19 K.

  20. Prediction and characterization of heat-affected zone formation due to neighboring nickel-aluminum multilayer foil reaction

    Energy Technology Data Exchange (ETDEWEB)

    Adams, David P. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Hirschfeld, Deidre A. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Hooper, Ryan J. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Manuel, Michelle V. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    Reactive multilayer foils have the potential to be used as local high intensity heat sources for a variety of applications. Much of the past research effort concerning these materials have focused on understanding the structure-property relationships of the foils that govern the energy released during a reaction. To enhance the ability of researchers to more rapidly develop technologies based on reactive multilayer foils, a deeper and more predictive understanding of the relationship between the heat released from the foil and microstructural evolution in the neighboring materials is needed. This work describes the development of a numerical model for the purpose of evaluating new foil-substrate combinations for screening and optimization. The model is experimentally validated using a commercially available Ni-Al multilayer foils and different alloys.

  1. Hydroxyl radical reaction with trans-resveratrol: initial carbon radical adduct formation followed by rearrangement to phenoxyl radical.

    Science.gov (United States)

    Li, Dan-Dan; Han, Rui-Min; Liang, Ran; Chen, Chang-Hui; Lai, Wenzhen; Zhang, Jian-Ping; Skibsted, Leif H

    2012-06-21

    In the reaction between trans-resveratrol (resveratrol) and the hydroxyl radical, kinetic product control leads to a short-lived hydroxyl radical adduct with an absorption maximum at 420 nm and a lifetime of 0.21 ± 0.01 μs (anaerobic acetonitrile at 25 °C) as shown by laser flash photolysis using N-hydroxypyridine-2(1H)-thione (N-HPT) as a "photo-Fenton" reagent. The transient spectra of the radical adduct are in agreement with density functional theory (DFT) calculations showing an absorption maximum at 442 or 422 nm for C2 and C6 hydroxyl adducts, respectively, and showing the lowest energy for the transition state leading to the C2 adduct compared to other radical products. From this initial product, the relative long-lived 4'-phenoxyl radical of resveratrol (τ = 9.9 ± 0.9 μs) with an absorption maximum at 390 nm is formed in a process with a time constant (τ = 0.21 ± 0.01 μs) similar to the decay constant for the C2 hydroxyl adduct (or a C2/C6 hydroxyl adduct mixture) and in agreement with thermodynamics identifying this product as the most stable resveratrol radical. The hydroxyl radical adduct to phenoxyl radical conversion with concomitant water dissociation has a rate constant of 5 × 10(6) s(-1) and may occur by intramolecular hydrogen atom transfer or by stepwise proton-assisted electron transfer. Photolysis of N-HPT also leads to a thiyl radical which adds to resveratrol in a parallel reaction forming a sulfur radical adduct with a lifetime of 0.28 ± 0.04 μs and an absorption maximum at 483 nm.

  2. Recent Theoretical Progress on Photochemical Reactions at the Solid/Solution Interface%固液界面光催化裂解水的理论进展

    Institute of Scientific and Technical Information of China (English)

    李晔飞; 刘智攀

    2012-01-01

    TiO2 nanoparticles have been widely utilized in photocatalysis,but the atomic level understanding on their working mechanism falls much short of expectations.In this short review,we briefly introduce the recent theoretical progress in photocatalysis carried out in our research group.Extensive density functional theory(DFT) calculations combined with the periodic continuum solvation model have been utilized to compute the electronic structure of extended surfaces,nanoparticles in aqueous solution and provide the reaction energetics for the key elementary reaction.It is demonstrated that the equilibrium shape of nanoparticle is sensitive to its size from 1 to 30 nm,and the sharp crystals possess much higher activity than the flat crystals in oxygen evolution of water splitting,which in combination lead to the morphology dependence of photocatalytic activity.%二氧化钛纳米颗粒作为一种光催化剂,目前已经得到了广泛的应用,但是对于光催化反应的理解,尤其是在原子水平上,还明显不足,如TiO2纳米颗粒的几何结构与光催化反应活性的构效关系。本文主要介绍了我们课题组在TiO2裂解水的一些理论研究进展。通过周期性密度泛函以及周期性连续介质模型的理论计算,我们研究了水析氧反应(OER)的机理,得出了反应的决速步骤是失去第一个质子的过程,同时研究了不同纳米颗粒对该决速步骤的影响。研究指出,TiO2纳米颗粒的热力学平衡构型在1—30nm内会受到其颗粒尺寸的显著影响;尖的TiO2纳米颗粒比扁的颗粒具有更高的OER反应活性。综合以上两个因素,最终导致了光催化反应的形态依赖性。

  3. Progressive developmental restriction, acquisition of left-right identity and cell growth behavior during lobe formation in mouse liver development.

    Science.gov (United States)

    Weiss, Mary C; Le Garrec, Jean-Francois; Coqueran, Sabrina; Strick-Marchand, Helene; Buckingham, Margaret

    2016-04-01

    To identify cell-based decisions implicated in morphogenesis of the mammalian liver, we performed clonal analysis of hepatocytes/hepatoblasts in mouse liver development, using a knock-in allele of Hnf4a/laacZ This transgene randomly undergoes a low frequency of recombination that generates a functional lacZ gene that produces β-galactosidase in tissues in which Hnf4a is expressed. Two types of β-galactosidase-positive clones were found. Most have undergone three to eight cell divisions and result from independent events (Luria-Delbrück fluctuation test); we calculate that they arose between E8.5 and E13.5. A second class was mega-clones derived from early endoderm progenitors, generating many descendants. Some originated from multi-potential founder cells, with labeled cells in the liver, pancreas and/or intestine. A few mega-clones populate only one side of the liver, indicating hepatic cell chirality. The patterns of labeled cells indicate cohesive and often oriented growth, notably in broad radial stripes, potentially implicated in the formation of liver lobes. This retrospective clonal analysis gives novel insights into clonal origins, cell behavior of progenitors and distinct properties of endoderm cells that underlie the formation and morphogenesis of the liver.

  4. STUDY OF REACTION SEQUENCES FOR FORMATION OF SOLID SOLUTION: 0,48 PbZrO3-0,47 PbTiO3-0,05 Pb (Cr1/5, Zn1/5, Sb 3/5 O3

    Directory of Open Access Journals (Sweden)

    N. Abdessalem

    2015-07-01

    Full Text Available To study the reaction sequences of formation of solid solution zirconate-lead titanate (PZT in this work, we took into account the effect of adding oxide dopants on the progress of the reaction, so we added oxides ZnO, Cr2O3, Sb2O3 to our material composition in small quantities so that the solid solution must verify the conditions of the perovskite structure. The results of the X-ray diffraction and thermal analysis allowed us to suggest a reaction mechanism. It is important to note that the substitution of a low concentration of ions forming the perovskite structure PZT (Pb2+, Zr4+ et Ti4+ by other ions (Zn2+, Cr3+ et Sb+5 in our study alters the reaction sequences training of the solid solution PZT and especially the formation of intermediate phase.

  5. Formation of NaCl-type monodeuteride LaD by the disproportionation reaction of LaD2.

    Science.gov (United States)

    Machida, A; Honda, M; Hattori, T; Sano-Furukawa, A; Watanuki, T; Katayama, Y; Aoki, K; Komatsu, K; Arima, H; Ohshita, H; Ikeda, K; Suzuya, K; Otomo, T; Tsubota, M; Doi, K; Ichikawa, T; Kojima, Y; Kim, D Y

    2012-05-18

    Previous x-ray diffraction measurements revealed the pressure-induced decomposition of an fcc LaH2.3 into H-rich and H-poor fcc phases around 11 GPa. The present neutron diffraction measurements on LaD2 confirm the formation of NaCl-type LaD as a counterpart of the D-rich LaD2+δ by disproportionation. First-principles enthalpy and lattice dynamic calculations demonstrate that the NaCl-type LaH is stabilized at high pressures and can be recovered at ambient conditions. Finding the NaCl-type LaH will pave the way for investigations on the site-dependent nature of hydrogen-metal interactions.

  6. Predictions of NO{sub x} formation in an NH{sub 3}-doped syngas flame using CFD combined with a detailed reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brink, A.; Norstroem, T.; Kilpinen, P.; Hupa, M. [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

    1997-12-31

    The formation of NO{sub x} in a CO/H{sub 2}/CH{sub 4}/NH{sub 3} jet in a co-flowing air stream was modeled by use of CFD combined with a comprehensive detailed reaction mechanism. The comprehensive mechanism involved 340 reversible elementary reactions between 55 species. Three different approaches to include the detailed reaction mechanism were tested. In approach I, all chemistry was described with the comprehensive mechanism. In approaches IIa and IIb the comprehensive mechanism was used in post-processing calculations of the nitrogen chemistry. In approach IIa, the temperatures of the reacting structures obtained in the main calculations were used, whereas in approach IIb, the inlet temperatures to the reacting structures were taken from the main calculation. In approach IIIa and IIIb, empirical reaction mechanisms describing the nitrogen chemistry were tested. The turbulence-chemistry interaction was accounted for with a new model, which combines the Eddy-Dissipation Concept with a model based on the `Exchange by Interaction with the Mean`. There was a clear difference between the computed results and the measured ones. The use of approach I resulted in an obvious overprediction of the lift-off height. The predicted molar NO{sub x} yield with the approaches IIa and IIb were 89 % and 85 %, respectively, whereas a yield of 23 % had been measured. With the empirical mechanisms used in approach IIIa, a similar NO{sub x} yield was predicted as with approaches IIa and IIb. With IIIb the predicted NO{sub x} yield was 40 %. However, in this case 67 % of the NH{sub 3} remained unreacted. The reason for the large difference between the calculated NO{sub x} yield and the measured one reported in the literature is a poor modeling of the initial part of the fuel jet. A possible reason for this is the coarse grid. (author) 15 refs.

  7. Genetic and biochemical analysis of solvent formation in Clostridium acetobutylicum. Progress report, September 1, 1992--July 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, G.N.; Rudolph, F.B.

    1997-01-01

    Several degenerate strains were isolated and characterized by sporulation, motility and growth properties. Cell appearance and colony morphology were also recorded. Enzymatic assays revealed reduced butyraldehyde dehydrogenase and Co-A transferase enzyme activities in the degenerates. DNA analysis revealed that in complete degenerate strains the genes of the solvent locus were absent. Gyrase inhibitors slightly reduced the growth rate and decreased acetone formation preferentially. In an effort to analyze the role of sporulation sigma factors in solvent gene expression, recombination experiments were conducted and led to strains with increased solvent production. Analysis of redox systems has resulted in the sequence analysis of a cluster encoding formyl transferase proteins and an oxidoreductase-like gene. The genes for the two subunits of an apparent electron transfer flavoprotein were sequenced and suggest this factor acts to carry electrons to the butyryl-CoA dehydrogenase. The genes encoding the Fo subunits of the membrane ATPase have been sequenced.

  8. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou

    2015-12-01

    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  9. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. V. Chemical dynamics of n-C4H3 formation from reaction of C(3Pj) with allene, H2CCCH2(X 1A1)

    Science.gov (United States)

    Kaiser, R. I.; Mebel, A. M.; Chang, A. H. H.; Lin, S. H.; Lee, Y. T.

    1999-06-01

    The crossed molecular beams technique was employed to investigate the reaction between ground state carbon atoms, C(3Pj), and allene, H2CCCH2(X 1A1), at two averaged collision energies of 19.6 and 38.8 kJ mol-1. Product angular distributions and time-of-flight spectra of C4H3 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The maximum translational energy release and the angular distributions combined with ab initio and RRKM calculations are consistent with the formation of the n-C4H3 radical in its electronic ground state. The channel to the i-C4H3 isomer contributes less than 1.5%. Reaction dynamics inferred from the experimental data indicate that the carbon atom attacks the π-orbitals of the allenic carbon-carbon double bond barrierless via a loose, reactant-like transition state located at the centrifugal barrier. The initially formed cyclopropylidene derivative rotates in a plane almost perpendicular to the total angular momentum vector around its C-axis and undergoes ring opening to triplet butatriene. At higher collision energy, the butatriene complex decomposes within 0.6 ps via hydrogen emission to form the n-C4H3 isomer and atomic hydrogen through an exit transition state located 9.2 kJ mol-1 above the products. The explicit identification of the n-C4H3 radical under single collision represents a further example of a carbon-hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a barrierless route to synthesize extremely reactive hydrocarbon radicals in combustion processes, interstellar chemistry, and hydrocarbon-rich atmospheres of Jupiter, Saturn, Titan, as well as Triton.

  10. CN radical hydrogenation from solid H2 reactions, an alternative way of HCN formation in the interstellar medium

    Science.gov (United States)

    Borget, Fabien; Müller, Sandra; Grote, Dirk; Theulé, Patrice; Vinogradoff, Vassilissa; Chiavassa, Thierry; Sander, Wolfram

    2017-01-01

    Context. Molecular hydrogen (H2) is the most abundant molecule of the interstellar medium (ISM) in gas phase and it has been assumed to exist in solid state or as coating on grains. Aims: Our goal is to show that solid H2 can act as a hydrogenation agent, reacting with CN radicals to form HCN. Methods: In a H2 matrix, we studied the hydrogenation of the CN radical generated from the vacuum ultraviolet photolysis (VUV-photolysis) of C2N2 at 3.8 K. We modified the wavelengths and the host gas in order to be sure that CN radicals can abstract H from H2 molecules. Results: HCN monomers, dimers, and oligomers have been characterised by Fourier transform infrared spectroscopy (FTIR). H2CN as well as CN radicals have also been clearly observed during the photolysis performed at 3.8 K. Conclusions: H2 is a hydrogenation reagent towards CN radicals producing HCN. This type of reaction should be taken into account for the reactivity at low temperature in contaminated H2 ice macro-particles (CHIMPs), H2 flakes or in the first sublayers of grains where solid H2 has accumulated.

  11. Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions.

    Science.gov (United States)

    Mel, Abdel-Aziz El; Tessier, Pierre-Yves; Buffiere, Marie; Gautron, Eric; Ding, JunJun; Du, Ke; Choi, Chang-Hwan; Konstantinidis, Stephanos; Snyders, Rony; Bittencourt, Carla; Molina-Luna, Leopoldo

    2016-06-01

    Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage.

  12. Progress in the Formation of Carbon-Hetero Bond Based on 2(5H)-Furanones%基于2(5H)-呋喃酮的碳-杂成键反应研究进展

    Institute of Scientific and Technical Information of China (English)

    谭越河; 李建晓; 洪文坤; 汪朝阳

    2011-01-01

    2(5H)-呋喃酮结构单元广泛存在于天然产物中,同时许多2(5H)-呋喃酮类化合物也是重要的有机合成中间体.因此,基于常见2(5H)-呋喃酮(1)的有机合成研究近年来引起了人们的关注.根据在有机合成反应中成键方式的不同,综述了在2(5H)-呋喃酮(1)环上形成C-O,C-N,C-S,C-P,C-Se,C-Si等碳-杂键的反应研究进展.%Recently, the organic synthesis based on 2(5H)-furanones (1) has attracted much attention owing to the unique carbon skeleton of 2(5H)-furanone which is widely present in a variety of natural products and their utility as valuable synthetic intermediates.Classified as different bond kinds, the progress in the formation reactions of carbon-oxygen bond, carbon-nitrogen bond, carbon-sulfur bond, carbon-phosphorus bond, carbon-selenium bond and carbon-silicon bond on 2(5H)-furanone ring is reviewed.

  13. Biogenic amine formation and nitrite reactions in meat batter as affected by high-pressure processing and chilled storage.

    Science.gov (United States)

    Ruiz-Capillas, C; Aller-Guiote, P; Carballo, J; Colmenero, F Jiménez

    2006-12-27

    Changes in biogenic amine formation and nitrite depletion in meat batters as affected by pressure-temperature combinations (300 MPa/30 min/7, 20, and 40 degrees C), cooking process (70 degrees C/30 min), and storage (54 days/2 degrees C) were studied. Changes in residual nitrite concentration in raw meat batters were conditioned by the temperature and not by the pressure applied. Cooking process decreased (P < 0.05) the residual nitrite concentration in all samples. High-pressure processing and cooking treatment increased (P < 0.05) the nitrate content. Whereas protein-bound nitrite concentration decreased with pressure processing, no effect was observed with the heating process of meat batters. High-pressure processing conditions had no effect on the rate of residual nitrite loss throughout the storage. The application of high pressure decreased (P < 0.05) the concentration of some biogenic amines (tyramine, agmatine, and spermine). Irrespective of the high processing conditions, generally, throughout storage biogenic amine levels did not change or increased, although quantitatively this effect was not very important.

  14. Matrix-isolation studies on the radiation-induced chemistry in H₂O/CO₂ systems: reactions of oxygen atoms and formation of HOCO radical.

    Science.gov (United States)

    Ryazantsev, Sergey V; Feldman, Vladimir I

    2015-03-19

    The radiation-induced transformations occurring upon X-ray irradiation of solid CO2/H2O/Ng systems (Ng = Ar, Kr, Xe) at 8-10 K and subsequent annealing up to 45 K were studied by Fourier transform infrared spectroscopy. The infrared (IR) spectra of deposited matrices revealed the presence of isolated monomers, dimers, and intermolecular H2O···CO2 complexes. Irradiation resulted in effective decomposition of matrix-isolated carbon dioxide and water yielding CO molecules and OH radicals, respectively. Annealing of the irradiated samples led to formation of O3, HO2, and a number of xenon hydrides of HXeY type (in the case of xenon matrices). The formation of these species was used for monitoring of the postirradiation thermally induced chemical reactions involving O and H atoms generated by radiolysis. It was shown that the radiolysis of CO2 in noble-gas matrices produced high yields of stabilized oxygen atoms. In all cases, the temperatures at which O atoms become mobile and react are lower than those of H atoms. Dynamics and reactivity of oxygen atoms was found to be independent of the precursor nature. In addition, the formation of HOCO radicals was observed in all the noble-gas matrices at remarkably low temperatures. The IR spectra of HOCO and DOCO were first characterized in krypton and xenon matrices. It was concluded that the formation of HOCO was mainly due to the radiation-induced evolution of the weakly bound H2O···CO2 complexes. This result indicates the significance of weak intermolecular interactions in the radiation-induced chemical processes in inert low-temperature media.

  15. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou

    2016-06-01

    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  16. Correlation between the Inhibition of Positronium Formation by Scavenger Molecules, and Chemical Reaction Rate of Electrons with these Molecules in Nonpolar Liquids

    DEFF Research Database (Denmark)

    Levay, B.; Mogensen, O. E.

    1977-01-01

    a correlation between the inhibition coefficient and the chemical rate constant of electrons with scavenger molecules. We found that the dependence of the inhibition coefficient on the work function (VOo)f electrons in different liquids shows a very unusual behavior, similar to that recently found...... for the chemical rate constants of quasifree electrons with the same scavenger molecules. The inhibition coefficient as a function of Vo had a maximum for C2HsBr, while it increased monotonously with decreasing V, for CC14. The inhibition coefficient for C2H5Br in a 1:l molar tetramethylsilane......-n-tetradecane mixture was found to be greater than in both of the pure components. The clear correlation found between electron scavenging rate constants and positronium inhibition constitutes the severest test to date of the spur reaction model of positronium formation. The importance of the positron annihilation...

  17. Formation of short-lived positron emitters in reactions of protons of energies up to 200 MeV with the target elements carbon, nitrogen and oxygen

    CERN Document Server

    Kettern, K; Qaim, S M; Shubin, Yu N; Steyn, G F; Van der Walt, T N; 10.1016/j.apradiso.2004.02.007

    2004-01-01

    Excitation functions were measured by the stacked-foil technique for proton induced reactions on carbon, nitrogen and oxygen leading to the formation of the short-lived positron emitters /sup 11/C (T/sub 1 /2/=20.38 min) and /sup 13/N (T/sub 1/2/=9.96 min). The energy region covered extended up to 200 MeV. The product activity was measured non-destructively via gamma -ray spectrometry. A careful decay curve analysis of the positron annihilation radiation was invariably performed. The experimental results were compared with theoretical data obtained using the modified hybrid nuclear model code ALICE-IPPE for intermediate energies. The agreement was found to be generally satisfactory. The data are of importance in proton therapy.

  18. Effect of different molecular weight chitosans on the mitigation of acrylamide formation and the functional properties of the resultant Maillard reaction products.

    Science.gov (United States)

    Chang, Yu-Wei; Sung, Wen-Chieh; Chen, Jing-Yi

    2016-05-15

    Mitigation of acrylamide formation and the functional properties of Maillard reaction products (MRPs) were investigated in a food model system. The system was composed of elements of mixtures and their combination including fructose, asparagine and different molecular weight chitosans. All solutions were heated, and then analyzed for acrylamide content, MRPs absorbance, pH, color, antioxidant capacity, antibacterial activity and kinematic viscosity. The fructose, asparagine and chitosan mixture had more MRPs compared to other mixtures. 1,1-Diphenyl-2-pricrylhydrazy (DPPH) radical scavenging activities, ferrous ion chelating abilities and reducing power results showed that all solutions containing a combination of two or three reactants had antioxidant capacities. Acrylamide content has a positive correlation with absorbance values at OD294 and OD420 but a negative correlation with the CIB L(∗) value of a solution (pacrylamide.

  19. Effect of theanine and polyphenols enriched fractions from decaffeinated tea dust on the formation of Maillard reaction products and sensory attributes of breads.

    Science.gov (United States)

    Culetu, Alina; Fernandez-Gomez, Beatriz; Ullate, Monica; del Castillo, Maria Dolores; Andlauer, Wilfried

    2016-04-15

    The antiglycoxidative properties of theanine (TEF) and polyphenols enriched fractions (PEF) prepared from tea dust were tested in a model system composed of bovine serum albumin (BSA) and methylglyoxal (MGO). PEF caused a decrease in available free amino groups of BSA in presence and absence of MGO, suggesting the simultaneous occurrence of glycoxidation reaction and phenols-protein interaction. The presence of PEF and TEF inhibited formation of fluorescent advanced glycation end-products (AGEs). Moreover, theanine (TB) and polyphenol-enriched bread (PB) were formulated. A significant increase in free amino groups was observed in TBs with a dose-response effect, while addition of PEF in bread produced a significant decrease (pfood ingredient allows obtaining a tasty food possessing health promoting properties and lower content of potential harmful compounds (AGEs).

  20. Mutational analysis of bacteriophage T4 RNA ligase 1. Different functional groups are required for the nucleotidyl transfer and phosphodiester bond formation steps of the ligation reaction.

    Science.gov (United States)

    Wang, Li Kai; Ho, C Kiong; Pei, Yi; Shuman, Stewart

    2003-08-08

    T4 RNA ligase 1 (Rnl1) exemplifies an ATP-dependent RNA ligase family that includes fungal tRNA ligase (Trl1) and a putative baculovirus RNA ligase. Rnl1 acts via a covalent enzyme-AMP intermediate generated by attack of Lys-99 N zeta on the alpha phosphorus of ATP. Mutation of Lys-99 abolishes ligase activity. Here we tested the effects of alanine mutations at 19 conserved positions in Rnl1 and thereby identified 9 new residues essential for ligase activity: Arg-54, Lys-75, Phe-77, Gly-102, Lys-119, Glu-227, Gly-228, Lys-240, and Lys-242. Seven of the essential residues are located within counterparts of conserved nucleotidyltransferase motifs I (99KEDG102), Ia (118SK119), IV (227EGYVA231), and V (238HFKIK242) that comprise the active sites of DNA ligases, RNA capping enzymes, and T4 RNA ligase 2. Three other essential residues, Arg-54, Lys-75 and Phe-77, are located upstream of the AMP attachment site within a conserved domain unique to the Rnl1-like ligase family. We infer a shared evolutionary history and active site architecture in Rnl1 (a tRNA repair enzyme) and Trl1 (a tRNA splicing enzyme). We determined structure-activity relationships via conservative substitutions and examined mutational effects on the isolated steps of Rnl1 adenylylation (step 1) and phosphodiester bond formation (step 3). Lys-75, Lys-240, and Lys-242 were found to be essential for step 1 and overall ligation of 5'-phosphorylated RNA but not for phosphodiester bond formation. These results suggest that the composition of the Rnl1 active site is different during steps 1 and 3. Mutations at Arg-54 and Lys-119 abolished the overall RNA ligation reaction without affecting steps 1 and 3. Arg-54 and Lys-119 are thereby implicated as specific catalysts of the RNA adenylation reaction (step 2) of the ligation pathway.

  1. Catalytic effects of silver plasmonic nanoparticles on the redox reaction leading to ABTS˙(+) formation studied using UV-visible and Raman spectroscopy.

    Science.gov (United States)

    Garcia-Leis, A; Jancura, D; Antalik, M; Garcia-Ramos, J V; Sanchez-Cortes, S; Jurasekova, Z

    2016-09-29

    ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) is a compound extensively employed to evaluate the free radical trapping capacity of antioxidant agents and complex mixtures such as biological fluids or foods. This evaluation is usually performed by using a colourimetric experiment, where preformed ABTS radical cation (ABTS˙(+)) molecules are reduced in the presence of an antioxidant causing an intensity decrease of the specific ABTS˙(+) UV-visible absorption bands. In this work we report a strong effect of silver plasmonic nanoparticles (Ag NPs) on ABTS leading to the formation of ABTS˙(+). The reaction of ABTS with Ag NPs has been found to be dependent on the interfacial and plasmonic properties of NPs. Specifically, this reaction is pronounced in the presence of spherical nanoparticles prepared by the reduction of silver nitrate with hydroxylamine (AgH) and in the case of star-shaped silver nanoparticles (AgNS). On the other hand, spherical nanoparticles prepared by the reduction of silver nitrate with citrate apparently do not react with ABTS. Additionally, the formation of ABTS˙(+) is investigated by surface-enhanced Raman scattering (SERS) and the assignment of the most intense vibrational bands of this compound is performed. The SERS technique enables us to detect this radical cation at very low concentrations of ABTS (∼2 μM). Altogether, these findings allow us to suggest the use of ABTS/Ag NPs-systems as reliable and easy going substrates to test the antioxidant capacity of various compounds, even at concentrations much lower than those usually used in the spectrophotometric assays. Moreover, we have suggested that ABTS could be employed as a suitable agent to investigate the interfacial and plasmonic properties of the metal nanoparticles and, thus, to characterize the nanoparticle metal systems employed for various purposes.

  2. Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

    Science.gov (United States)

    Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

    2017-03-01

    The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

  3. Epitope reactions can be gauged by relative antibody discriminating specificity (RADS values supported by deletion, substitution and cysteine bridge formation analyses: potential uses in pathogenesis studies

    Directory of Open Access Journals (Sweden)

    Falconar Andrew K I

    2012-07-01

    Full Text Available Abstract Background Epitope-mapping of infectious agents is essential for pathogenesis studies. Since polyclonal antibodies (PAbs and monoclonal antibodies (MAbs are always polyspecific and can react with multiple epitopes, it is important to distinguish between specific and non-specific reactions. Relative antibody discriminating specificity (RADS values, obtained from their relative ELISA reactions with L-amino acid peptides prepared in the natural versus reverse orientations (x-fold absorbance natural/absorbance reverse = RADS value may be valuable for this purpose. PAbs generated against the dengue type-2 virus (DENV-2 nonstructural-1 (NS1 glycoprotein candidate vaccine also reacted with both DENV envelope (E glycoproteins and blood-clotting proteins. New xKGSx/xSGKx amino acid motifs were identified on DENV-2 glycoproteins, HIV-1 gp41 and factor IXa. Their potential roles in DENV and HIV-1 antibody-enhanced replication (AER and auto-immunity were assessed. In this study, a RADS values were determined for MAbs and PAbs, generated in congeneic (H2: class II mice against DENV NS1 glycoprotein epitopes, to account for their cross-reaction patterns, and b MAb 1G5.3 reactions with xKGSx/xSGKx motifs present in the DENV-4 NS1, E and HIV-1 glycoproteins and factor IXa were assessed after the introduction of amino acid substitutions, deletions, or intra-/inter-cysteine (C-C bridges. Results MAbs 1H7.4, 5H4.3, 3D1.4 and 1G5.3 had high (4.23- to 16.83-fold RADS values against single epitopes on the DENV-2 NS1 glycoprotein, and MAb 3D1.4 defined the DENV complex-conserved LX1 epitope. In contrast, MAbs 1G5.4-A1-C3 and 1C6.3 had low (0.47- to 1.67-fold RADS values against multiple epitopes. PAb DENV complex-reactions occurred through moderately-high (2.77- and 3.11-fold RADS values against the LX1 epitope. MAb 1G5.3 reacted with xSGKx motifs present in DENV-4 NS1 and E glycoproteins, HIV-1 gp41 and factor IXa, while natural C-C bridge formations or

  4. The reaction of the acrylonitrile ion CH 2dbnd CH-C tbnd N rad + with HCN: Proton-transport catalysis vs formation of ionized pyrimidine

    Science.gov (United States)

    Ervasti, Henri K.; Jobst, Karl J.; Gerbaux, Pascal; Burgers, Peter C.; Ruttink, Paul J. A.; Terlouw, Johan K.

    2009-11-01

    The CBS-QB3 model chemistry predicts that the title ion-molecule reaction, of potential interest in astrochemistry, yields a stable head-to-tail dimer, [HC dbnd N-CH 2C(H)C tbnd N] rad + ( D1). Cyclization of D1 into ionized pyrimidine seems possible, but the initiating 1,2-H shift is close in energy to back-dissociation into CH 2dbnd C(H)CN rad + ( AN) + HCN. Less energy demanding is formation of the H-bridged isomers [CH 2dbnd C(CN)H--N tbnd CH] rad + and [HC tbnd N--HC(H) dbnd C(H)CN] rad +, whose HCN component may catalyze isomerization of AN into CH 2dbnd C dbnd C dbnd NH rad + ( AN1) and CH dbnd C(H)C dbnd NH rad + ( AN2) respectively. Tandem mass spectrometry based experiments using 15N/ 13C labelling show that cyclization of D1 does not occur and that AN1 is the predominant reaction product instead.

  5. Formation of CoAl2O4 Nanoparticles via Low-Temperature Solid-State Reaction of Fine Gibbsite and Cobalt Precursor

    Directory of Open Access Journals (Sweden)

    Natpakan Srisawad

    2012-01-01

    Full Text Available Nanocrystalline cobalt aluminate (CoAl2O4 was synthesized by the solid-state reaction method with cobalt chloride hexahydrate (CoCl2 · 6H2O as the source of Co and gibbsite (Al(OH3 as the source of Al, respectively. The effects of particle size of the starting fine gibbsite (0.6 and 13 μm and calcination temperatures (450, 550, and 650°C on the properties of CoAl2O4 were investigated by means of X-ray diffraction (XRD, thermogravimetry analysis and differential thermal analysis (TG/DTA, X-ray photoelectron spectroscopy (XPS, UV-visible absorption spectroscopy (UV-Vis, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. Increasing of calcination temperature promoted the insertion amounts of Co2+ in alumina matrix in CoAl2O4 structure, which resulted in the brighter blue particles and increasing of UV spectra band. The lowest temperature for the formation of nanocrystalline CoAl2O4 particles was 550°C for the solid-state reaction of cobalt chloride and 0.6 μm fine gibbsite.

  6. Reactions of the class II peroxidases, lignin peroxidase and Arthromyces ramosus peroxidase, with hydrogen peroxide. Catalase-like activity, compound III formation, and enzyme inactivation.

    Science.gov (United States)

    Hiner, Alexander N P; Hernández-Ruiz, Josefa; Rodríguez-López, José Neptuno; García-Cánovas, Francisco; Brisset, Nigel C; Smith, Andrew T; Arnao, Marino B; Acosta, Manuel

    2002-07-26

    The reactions of the fungal enzymes Arthromyces ramosus peroxidase (ARP) and Phanerochaete chrysosporium lignin peroxidase (LiP) with hydrogen peroxide (H(2)O(2)) have been studied. Both enzymes exhibited catalase activity with hyperbolic H(2)O(2) concentration dependence (K(m) approximately 8-10 mm, k(cat) approximately 1-3 s(-1)). The catalase and peroxidase activities of LiP were inhibited within 10 min and those of ARP in 1 h. The inactivation constants were calculated using two independent methods; LiP, k(i) approximately 19 x 10(-3) s(-1); ARP, k(i) approximately 1.6 x 10(-3) s(-1). Compound III (oxyperoxidase) was detected as the majority species after the addition of H(2)O(2) to LiP or ARP, and its formation was accompanied by loss of enzyme activity. A reaction scheme is presented which rationalizes the turnover and inactivation of LiP and ARP with H(2)O(2). A similar model is applicable to horseradish peroxidase. The scheme links catalase and compound III forming catalytic pathways and inactivation at the level of the [compound I.H(2)O(2)] complex. Inactivation does not occur from compound III. All peroxidases studied to date are sensitive to inactivation by H(2)O(2), and it is suggested that the model will be generally applicable to peroxidases of the plant, fungal, and prokaryotic superfamily.

  7. Employing CO2 as reaction medium for in-situ suppression of the formation of benzene derivatives and polycyclic aromatic hydrocarbons during pyrolysis of simulated municipal solid waste.

    Science.gov (United States)

    Lee, Jechan; Choi, Dongho; Tsang, Yiu Fai; Oh, Jeong-Ik; Kwon, Eilhann E

    2017-05-01

    This study proposes a strategic principle to enhance the thermal efficiency of pyrolysis of municipal solid waste (MSW). An environmentally sound energy recovery platform was established by suppressing the formation of harmful organic compounds evolved from pyrolysis of MSW. Using CO2 as reaction medium/feedstock, CO generation was enhanced through the following: 1) expediting the thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of the MSWs and 2) directly reacting VOCs with CO2. This particular influence of CO2 on pyrolysis of the MSWs also led to the in-situ mitigation of harmful organic compounds (e.g., benzene derivatives and polycyclic aromatic hydrocarbons (PAHs)) considering that CO2 acted as a carbon scavenger to block reaction pathways toward benzenes and PAHs in pyrolysis. To understand the fundamental influence of CO2, simulated MSWs (i.e., various ratios of biomass to polymer) were used to avoid any complexities arising from the heterogeneous matrix of MSW. All experimental findings in this study suggested the foreseeable environmental application of CO2 to energy recovery from MSW together with disposal of MSW. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2

    Science.gov (United States)

    Maeda, Fumiya; Ohtani, Eiji; Kamada, Seiji; Sakamaki, Tatsuya; Hirao, Naohisa; Ohishi, Yasuo

    2017-01-01

    Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle. PMID:28084421

  9. Replacement of tyrosine residues by phenylalanine in cytochrome P450cam alters the formation of Cpd II-like species in reactions with artificial oxidants.

    Science.gov (United States)

    Spolitak, Tatyana; Dawson, John H; Ballou, David P

    2008-05-01

    Our previous rapid-scanning stopped-flow studies of the reaction of substrate-free cytochrome P450cam with peracids [Spolitak et al. (2005) J Biol Chem 280:20300-20309; (2006) J Inorg Biochem 100:2034-2044] spectrally characterized compound I [ferryl iron plus a porphyrin pi-cation radical (Fe(IV) = O/Por(+))], as well as Cpd ES (Fe(IV) = O/Tyr.). In the present studies, we report how the substitutions in Y75F, Y96F, and Y96F/Y75F P450cam variants permit the formation of a species we attribute to Cpd II (Fe(IV) = O) in reactions with peracids and cumene hydroperoxide. These variants produce changes in hydrogen bonding patterns and increased hydrophobicity that affect the ratio of heterolytic to homolytic pathways in reactions with cumene hydroperoxide, resulting in a shift of this ratio from 84/16 for WT to 72/28 for the Y96F/Y75F double mutant. Various ways of generating the Cpd II-like species were explored, and it was possible, especially with the more hydrophobic variants, to generate large fractions of the P450cam variants as Cpd II. The Cpd II-like species is ineffective at hydroxylating camphor, but can be readily reduced by ascorbate (as well as other peroxidase substrates) to ferric P450cam, which could then bind camphor to form the high-spin heme. The difference in the spectral properties of Cpd ES and Cpd II was rationalized as possibly being due to different states of protonation.

  10. The geochemical reactions resulting from CO{sub 2} injection into the Midale Formation, Weyburn oilfield : a laboratory experimental and modelling study

    Energy Technology Data Exchange (ETDEWEB)

    Azaroual, M.; Durst, P.; Czernichowski-Lauriol, I. [Bureau de Recherches Geologiques et Minieres, Orleans (France); Olsen, D.; Stentoft, N.; Springer, N. [Geological Survey of Denmark and Greenland (Denmark); Rochelle, C.A.; Pearce, J.; Bateman, K.; Birchall, D. [British Geological Survey, Nottingham (United Kingdom)

    2005-07-01

    One aspect of the International Energy Agency's (IEA) Weyburn CO2 Monitoring and Storage Project is the identification of geochemical changes that occur following the injection of carbon dioxide (CO{sub 2}) into the Midale Formation of the Weyburn Field in southern Saskatchewan. This paper summarized the fluid chemical and mineralogical changes noted during laboratory experiments on Midale core from the Weyburn Field. The reactions between injected CO{sub 2}, Midale lithologies and porewaters under temperatures and pressures representative of in-situ conditions were explored. The laboratory studies involved closed system batch experiments reacting samples of Midale reservoir rocks and cap rock with synthetic saline reservoir porewaters. Flow experiments were also performed based on both core flood approaches and column experiments. The duration of experiments ranged from 1 week to 6 months. Changes in fluid chemistry, mineralogy, porosity and permeability were measured. The results were then used to verify predictions from geochemical modelling activities. Experimental and theoretical studies of the effects of CO{sub 2} injection into the Midale lithologies showed variable amounts of carbonate mineral dissolution, some precipitation of gypsum, inhibition of anhydrite dissolution, and slow reactivity of alumino-silicate minerals. These indications helped develop an hypothesis and approaches to simulate the long term evolution of a one dimensional model representing CO{sub 2} injection into the host Midale Marly formation. . 3 refs., 4 figs.

  11. H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices: an extended view on complex organic molecule formation

    CERN Document Server

    Chuang, K -J; Ioppolo, S; van Dishoeck, E F; Linnartz, H

    2016-01-01

    Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-H2CO-CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical&chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addit...

  12. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    Science.gov (United States)

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK.

  13. Construction, Modeling and Testing of a Low-Flow, Large-Diameter Aerosol Flow System for the Study of the Formation and Reactions of Tropospheric Aerosols

    Science.gov (United States)

    Ezell, M. J.; Johnson, S. N.; Yu, Y.; Pokkunuri, P.; Perraud, V.; Bruns, E.; Alexander, M.; Zelenyuk, A.; Dabdub, D.; Finlayson-Pitts, B. J.

    2008-12-01

    A unique, high-volume, low-flow, stainless steel aerosol flow system for the study of the formation and reactions of aerosols relevant to the troposphere has been constructed, modeled and experimentally tested. The total flow tube length is 7.3 m which includes a 1.2 m section used for mixing. The flow tube is equipped with ultraviolet lamps for photolysis. The diameter of 0.45 m results in a smaller surface to volume ratio than is found in many other flow systems and reduces the contribution of wall reactions. The latter is also reduced by frequent cleaning of the flow tube walls which is feasible due to the ease of disassembly of the flow tube. Flow systems present a major advantage over chamber studies in that continuous sampling under stable conditions over long periods of time is possible, increasing the amount of sample available for analysis and permitting a wide variety of analytical techniques to be applied simultaneously. In this system, the large volume (1000 L) and low flow speed (2 cm/minute) result in a residence time of nearly an hour; and equally spaced sampling ports allow for time-resolved measurements of aerosol and gas-phase products. The central features of this system have been modeled using computational fluid dynamics software and experimentally probed using inert gases and aerosols. Instrumentation attached directly to this flow system includes a NOx analyzer, an ozone analyzer, relative humidity and temperature probes, a scanning mobility particle sizer (SMPS) spectrometer, an aerodynamic particle sizer (APS) spectrometer, GC-MS, integrating nephelometer, and FTIR. Particles are collected using impactors and filters, and analyzed by a variety of techniques including FTIR, electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS), GC-MS, HPLC-UV and HPLC-MS. In addition, for selected studies, an aerosol mass spectrometer (AMS), a single particle mass spectrometer (SPLAT II) and

  14. Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2 -Scrubbing Solutions.

    Science.gov (United States)

    Scott, Martin; Blas Molinos, Beatriz; Westhues, Christian; Franciò, Giancarlo; Leitner, Walter

    2017-03-22

    Aqueous biphasic systems were investigated for the production of formate-amine adducts by metal-catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm)2 Cl2 ] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate-amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h(-1) and an initial TOF of approximately 180 000 h(-1) was achieved in the presence of NEt3 . Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2 -scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5-10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×10(3)  h(-1) with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization.

  15. PETROGENESIS OF THE METACARBONATE AND RELATED ROCKS OF THE SILGARÁ FORMATION, CENTRAL SANTANDER MASSIF, COLOMBIAN ANDES: AN OVERVIEW OF A “REACTION CALCIC EXOSCARN”

    Directory of Open Access Journals (Sweden)

    Castellanos O.M

    2008-06-01

    Full Text Available Metacarbonate rocks (pure and impure marbles, carbonate-silicate rocks, calc-silicate rocks and carbonate-bearing silicate rocks form a very complex group within the metamorphic sequence of the Silgará Formation at the central Santander Massif (CSM. These rocks are interpreted as derived from a sedimentary sequence (including limestones and dolostones, carbonate-bearing mudstones,  sandstones, tuffaceous and evaporitic sediments and marlstones overprinted by near-isochemical regional metamorphism. They usually appear as scarce intercalations from millimeter up to meter scale, within the high-grade pelitic rocks, in the lower part of the metamorphic section, although the proportion of metacarbonate rocks can be higher and different marble layers are exploited. We report for the first time the occurrence of a "reaction calcic exoskarn", which corresponds to
    such metacarbonate rocks, taking into account that a skarn can be developed during regional metamorphism and by different metasomatic processes, adjacent to intrusive bodies, along faults and shear zones, and what defines these rocks as a skarn is its mineralogy, which includes a variety of calc-silicate and associated minerals, usually dominated by garnet and pyroxene. Therefore, this paper focus attention to the occurrence of metacarbonate and
    related rocks, which occurs as small scale reactions zones that show a gradational contact from garnet-bearing pelitic rocks to marbles or carbonate-silicate rocks, giving particular interest to the calc-silicate rocks, which are characterized by the presence of elongated grains of banded clinopyroxene (diopside and scapolite and massive
    or scattered garnet. Several reaction-zones occur in the contact between impure calcite marble and garnet-bearing metapelite and the sequence of mineral assemblages in these reaction zones is: biotite + plagioclase K-feldspar garnet (Zone I, biotite + plagioclase K-feldspar garnet staurolite epidote

  16. Dicarbonyl Intermediates in the Maillard Reaction

    National Research Council Canada - National Science Library

    THORNALLEY, PAUL J

    2005-01-01

    A bstract : The complexity of the Maillard reaction arises partly from multiple fragmentation reactions of the sugar moiety, constituting branch points in the reaction progress and establishing many parallel reaction pathways...

  17. Histone deacetylase inhibitors SAHA and sodium butyrate block G1-to-S cell cycle progression in neurosphere formation by adult subventricular cells

    Directory of Open Access Journals (Sweden)

    Doughty Martin L

    2011-05-01

    Full Text Available Abstract Background Histone deacetylases (HDACs are enzymes that modulate gene expression and cellular processes by deacetylating histones and non-histone proteins. While small molecule inhibitors of HDAC activity (HDACi are used clinically in the treatment of cancer, pre-clinical treatment models suggest they also exert neuroprotective effects and stimulate neurogenesis in neuropathological conditions. However, the direct effects of HDACi on cell cycle progression and proliferation, two properties required for continued neurogenesis, have not been fully characterized in adult neural stem cells (NSCs. In this study, we examined the effects of two broad class I and class II HDACi on adult mouse NSCs, the hydroxamate-based HDACi suberoylanilide hydroxamic acid (vorinostat, SAHA and the short chain fatty acid HDACi sodium butyrate. Results We show that both HDACi suppress the formation of neurospheres by adult mouse NSCs grown in proliferation culture conditions in vitro. DNA synthesis is significantly inhibited in adult mouse NSCs exposed to either SAHA or sodium butyrate and inhibition is associated with an arrest in the G1 phase of the cell cycle. HDACi exposure also resulted in transcriptional changes in adult mouse NSCs. Cdk inhibitor genes p21 and p27 transcript levels are increased and associated with elevated H3K9 acetylation levels at proximal promoter regions of p21 and p27. mRNA levels for notch effector Hes genes and Spry-box stem cell transcription factors are downregulated, whereas pro-neural transcription factors Neurog1 and Neurod1 are upregulated. Lastly, we show HDAC inhibition under proliferation culture conditions leads to long-term changes in cell fate in adult mouse NSCs induced to differentiate in vitro. Conclusion SAHA and sodium butyrate directly regulate cdk inhibitor transcription to control cell cycle progression in adult mouse NSCs. HDAC inhibition results in G1 arrest in adult mouse NSCs and transcriptional changes

  18. Solving The Long-Standing Problem Of Low-Energy Nuclear Reactions At The Highest Microscopic Level. Annual Continuation And Progress Report, August 15, 2014 -- August 14, 2015

    Energy Technology Data Exchange (ETDEWEB)

    Quaglioni, Sofia [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2015-03-19

    The aim of this project is to develop a comprehensive framework that will lead to a fundamental description of both structural properties and reactions of light nuclei in terms of constituent protons and neutrons interacting through nucleon-nucleon (NN) and three-nucleon (3N) forces. This project will provide the research community with the theoretical and computational tools what will enable: an accurate prediction for fusion reactions that power stars and Earth-based fusion facilities; an improved description of the spectroscopy of exotic nuclei, including light Borromean systems; and, a fundamental understanding of the three-nucleon force in nuclear reaction and nuclei at the drip line.

  19. Nuclear excitations and reaction mechanisms. Progress report, 1 November 1979-30 September 1980. [Dept. of Physics, Brown Univ. , Providence, Rhode Island

    Energy Technology Data Exchange (ETDEWEB)

    1980-10-01

    Among the topics investigated were the following: photon scattering and consistency condition between seagull quadrupole terms and the absorption sum rule; Raman scattering to negative-parity states; nonlocal terms due to exchange and retardation effects in charge-transfer reactions; consistency and meaning of various approximate channel coupling array equations; derivation of equations used in empirical nuclear reaction analyses; multicluster, n-particle scattering theory; converged molecular bound state calculations; c