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Sample records for hemoglobin chemical reactivity

  1. Chemical Reactivity Test (CRT)

    Energy Technology Data Exchange (ETDEWEB)

    Zaka, F. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-13

    The Chemical Reactivity Test (CRT) is used to determine the thermal stability of High Explosives (HEs) and chemical compatibility between (HEs) and alien materials. The CRT is one of the small-scale safety tests performed on HE at the High Explosives Applications Facility (HEAF).

  2. Interactive chemical reactivity exploration.

    Science.gov (United States)

    Haag, Moritz P; Vaucher, Alain C; Bosson, Maël; Redon, Stéphane; Reiher, Markus

    2014-10-20

    Elucidating chemical reactivity in complex molecular assemblies of a few hundred atoms is, despite the remarkable progress in quantum chemistry, still a major challenge. Black-box search methods to find intermediates and transition-state structures might fail in such situations because of the high-dimensionality of the potential energy surface. Here, we propose the concept of interactive chemical reactivity exploration to effectively introduce the chemist's intuition into the search process. We employ a haptic pointer device with force feedback to allow the operator the direct manipulation of structures in three dimensions along with simultaneous perception of the quantum mechanical response upon structure modification as forces. We elaborate on the details of how such an interactive exploration should proceed and which technical difficulties need to be overcome. All reactivity-exploration concepts developed for this purpose have been implemented in the samson programming environment. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Interactive Chemical Reactivity Exploration

    CERN Document Server

    Haag, Moritz P; Bosson, Mael; Redon, Stephane; Reiher, Markus

    2014-01-01

    Elucidating chemical reactivity in complex molecular assemblies of a few hundred atoms is, despite the remarkable progress in quantum chemistry, still a major challenge. Black-box search methods to find intermediates and transition-state structures might fail in such situations because of the high-dimensionality of the potential energy surface. Here, we propose the concept of interactive chemical reactivity exploration to effectively introduce the chemist's intuition into the search process. We employ a haptic pointer device with force-feedback to allow the operator the direct manipulation of structures in three dimensions along with simultaneous perception of the quantum mechanical response upon structure modification as forces. We elaborate on the details of how such an interactive exploration should proceed and which technical difficulties need to be overcome. All reactivity-exploration concepts developed for this purpose have been implemented in the Samson programming environment.

  4. Reactivation of fetal hemoglobin in thalassemia and sickle cell disease

    Directory of Open Access Journals (Sweden)

    Sandro Eridani

    2014-09-01

    Full Text Available Considerable attention has been recently devoted to mechanisms involved in the perinatal hemoglobin switch, as it was long ago established that the survival of fetal hemoglobin (HbF production in significant amount can reduce the severity of the clinical course in severe disorders like β-thalassemia and sickle cell disease (SCD. For instance, when β-thalassemia is associated with hereditary persistence of fetal hemoglobin (HPFH the disease takes a mild course, labeled as thalassemia intermedia. The same clinical amelioration occurs for the association between HPFH and SCD. As for the mechanism of this effect, some information has been obtained from the study of natural mutations at the human β-globin locus in patients with increased HbF, like the Corfu thalassemia mutations. Important evidence came from the discovery that drugs capable of improving the clinical picture of SCD, like decitabine ad hydroxycarbamide, are acting through the reactivation, to some extent, of HbF synthesis. The study of the mechanism of action of these compounds was followed by the identification of some genetic determinants, which promote this event. In particular, among a few genetic factors involved in this process, the most relevant appears the BCL11A gene, which is now credited to be able to silence γ-globin genes in the perinatal period by interaction with several erythroid-specific transcription factors and is actually considered as a barrier to HbF reactivation by known HbF inducing agents. Epigenetics is also a player in the process, mainly through DNA demethylation. This is certified by the recent demonstration that hypomethylating agents such as 5-azacytidine and decitabine, the first compounds used for HbF induction by pharmacology, act as irreversible inhibitors of demethyltransferase enzymes. Great interest has also been raised by the finding that several micro-RNAs, which act as negative regulators of gene expression, have been implicated in the

  5. Hemoglobin induces colon cancer cell proliferation by release of reactive oxygen species

    Institute of Scientific and Technical Information of China (English)

    Ryung-Ah Lee; Hyun-Ah Kim; Bo-Young Kang; Kwang-Ho Kim

    2006-01-01

    AIM: To study whether hemoglobin could amplify colon cancer cell proliferation via reactive oxygen species (ROS)production.METHODS: Colon cancer cell line HT-29 was grown in the conventional method using RPMI1640 media. The viability of the cells was measured using the colorimetric MTT [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide] assay after adding hemoglobin. We determined reactive oxygen species levels to be indicators of oxidative stress in HT 29 cell lines with and without hemoglobin and/or 5-fluorouracil (5-FU), 5'-deoxy-5-fluorouridine (5-DFUR) using fluorometric dichlorofluorescin diacetate (DCFH-DA) assay.RESULTS: Cellular proliferation was increased with hemoglobin in a concentration-dependent manner. A significant increment on ROS levels was found in HT 29 cells following hemoglobin incubation. The cytotoxic effects of 5-FU and 5-DFUR were significantly blunted by administration of hemoglobin. There was a slight increase of peroxiredoxin 1, superoxide dismutase 1 concentration according to different hemoglobin concentrations.CONCLUSION: Hemoglobin has a cellular proliferative effect on HT-29 colon cancer cell line by production of ROS. Also, hemoglobin abates cytotoxic effects of chemotherapeutic agents such as 5-FU and 5-DFUR.

  6. Quantum Entanglement and Chemical Reactivity.

    Science.gov (United States)

    Molina-Espíritu, M; Esquivel, R O; López-Rosa, S; Dehesa, J S

    2015-11-10

    The water molecule and a hydrogenic abstraction reaction are used to explore in detail some quantum entanglement features of chemical interest. We illustrate that the energetic and quantum-information approaches are necessary for a full understanding of both the geometry of the quantum probability density of molecular systems and the evolution of a chemical reaction. The energy and entanglement hypersurfaces and contour maps of these two models show different phenomena. The energy ones reveal the well-known stable geometry of the models, whereas the entanglement ones grasp the chemical capability to transform from one state system to a new one. In the water molecule the chemical reactivity is witnessed through quantum entanglement as a local minimum indicating the bond cleavage in the dissociation process of the molecule. Finally, quantum entanglement is also useful as a chemical reactivity descriptor by detecting the transition state along the intrinsic reaction path in the hypersurface of the hydrogenic abstraction reaction corresponding to a maximally entangled state.

  7. Green chemical engineering aspects of reactive distillation.

    Science.gov (United States)

    Malone, Michael F; Huss, Robert S; Doherty, Michael F

    2003-12-01

    Reactive or catalytic distillation technology combines chemical synthesis steps with separations by distillation. This combination can lead to intensified, high-efficiency process systems with significant green engineering attributes. New applications and understanding have prompted growth in the use of reactive distillation for a variety of chemical syntheses, especially esterifications and etherifications involving oxygenated hydrocarbons. We describe several applications and the potential and tradeoffs for reactive distillation technology in the context of green engineering principles.

  8. Hemoglobin fructation promotes heme degradation through the generation of endogenous reactive oxygen species.

    Science.gov (United States)

    Goodarzi, M; Moosavi-Movahedi, A A; Habibi-Rezaei, M; Shourian, M; Ghourchian, H; Ahmad, F; Farhadi, M; Saboury, A A; Sheibani, N

    2014-09-15

    Protein glycation is a cascade of nonenzymatic reactions between reducing sugars and amino groups of proteins. It is referred to as fructation when the reducing monosaccharide is fructose. Some potential mechanisms have been suggested for the generation of reactive oxygen species (ROS) by protein glycation reactions in the presence of glucose. In this state, glucose autoxidation, ketoamine, and oxidative advance glycation end products (AGEs) formation are considered as major sources of ROS and perhaps heme degradation during hemoglobin glycation. However, whether fructose mediated glycation produces ROS and heme degradation is unknown. Here we report that ROS (H2O2) production occurred during hemoglobin fructation in vitro using chemiluminescence methods. The enhanced heme exposure and degradation were determined using UV-Vis and fluorescence spectrophotometry. Following accumulation of ROS, heme degradation products were accumulated reaching a plateau along with the detected ROS. Thus, fructose may make a significant contribution to the production of ROS, glycation of proteins, and heme degradation during diabetes.

  9. Hemoglobin fructation promotes heme degradation through the generation of endogenous reactive oxygen species

    Science.gov (United States)

    Goodarzi, M.; Moosavi-Movahedi, A. A.; Habibi-Rezaei, M.; Shourian, M.; Ghourchian, H.; Ahmad, F.; Farhadi, M.; Saboury, A. A.; Sheibani, N.

    2014-09-01

    Protein glycation is a cascade of nonenzymatic reactions between reducing sugars and amino groups of proteins. It is referred to as fructation when the reducing monosaccharide is fructose. Some potential mechanisms have been suggested for the generation of reactive oxygen species (ROS) by protein glycation reactions in the presence of glucose. In this state, glucose autoxidation, ketoamine, and oxidative advance glycation end products (AGEs) formation are considered as major sources of ROS and perhaps heme degradation during hemoglobin glycation. However, whether fructose mediated glycation produces ROS and heme degradation is unknown. Here we report that ROS (H2O2) production occurred during hemoglobin fructation in vitro using chemiluminescence methods. The enhanced heme exposure and degradation were determined using UV-Vis and fluorescence spectrophotometry. Following accumulation of ROS, heme degradation products were accumulated reaching a plateau along with the detected ROS. Thus, fructose may make a significant contribution to the production of ROS, glycation of proteins, and heme degradation during diabetes.

  10. Hydrophobic interactions and chemical reactivity

    NARCIS (Netherlands)

    Otto, Sijbren; Engberts, Jan B.F.N.

    2003-01-01

    This perspective describes how kinetic studies of organic reactions can be used to increase our understanding of hydrophobic interactions. In turn, our understanding of hydrophobic interactions can be used as a tool to influence chemical reactions.

  11. Hydrophobic interactions and chemical reactivity

    NARCIS (Netherlands)

    Otto, Sijbren; Engberts, Jan B.F.N.

    2003-01-01

    This perspective describes how kinetic studies of organic reactions can be used to increase our understanding of hydrophobic interactions. In turn, our understanding of hydrophobic interactions can be used as a tool to influence chemical reactions.

  12. Studying chemical reactivity in a virtual environment.

    Science.gov (United States)

    Haag, Moritz P; Reiher, Markus

    2014-01-01

    Chemical reactivity of a set of reactants is determined by its potential (electronic) energy (hyper)surface. The high dimensionality of this surface renders it difficult to efficiently explore reactivity in a large reactive system. Exhaustive sampling techniques and search algorithms are not straightforward to employ as it is not clear which explored path will eventually produce the minimum energy path of a reaction passing through a transition structure. Here, the chemist's intuition would be of invaluable help, but it cannot be easily exploited because (1) no intuitive and direct tool for the scientist to manipulate molecular structures is currently available and because (2) quantum chemical calculations are inherently expensive in terms of computational effort. In this work, we elaborate on how the chemist can be reintroduced into the exploratory process within a virtual environment that provides immediate feedback and intuitive tools to manipulate a reactive system. We work out in detail how this immersion should take place. We provide an analysis of modern semi-empirical methods which already today are candidates for the interactive study of chemical reactivity. Implications of manual structure manipulations for their physical meaning and chemical relevance are carefully analysed in order to provide sound theoretical foundations for the interpretation of the interactive reactivity exploration.

  13. Steam-chemical reactivity for irradiated beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Anderl, R.A.; McCarthy, K.A.; Oates, M.A.; Petti, D.A.; Pawelko, R.J.; Smolik, G.R. [Idaho National Engineering and Environmental Lab., Idaho Falls, ID (United States)

    1998-01-01

    This paper reports the results of an experimental investigation to determine the influence of neutron irradiation effects and annealing on the chemical reactivity of beryllium exposed to steam. The work entailed measurements of the H{sub 2} generation rates for unirradiated and irradiated Be and for irradiated Be that had been previously annealed at different temperatures ranging from 450degC to 1200degC. H{sub 2} generation rates were similar for irradiated and unirradiated Be in steam-chemical reactivity experiments at temperatures between 450degC and 600degC. For irradiated Be exposed to steam at 700degC, the chemical reactivity accelerated rapidly and the specimen experienced a temperature excursion. Enhanced chemical reactivity at temperatures between 400degC and 600degC was observed for irradiated Be annealed at temperatures of 700degC and higher. This reactivity enhancement could be accounted for by the increased specific surface area resulting from development of a surface-connected porosity in the irradiated-annealed Be. (author)

  14. Haptenation: Chemical Reactivity and Protein Binding

    Directory of Open Access Journals (Sweden)

    Itai Chipinda

    2011-01-01

    Full Text Available Low molecular weight chemical (LMW allergens are commonly referred to as haptens. Haptens must complex with proteins to be recognized by the immune system. The majority of occupationally related haptens are reactive, electrophilic chemicals, or are metabolized to reactive metabolites that form covalent bonds with nucleophilic centers on proteins. Nonelectrophilic protein binding may occur through disulfide exchange, coordinate covalent binding onto metal ions on metalloproteins or of metal allergens, themselves, to the major histocompatibility complex. Recent chemical reactivity kinetic studies suggest that the rate of protein binding is a major determinant of allergenic potency; however, electrophilic strength does not seem to predict the ability of a hapten to skew the response between Th1 and Th2. Modern proteomic mass spectrometry methods that allow detailed delineation of potential differences in protein binding sites may be valuable in predicting if a chemical will stimulate an immediate or delayed hypersensitivity. Chemical aspects related to both reactivity and protein-specific binding are discussed.

  15. Cranberry phytochemicals inhibit glycation of human hemoglobin and serum albumin by scavenging reactive carbonyls.

    Science.gov (United States)

    Liu, Haiyan; Liu, Hanwei; Wang, Wei; Khoo, Christina; Taylor, James; Gu, Liwei

    2011-08-01

    Protein glycation caused by sugars and reactive carbonyls is a contributing factor to diabetic complications, aging, and other chronic diseases. The objective of this study was to investigate the inhibitory effects of cranberry phytochemicals on protein glycation. Cranberries, purified to yield sugar-free phytochemical powder, were fractionated into ethyl acetate and water fractions. Water fraction was further separated into water fraction I, II, and III on a Sephadex LH-20 column. Cranberry phytochemical powder and its fractions significantly inhibited the formation of glycated hemoglobin. The concentrations of cranberry phytochemicals required to inhibit 50% of albumin glycation (EC(50)) in albumin-glucose assay were lower than that of aminoguanidine except for water fraction I. Cranberry phytochemicals inhibited glycation of human serum albumin mediated by methylglyoxal, but the EC(50) were higher than that of aminoguanidine. Carbonyl scavenging assay showed that water fraction II scavenged 89.3% of methylglyoxal at 6 h of reaction. Fractions enriched with procyanidins showed higher antiglycation activities, suggesting procyanidins were the major active components. The hypothesis whether cranberry procyanidins scavenged reactive carbonyls by forming adducts was tested. Epicatechin was used as a model compound to react with methylglyoxal and glyoxal at pH 7.4. Five adducts were detected and their structures were tentatively identified using HPLC-ESI-MS/MS.

  16. Chemical reactivity assessments in R&D.

    Science.gov (United States)

    Leggett, David

    2004-11-11

    The evaluation of reactive chemical hazards at the pilot and manufacturing scale, using laboratory testing, is increasingly used and has been well documented. However, reactive chemical hazard evaluation at the R&D scale presents special challenges. The typical hazard testing program requires a significant amount of sample, often takes time (>3 days) to complete, and is can be quite costly. On the other hand, the synthesis of new molecules in the R&D environment often produces only a few grams, occurs quickly (R&D stage of product development to define the critical limits of temperature, pressure, concentration, and safe dosing rates of processes it is possible to identify the potential hazards of the planned synthesis. This paper describes a staged approach for chemical reactivity hazard evaluation and assessment applicable to an R&D environment. We will describe these initial phases of the R&D hazard evaluation process that rely on only data that can be obtained from the open literature. We will also indicate how the need for additional assessments can be determined from this initial hazard review.

  17. ROLE OF STEM CELL FACTOR IN THE REACTIVATION OF HUMAN FETAL HEMOGLOBIN

    Directory of Open Access Journals (Sweden)

    Marco Gabbianelli

    2009-11-01

    In vitro and in vivo models have led to the identification of several chemical compounds able to reactivate HbF synthesis in adult erythroid cells. Although the impact of these HbF inducers, including hypomethylating agents, histone deacetylase inhibitors and hydroxyurea, was clear on the natural history of sickle cell anemia, the benefit on the clinical course of -thalassemia was only limited: particularly, the toxicity and the modest increase in γ-globin reactivation indicated the need for improved agents able to induce higher levels of HbF. In the present review we describe the biologic properties of Stem Cell Factor (SCF, a cytokine sustaining the survival and proliferation of erythroid cells, that at pharmacological doses acts as a potent stimulator of HbF synthesis in adult erythroid cells.

  18. Tailoring protein nanomechanics with chemical reactivity.

    Science.gov (United States)

    Beedle, Amy E M; Mora, Marc; Lynham, Steven; Stirnemann, Guillaume; Garcia-Manyes, Sergi

    2017-06-06

    The nanomechanical properties of elastomeric proteins determine the elasticity of a variety of tissues. A widespread natural tactic to regulate protein extensibility lies in the presence of covalent disulfide bonds, which significantly enhance protein stiffness. The prevalent in vivo strategy to form disulfide bonds requires the presence of dedicated enzymes. Here we propose an alternative chemical route to promote non-enzymatic oxidative protein folding via disulfide isomerization based on naturally occurring small molecules. Using single-molecule force-clamp spectroscopy, supported by DFT calculations and mass spectrometry measurements, we demonstrate that subtle changes in the chemical structure of a transient mixed-disulfide intermediate adduct between a protein cysteine and an attacking low molecular-weight thiol have a dramatic effect on the protein's mechanical stability. This approach provides a general tool to rationalize the dynamics of S-thiolation and its role in modulating protein nanomechanics, offering molecular insights on how chemical reactivity regulates protein elasticity.

  19. Tailoring protein nanomechanics with chemical reactivity

    Science.gov (United States)

    Beedle, Amy E. M.; Mora, Marc; Lynham, Steven; Stirnemann, Guillaume; Garcia-Manyes, Sergi

    2017-06-01

    The nanomechanical properties of elastomeric proteins determine the elasticity of a variety of tissues. A widespread natural tactic to regulate protein extensibility lies in the presence of covalent disulfide bonds, which significantly enhance protein stiffness. The prevalent in vivo strategy to form disulfide bonds requires the presence of dedicated enzymes. Here we propose an alternative chemical route to promote non-enzymatic oxidative protein folding via disulfide isomerization based on naturally occurring small molecules. Using single-molecule force-clamp spectroscopy, supported by DFT calculations and mass spectrometry measurements, we demonstrate that subtle changes in the chemical structure of a transient mixed-disulfide intermediate adduct between a protein cysteine and an attacking low molecular-weight thiol have a dramatic effect on the protein's mechanical stability. This approach provides a general tool to rationalize the dynamics of S-thiolation and its role in modulating protein nanomechanics, offering molecular insights on how chemical reactivity regulates protein elasticity.

  20. Reactivity of Tourmaline by Quantum Chemical Calculations

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    ZnAb initio calculations on reactivity of tourmaline were performed using both Gaussian and density function theory discrete variation method (DFT-DVM). The HF, B3LYP methods and basis sets STO-3G(3d,3p),6-31G(3d,3p) and 6-311++G(3df,3pd) were used in the calculations. The experimental results show energy value obtained from B3LYP and 6-31++1G(3df,3pd) basis sets is more accurate than those from other methods. The highest occupied molecular orbital (HOMO) of the tourmaline cluster mainly consists of O atom of hydroxyl group with relative higher energy level, suggesting that chemical bond between those of electron acceptor and this site may readily form, indicating the higher reactivity of hydroxyl group. The lowest unoccupied molecular orbital (LUMO) of the tourmaline cluster are dominantly composed of Si, O of tetrahedron and Na with relative lower energy level, suggesting that these atoms may tend to form chemical bond with those of electron donor. The results also prove that the O atoms of the tourmaline cluster have stronger reactivity than other atoms.

  1. Reduced hemoglobin and increased C-reactive protein are associated with upper gastrointestinal bleeding.

    Science.gov (United States)

    Tomizawa, Minoru; Shinozaki, Fuminobu; Hasegawa, Rumiko; Togawa, Akira; Shirai, Yoshinori; Ichiki, Noboru; Motoyoshi, Yasufumi; Sugiyama, Takao; Yamamoto, Shigenori; Sueishi, Makoto

    2014-02-07

    To investigate the early upper gastrointestinal endoscopy (endoscopy) significantly reduces mortality resulting from upper gastrointestinal (GI) bleeding. Upper GI bleeding was defined as 1a, 1b, 2a, and 2b according to the Forrest classification. The hemoglobin (Hb), and C-reactive protein (CRP) were examined at around the day of endoscopy and 3 mo prior to endoscopy. The rate of change was calculated as follows: (the result of blood examination on the day of endoscopy - the results of blood examination 3 mo prior to endoscopy)/(results of blood examination 3 mo prior to endoscopy). Receiver operating characteristic curves were created to determine threshold values. Seventy-nine men and 77 women were enrolled. There were 17 patients with upper GI bleeding: 12 with a gastric ulcer, 3 with a duodenal ulcer, 1 with an acute gastric mucosal lesion, and 1 with gastric cancer. The area under the curve (AUC), threshold, sensitivity, and specificity of Hb around the day of endoscopy were 0.902, 11.7 g/dL, 94.1%, and 77.1%, respectively, while those of CRP were 0.722, 0.5 mg/dL, 70.5%, and 73%, respectively. The AUC, threshold, sensitivity, and specificity of the rate of change of Hb were 0.851, -21.3%, 76.4%, and 82.6%, respectively, while those of CRP were 0.901, 100%, 100%, and 82.5%, respectively. Predictors for upper GI bleeding were Hb 21.3% and an increase in the CRP > 100%, 3 mo before endoscopy.

  2. An autonomous organic reaction search engine for chemical reactivity

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

    2017-06-01

    The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

  3. An autonomous organic reaction search engine for chemical reactivity.

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Henson, Alon B; Granda, Jaroslaw M; Cronin, Leroy

    2017-06-09

    The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

  4. Reactive Chemical Transport Under Multiphase System

    Science.gov (United States)

    Fang, Y.; Yeh, G.

    2001-12-01

    A numerical model, HYDROBIOGEOCHEM, is developed for modeling reactive chemical transport under multiphase flow systems. The chemistry part of this model is derived from BIOGEOCHEM, which is a general computer code that simulates biogeochemial processes from a reaction-based mechanistic point of view. To reduce primary dependent variables (PDVs), Gauss-Jordan decomposition is applied to the governing matrix equations for transport, resulting in mobile components and mobile kinetic variables as PDVs. Options of sequential iteration approach (SIA), predictor corrector and operator splitting method are incorporated in the code to make it versatile. The model is a practical tool for assessing migration of subsurface contamination and proper designing of remediation technologies. Examples are presented to demonstrate the capability of the new model.

  5. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft

    2002-04-01

    Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

  6. Chemical Reactivity Perspective into the Group 2B Metals Halides.

    Science.gov (United States)

    Özen, Alimet Sema; Akdeniz, Zehra

    2016-06-30

    Chemical reactivity descriptors within the conceptual density functional theory can be used to understand the nature of the interactions between two monomers of the Group 2B metal halides. This information might be valuable in the development of adequate force law parameters for simulations in the liquid state. In this study, MX2 monomers and dimers, where M = Zn, Cd, Hg and X = F, Cl, Br, I, were investigated in terms of chemical reactivity descriptors. Relativistic effects were taken into account using the effective core potential (ECP) approach. Correlations were produced between global and local reactivity descriptors and dimerization energies. Results presented in this work represent the first systematic investigation of Group 2B metal halides in the literature from a combined point of view of both relativistic effects and chemical reactivity descriptors. Steric effects were found to be responsible for the deviation from the chemical reactivity principles. They were introduced into the chemical reactivity descriptors such as local softness.

  7. Fluxes of chemically reactive species inferred from mean concentration measurements

    NARCIS (Netherlands)

    Galmarini, S.; Vilà-Guerau De Arellano, J.; Duyzer, J.H.

    1997-01-01

    A method is presented for the calculation of the fluxes of chemically reactive species on the basis of routine measurements of meteorological variables and chemical species. The method takes explicity into account the influence of chemical reactions on the fluxes of the species. As a demonstration o

  8. The Hazards of Reactive Chemicals in High School Laboratories.

    Science.gov (United States)

    Forlin, Peter

    Chemical reactivity is a major area of risk in high school laboratories. This paper reports on a study that has provided a research-based framework for risk management in Australian chemical education. The chemical practice model of risk management is considered with respect to kinetic factors; catalysts; concentrations and proportions;…

  9. Reactivating Fetal Hemoglobin Expression in Human Adult Erythroblasts Through BCL11A Knockdown Using Targeted Endonucleases

    Directory of Open Access Journals (Sweden)

    Carmen F Bjurström

    2016-01-01

    Full Text Available We examined the efficiency, specificity, and mutational signatures of zinc finger nucleases (ZFNs, transcriptional activator-like effector nucleases (TALENs, and clustered regularly interspaced short palindromic repeat (CRISPR/Cas9 systems designed to target the gene encoding the transcriptional repressor BCL11A, in human K562 cells and human CD34+ progenitor cells. ZFNs and TALENs were delivered as in vitro transcribed mRNA through electroporation; CRISPR/Cas9 was codelivered by Cas9 mRNA with plasmid-encoded guideRNA (gRNA (pU6.g1 or in vitro transcribed gRNA (gR.1. Analyses of efficacy revealed that for these specific reagents and the delivery methods used, the ZFNs gave rise to more allelic disruption in the targeted locus compared to the TALENs and CRISPR/Cas9, which was associated with increased levels of fetal hemoglobin in erythroid cells produced in vitro from nuclease-treated CD34+ cells. Genome-wide analysis to evaluate the specificity of the nucleases revealed high specificity of this specific ZFN to the target site, while specific TALENs and CRISPRs evaluated showed off-target cleavage activity. ZFN gene-edited CD34+ cells had the capacity to engraft in NOD-PrkdcSCID-IL2Rγnull mice, while retaining multi-lineage potential, in contrast to TALEN gene-edited CD34+ cells. CRISPR engraftment levels mirrored the increased relative plasmid-mediated toxicity of pU6.g1/Cas9 in hematopoietic stem/progenitor cells (HSPCs, highlighting the value for the further improvements of CRISPR/Cas9 delivery in primary human HSPCs.

  10. Electronegativity, Bond Energy, and Chemical Reactivity.

    Science.gov (United States)

    Myers, R. Thomas

    1979-01-01

    Discusses the Pauling electronegativity concept which rationalizes several kinds of chemical reactions of covalent substances. Electronegativity differences applied to some reactions are demonstrated. (SA)

  11. Use and Misuse of Chemical Reactivity Spreadsheets

    Energy Technology Data Exchange (ETDEWEB)

    Simmons, F

    2005-09-20

    Misidentifying chemical hazards can have serious deleterious effects. Consequences of not identifying a chemical are obvious and include fires, explosions, injury to workers, etc. Consequences of identifying hazards that are really not present can be equally as bad. Misidentifying hazards can result in increased work with loss of productivity, increased expenses, utilization/consumption of scarce resources, and the potential to modify the work to include chemicals or processes that are actually more hazardous than those originally proposed. For these reasons, accurate hazard identification is critical to any safety program. Hazard identification in the world of chemistry is, at best, a daunting task. The knowing or understanding, of the reactions between any of approximately twelve million known chemicals that may be hazardous, is the reason for this task being so arduous. Other variables, such as adding other reactants/contaminants or changing conditions (e.g., temperature, pressure, or concentration), make hazard determination something many would construe as being more than impossibly difficult. Despite these complexities, people who do not have an extensive background in the chemical sciences can be called upon to perform chemical hazard identification. Because hazard identification in the area of chemical safety is so burdensome and because people with a wide variety of training are called upon to perform this work, tools are required to aid in chemical hazard identification. Many tools have been developed. Unfortunately, many of these tools are not seen as the limited resource that they are and are used inappropriately.

  12. Chemical reactor modeling multiphase reactive flows

    CERN Document Server

    Jakobsen, Hugo A

    2014-01-01

    Chemical Reactor Modeling closes the gap between Chemical Reaction Engineering and Fluid Mechanics.  The second edition consists of two volumes: Volume 1: Fundamentals. Volume 2: Chemical Engineering Applications In volume 1 most of the fundamental theory is presented. A few numerical model simulation application examples are given to elucidate the link between theory and applications. In volume 2 the chemical reactor equipment to be modeled are described. Several engineering models are introduced and discussed. A survey of the frequently used numerical methods, algorithms and schemes is provided. A few practical engineering applications of the modeling tools are presented and discussed. The working principles of several experimental techniques employed in order to get data for model validation are outlined. The monograph is based on lectures regularly taught in the fourth and fifth years graduate courses in transport phenomena and chemical reactor modeling, and in a post graduate course in modern reactor m...

  13. Ultraviolet Spectrum And Chemical Reactivity Of CIO Dimer

    Science.gov (United States)

    Demore, William B.; Tschuikow-Roux, E.

    1992-01-01

    Report describes experimental study of ultraviolet spectrum and chemical reactivity of dimer of chlorine monoxide (CIO). Objectives are to measure absorption cross sections of dimer at near-ultraviolet wavelengths; determine whether asymmetrical isomer (CIOCIO) exists at temperatures relevant to Antarctic stratosphere; and test for certain chemical reactions of dimer. Important in photochemistry of Antarctic stratosphere.

  14. Using Protein-Confined Proximity To Determine Chemical Reactivity.

    Science.gov (United States)

    Kobayashi, Tomonori; Hoppmann, Christian; Yang, Bing; Wang, Lei

    2016-11-16

    Chemical reactivity is essential for functional modification of biomolecules with small molecules and the development of covalent drugs. The reactivity between a chemical functional group of a small molecule and that of a large biomolecule cannot be reliably predicted from the reactivity of the corresponding functional groups separately installed on two small molecules, because the proximity effect on reactivity resulting from the binding of the small molecule to the biomolecule is challenging to achieve by mixing two small molecules. Here we present a new strategy to determine the chemical reactivity of two functional groups in the context of close proximity afforded by proteins. The functional groups to be tested were separately installed at the interface of two interacting proteins in the format of amino acid side chains via the expansion of the genetic code. Reaction of the two functional groups resulted in covalent cross-linking of interacting proteins, readily detectable by gel electrophoresis. Using this strategy, we evolved new synthetases to genetically encode N(ε)-fluoroacetyllysine (FAcK), an isosteric fluorine analogue of acetyllysine. We demonstrated that fluoroacetamide installed on FAcK, previously thought inert to biological functional groups, actually reacted with the thiol group of cysteine when in proximity. This strategy should be valuable for accurately evaluating chemical reactivity of small molecules toward large biomolecules, which will help avoid undesired side reactions of drugs and expand the repertoire of functional groups to covalently target biomolecules.

  15. Metal ion coordination in `R’ and `T’ state hybrid hemoglobins as revealed by optical, EPR and sulphhydryl reactivity studies

    Indian Academy of Sciences (India)

    S Ramasamy; Swarnalatha Venkateshrao; J M Rifkind; P T Manoharan

    2005-03-01

    The sulphhydryl environment in various mixed-metal hybrid hemoglobins, viz. 2(Cu)-2(FeCO), 2(FeCO)-2(Cu), 2(Cu)-2(Ni), 2(Ni)-2(Cu), was studied by reacting them with the sulphhydryl reagent, 4,4'-dithiodipyridine (4-PDS). The reactivity was compared with that of HbCO, NiHb and CuHb. It is found that there exists a correlation between conformational change and metal ion environment, not only at the extreme R and T states but also the intermediate conformations. EPR examinations of these hybrids show that both in 4R state-[Cu(II)-Fe(II)] and state-[Cu(II)-Ni(II)] hybrids at neutral pH and in the absence of IHP, CuPPIX, irrespective of the subunit in which it is present, has a mixed-metal ion environment: Species 1, a five-coordinated Cu2+ complex with strong proximal histidine bond and species 2, a four-coordinated complex without any covalent linkage with N F8-histidine.

  16. Gender-Specific Prognosis and Risk Impact of C-Reactive Protein, Hemoglobin and Platelet in the Development of Coronary Spasm

    Directory of Open Access Journals (Sweden)

    Ming-Yow Hung, Kuang-Hung Hsu, Wei-Syun Hu, Nen-Chung Chang, Chun-Yao Huang, Ming-Jui Hung

    2013-01-01

    Full Text Available Background: Scarce data are available on hemoglobin and platelet in relation to coronary artery spasm (CAS development. We sought to determine the roles that high-sensitivity C-reactive protein (hs-CRP, hemoglobin and platelet play in CAS patients.Methods: Patients (337 women and 532 men undergoing coronary angiography with or without CAS but without obstructive coronary artery disease were evaluated during a 12-year period.Results: Among women with high hemoglobin levels, the odds ratios (OR from the lowest (<1 mg/l to the highest tertiles (>3 mg/l of hs-CRP were 1.21, 2.15, and 5.93 (p=0.009. In women with low hemoglobin levels, an elevated risk was found from the middle to the highest tertiles of hs-CRP (OR 0.59 to 3.85 (p=0.004. This relationship was not observed in men. In men, platelet count was the most significant risk factor for CAS (p=0.004. The highest likelihood of developing CAS was found among women with the highest hs-CRP tertile and low platelet counts (OR 8.77; 95% confidence interval [CI] 2.20-35.01 and among men with the highest hs-CRP tertile and high platelet counts (OR 4.58; 95% CI 0.48-43.97. Neither hemoglobin level nor platelet count was associated with frequent recurrent angina in both genders with CAS whereas death and myocardial infarction were rare.Conclusions: There are positive interactions among hs-CRP, hemoglobin and platelet in women with this disease, but not in men. While hemoglobin is a modifier in CAS development in women, platelet count is an independent risk factor for men. Both women and men have good prognosis of CAS.

  17. Reactivity indicators for degenerate states in the density-functional theoretic chemical reactivity theory.

    Science.gov (United States)

    Cárdenas, Carlos; Ayers, Paul W; Cedillo, Andrés

    2011-05-07

    Density-functional-theory-based chemical reactivity indicators are formulated for degenerate and near-degenerate ground states. For degenerate states, the functional derivatives of the energy with respect to the external potential do not exist, and must be replaced by the weaker concept of functional variation. The resultant reactivity indicators depend on the specific perturbation. Because it is sometimes impractical to compute reactivity indicators for a specific perturbation, we consider two special cases: point-charge perturbations and Dirac delta function perturbations. The Dirac delta function perturbations provide upper bounds on the chemical reactivity. Reactivity indicators using the common used "average of degenerate states approximation" for degenerate states provide a lower bound on the chemical reactivity. Unfortunately, this lower bound is often extremely weak. Approximate formulas for the reactivity indicators within the frontier-molecular-orbital approximation and special cases (two or three degenerate spatial orbitals) are presented in the supplementary material. One remarkable feature that arises in the frontier molecular orbital approximation, and presumably also in the exact theory, is that removing electrons sometimes causes the electron density to increase at the location of a negative (attractive) Dirac delta function perturbation. That is, the energetic response to a reduction in the external potential can increase even when the number of electrons decreases.

  18. Enhanced chemical reactivity of graphene induced by mechanical strain.

    Science.gov (United States)

    Bissett, Mark A; Konabe, Satoru; Okada, Susumu; Tsuji, Masaharu; Ago, Hiroki

    2013-11-26

    Control over chemical reactivity is essential in the field of nanotechnology. Graphene is a two-dimensional atomic sheet of sp(2) hybridized carbon with exceptional properties that can be altered by chemical functionalization. Here, we transferred single-layer graphene onto a flexible substrate and investigated the functionalization using different aryl diazonium molecules while applying mechanical strain. We found that mechanical strain can alter the structure of graphene, and dramatically increase the reaction rate, by a factor of up to 10, as well as increase the final degree of functionalization. Furthermore, we demonstrate that mechanical strain enables functionalization of graphene for both p- and n-type dopants, where unstrained graphene showed negligible reactivity. Theoretical calculations were also performed to support the experimental findings. Our findings offer a simple approach to control the chemical reactivity of graphene through the application of mechanical strain, allowing for a tuning of the properties of graphene.

  19. Modeling food matrix effects on chemical reactivity: Challenges and perspectives.

    Science.gov (United States)

    Capuano, Edoardo; Oliviero, Teresa; van Boekel, Martinus A J S

    2017-06-29

    The same chemical reaction may be different in terms of its position of the equilibrium (i.e., thermodynamics) and its kinetics when studied in different foods. The diversity in the chemical composition of food and in its structural organization at macro-, meso-, and microscopic levels, that is, the food matrix, is responsible for this difference. In this viewpoint paper, the multiple, and interconnected ways the food matrix can affect chemical reactivity are summarized. Moreover, mechanistic and empirical approaches to explain and predict the effect of food matrix on chemical reactivity are described. Mechanistic models aim to quantify the effect of food matrix based on a detailed understanding of the chemical and physical phenomena occurring in food. Their applicability is limited at the moment to very simple food systems. Empirical modeling based on machine learning combined with data-mining techniques may represent an alternative, useful option to predict the effect of the food matrix on chemical reactivity and to identify chemical and physical properties to be further tested. In such a way the mechanistic understanding of the effect of the food matrix on chemical reactions can be improved.

  20. Chemical reactivity evaluation: The CCPS program. [CCPS (Center for Chemical Process Safety)

    Energy Technology Data Exchange (ETDEWEB)

    West, A.S. (American Institute of Chemical Engineers, New York, NY (United States))

    1993-01-01

    A summary is presented of the chemical reactivity evaluation aspects of the soon to be published [open quotes]Guidelines for Chemical Reactivity Evaluation and Application to Process Design[close quotes] developed under the sponsorship of the Center for Chemical Process Safety. Emphasis is placed on strategies for thermochemical evaluation of industrial chemical substances. Certain structural entities, for example, high degrees of unsaturation and nitrogen-halogen linkages, will likely identify hazardous reactive chemicals. The effects of impurities in the chemicals, as well as, for example, incidental contact with water and air (oxygen), must also be considered in the evaluation of potential reactivity hazards, representing undesired reactions. Various test methods are indicated briefly along with the rationale for use of specific methods in hazard evaluation. 30 refs., 1 fig., 9 tabs.

  1. Effect of chemical degradation on fluxes of reactive compounds

    Directory of Open Access Journals (Sweden)

    J. Rinne

    2011-12-01

    Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the emission at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a~major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

  2. Reactive chemical dynamics through conical intersections

    Indian Academy of Sciences (India)

    S Ghosal; B Jayachander Rao; S Mahapatra

    2007-09-01

    Reaction dynamics of prototypical, D + H2 and Cl (2P) + H2, chemical reactions occurring through the conical intersections of the respective coupled multi-sheeted potential energy surfaces is examined here. In addition to the electronic coupling, nonadiabatic effects due to relativistic spin-orbit coupling are also considered for the latter reaction. A time-dependent wave packet propagation approach is undertaken and the quantum dynamical observables viz., energy resolved reaction probabilities, integral reaction cross-sections and thermal rate constants are reported.

  3. Hemoglobin derivatives

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/003371.htm Hemoglobin derivatives To use the sharing features on this page, please enable JavaScript. Hemoglobin derivatives are altered forms of hemoglobin . Hemoglobin is ...

  4. Spinodal decomposition of chemically reactive binary mixtures

    Science.gov (United States)

    Lamorgese, A.; Mauri, R.

    2016-08-01

    We simulate the influence of a reversible isomerization reaction on the phase segregation process occurring after spinodal decomposition of a deeply quenched regular binary mixture, restricting attention to systems wherein material transport occurs solely by diffusion. Our theoretical approach follows a diffuse-interface model of partially miscible binary mixtures wherein the coupling between reaction and diffusion is addressed within the frame of nonequilibrium thermodynamics, leading to a linear dependence of the reaction rate on the chemical affinity. Ultimately, the rate for an elementary reaction depends on the local part of the chemical potential difference since reaction is an inherently local phenomenon. Based on two-dimensional simulation results, we express the competition between segregation and reaction as a function of the Damköhler number. For a phase-separating mixture with components having different physical properties, a skewed phase diagram leads, at large times, to a system converging to a single-phase equilibrium state, corresponding to the absolute minimum of the Gibbs free energy. This conclusion continues to hold for the critical phase separation of an ideally perfectly symmetric binary mixture, where the choice of final equilibrium state at large times depends on the initial mean concentration being slightly larger or less than the critical concentration.

  5. Chemical Reactivity Theory Study of Advanced Glycation Endproduct Inhibitors.

    Science.gov (United States)

    Frau, Juan; Glossman-Mitnik, Daniel

    2017-02-02

    Several compounds with the known ability to perform as inhibitors of advanced glycation endproducts (AGE) have been studied with Density Functional Theory (DFT) through the use of anumberofdensityfunctionalswhoseaccuracyhasbeentestedacrossabroadspectrumofdatabases in Chemistry and Physics. The chemical reactivity descriptors for these systems have been calculated through Conceptual DFT in an attempt to relate their intrinsic chemical reactivity with the ability to inhibit the action of glycating carbonyl compounds on amino acids and proteins. This knowledge could be useful in the design and development of new drugs which can be potential medicines for diabetes and Alzheimer's disease.

  6. Chemical Safety Alert: Identifying Chemical Reactivity Hazards Preliminary Screening Method

    Science.gov (United States)

    Introduces small-to-medium-sized facilities to a method developed by Center for Chemical Process Safety (CCPS), based on a series of twelve yes-or-no questions to help determine hazards in warehousing, repackaging, blending, mixing, and processing.

  7. Chemical reactivity of the Martian soil

    Science.gov (United States)

    Zent, A. P.; Mckay, C. P.

    1992-01-01

    The Viking life sciences experimental packages detected extraordinary chemical activity in the martian soil, probably the result of soil-surface chemistry. At least one very strong oxidant may exist in the martian soil. The electrochemical nature of the martian soil has figured prominently in discussions of future life sciences research on Mars. Putative oxidants in the martian soil may be responsible for the destruction of organic material to considerable depth, precluding the recovery of reducing material that may be relic of early biological forms. Also, there have been serious expressions of concern regarding the effect that soil oxidants may have on human health and safety. The concern here has centered on the possible irritation of the respiratory system due to dust carried into the martian habitat through the air locks.

  8. The direct peptide reactivity assay: selectivity of chemical respiratory allergens.

    Science.gov (United States)

    Lalko, Jon F; Kimber, Ian; Gerberick, G Frank; Foertsch, Leslie M; Api, Anne Marie; Dearman, Rebecca J

    2012-10-01

    It is well known that some chemicals are capable of causing allergic diseases of the skin and respiratory tract. Commonly, though not exclusively, chemical allergens are associated with the selective development of skin or respiratory sensitization. The reason for this divergence is unclear, although it is hypothesized that the nature of interactions between the chemical hapten and proteins is influential. The direct peptide reactivity assay (DPRA) has been developed as a screen for the identification of skin-sensitizing chemicals, and here we describe the use of this method to explore whether differences exist between skin and respiratory allergens with respect to their peptide-binding properties. Known skin and respiratory sensitizers were reacted with synthetic peptides containing either lysine (Lys) or cysteine (Cys) for 24 h. The samples were analyzed by HPLC/UV, and the loss of peptide from the reaction mixture was expressed as the percent depletion compared with the control. The potential for preferential reactivity was evaluated by comparing the ratio of Lys to Cys depletion (Lys:Cys ratio). The results demonstrate that the majority of respiratory allergens are reactive in the DPRA, and that in contrast to most skin-sensitizing chemicals, preferentially react with the Lys peptide. These data suggest that skin and respiratory chemical allergens can result in different protein conjugates, which may in turn influence the quality of induced immune responses. Overall, these investigations reveal that the DPRA has considerable potential to be incorporated into tiered testing approaches for the identification and characterization of chemical respiratory allergens.

  9. Tracking thermal fronts with temperature-sensitive, chemically reactive tracers

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, B.A.; Birdsell, S.A.

    1987-01-01

    Los Alamos is developing tracer techniques using reactive chemicals to track thermal fronts in fractured geothermal reservoirs. If a nonadsorbing tracer flowing from the injection to production well chemically reacts, its reaction rate will be a strong function of temperature. Thus the extent of chemical reaction will be greatest early in the lifetime of the system, and less as the thermal front progresses from the injection to production well. Early laboratory experiments identified tracers with chemical kinetics suitable for reservoirs in the temperature range of 75 to 100/sup 0/C. Recent kinetics studies have focused on the kinetics of hydrolysis of derivatives of bromobenzene. This class of reactions can be used in reservoirs ranging in temperature from 150 to 275/sup 0/C, which is of greater interest to the geothermal industry. Future studies will include laboratory adsorption experiments to identify possibly unwanted adsorption on granite, development of sensitive analytical techniques, and a field demonstration of the reactive tracer concept.

  10. Chemical reactivity in the framework of pair density functional theories.

    Science.gov (United States)

    Otero, Nicolás; Mandado, Marcos

    2012-05-15

    Chemical reactivity descriptors are derived within the framework of the pair density functional theory. These indices provide valuable information about bonding rearrangements and activating mechanisms upon electrophilic or nucleophilic reactions. Indices derived and tested in this work represent nonlocal counterparts of the local reactivity indices derived in the context of conceptual density functional theory (CDFT) and frequently used in reactivity studies; the Fukui function, the local softness and the dual descriptor. In this work, we show how these nonlocal indices provide a quantum chemical basis to explain the success of qualitative resonance models in chemical reactivity predictions. Also, local information is implicitly contained as CDFT indices are obtained by simple integration. As illustrative examples, we have considered in this work the Markovnikov's rule, the reactivity of enolate anion, the nucleophilic conjugate addition to α,β-unsaturated compounds and the electrophilic aromatic substitution of benzene derivatives. The densities used in this work were obtained with Hartree-Fock, Kohn-Sham DFT, and singles and doubles configuration interaction (CISD) approaches. Copyright © 2012 Wiley Periodicals, Inc.

  11. Local Chemical Reactivity of a Metal Alloy Surface

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Scheffler, Matthias

    1995-01-01

    The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

  12. Fish hemoglobins

    Directory of Open Access Journals (Sweden)

    P.C. de Souza

    2007-06-01

    Full Text Available Vertebrate hemoglobin, contained in erythrocytes, is a globular protein with a quaternary structure composed of 4 globin chains (2 alpha and 2 beta and a prosthetic group named heme bound to each one. Having myoglobin as an ancestor, hemoglobin acquired the capacity to respond to chemical stimuli that modulate its function according to tissue requirements for oxygen. Fish are generally submitted to spatial and temporal O2 variations and have developed anatomical, physiological and biochemical strategies to adapt to the changing environmental gas availability. Structurally, most fish hemoglobins are tetrameric; however, those from some species such as lamprey and hagfish dissociate, being monomeric when oxygenated and oligomeric when deoxygenated. Fish blood frequently possesses several hemoglobins; the primary origin of this finding lies in the polymorphism that occurs in the globin loci, an aspect that may occasionally confer advantages to its carriers or even be a harmless evolutionary remnant. On the other hand, the functional properties exhibit different behaviors, ranging from a total absence of responses to allosteric regulation to drastic ones, such as the Root effect.

  13. Reactivity of chemical respiratory allergens in the Peroxidase Peptide Reactivity Assay.

    Science.gov (United States)

    Lalko, J F; Dearman, R J; Gerberick, G F; Troutman, J A; Api, A M; Kimber, I

    2013-03-01

    Sensitizing chemicals are commonly associated primarily with either skin or respiratory sensitization. In the Direct Peptide Reactivity Assay (DPRA), when compared with skin sensitizers, respiratory allergens have been demonstrated to selectively react with lysine rather than cysteine. The Peroxidase Peptide Reactivity Assay (PPRA) has been developed as a refinement to the DPRA. The PPRA incorporates dose-response analyses, mass spectroscopy for peptide detection and a horseradish peroxidase-hydrogen peroxide enzymatic system, increasing the potential to identify pro-haptens. In the investigations reported here, the PPRA was evaluated to determine whether it provides advantages for the identification of respiratory allergens. Twenty respiratory sensitizers, including five predicted to be pre-/pro-haptens were evaluated. The PPRA performed similarly to the DPRA with respect to identifying inherently reactive respiratory sensitizers. However, three respiratory sensitizers predicted to be pre-/pro-haptens (chlorhexidine, ethylenediamine and piperazine) were non-reactive and the general selectivity of the respiratory allergens for lysine was lost in the PPRA. Overall, the data indicate that the PPRA does not provide an advantage over the DPRA for discriminating allergens as either contact or respiratory sensitizers. Nevertheless, the PPRA provides a number of refinements to the DPRA that allow for an enhanced characterization of reactivity for both classes of chemical allergens. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Hemoglobin Variants in Mice

    Energy Technology Data Exchange (ETDEWEB)

    Popp, Raymond A.

    1965-04-22

    Variability among mammalian hemoglobins was observed many years ago (35). The chemical basis for differences among hemoglobins from different species of mammals has been studied by several investigators (5, 11, 18, 48). As well as interspecies differences, hemoglobin variants are frequently found within a species of mammals (2, 3, 7, 16) The inheritance of these intraspecies variants can be studied, and pedigrees indicate that the type of hemoglobin synthesized in an individual is genetically controlled (20). Several of the variant human hemoglobins are f'unctionally deficient (7, 16). Such hemoglobin anomalies are of basic interest to man because of the vital role of hemoglobin for transporting oxygen to all tissues of the body.

  15. The unique chemical reactivity of a graphene nanoribbon's zigzag edge

    CERN Document Server

    Jiang, D; Sumpter, B G; Dai, Sheng; Jiang, De-en; Sumpter, Bobby G.

    2007-01-01

    The zigzag edge of a graphene nanoribbon possesses a unique electronic state that is near the Fermi level and localized at the edge carbon atoms. We investigate the chemical reactivity of these zigzag edge sites by examining their reaction energetics with common radicals from first principles. A "partial radical" concept for the edge carbon atoms is introduced to characterize their chemical reactivity, and the validity of this concept is verified by comparing the dissociation energies of edge-radical bonds with similar bonds in molecules. In addition, the uniqueness of the zigzag-edged graphene nanoribbon is further demonstrated by comparing it with other forms of sp2 carbons, including a graphene sheet, nanotubes, and an armchair-edged graphene nanoribbon.

  16. Quantum chemical studies on the reactivity of oxazole derivatives

    Science.gov (United States)

    Hosseinzadeh, Behzad; Eskandari, Khalil; Zarandi, Maryam; Asli, Reza

    2016-11-01

    The quantum chemical study of the reactivity of a series of oxazole derivatives substituted at 2, 4, and 5 positions was performed using B3LYP/6-311++G( d, p) and MP2/6-311++G( d, p) levels of theory. Different substituents have been applied to cover a wide range of electronic effects. On the basis of Fukui functions, oxazole derivatives in the gas phase are found to be suitable nucleophilic sites. For the most of studied substituents, it was observed that the calculated Fukui function f k - values at the N-position are small in case of electron-withdrawing substituents, resulting a preferred N-position for hard reactions. In contrast, large f k - values in case of electron-donating groups show a preferred N-position for soft reactions. These two local reactivity descriptors predicted the reactivity of the electron-rich oxazoles sequence to be 2-substituted oxazoles > 5-substituted oxazoles > 4-substituted oxazoles, where due to resonance effect, the reactivity toward electrophilic attack at the pyridine nitrogen atom is enhanced by electron donor substituents.

  17. Reactive iron(III) in sediments: Chemical versus microbial extractions

    Science.gov (United States)

    Hyacinthe, C.; Bonneville, S.; Van Cappellen, P.

    2006-08-01

    The availability of particulate Fe(III) to iron reducing microbial communities in sediments and soils is generally inferred indirectly by performing chemical extractions. In this study, the bioavailability of mineral-bound Fe(III) in intertidal sediments of a eutrophic estuary is assessed directly by measuring the kinetics and extent of Fe(III) utilization by the iron reducing microorganism Shewanella putrefaciens, in the presence of excess electron donor. Microbial Fe(III) reduction is compared to chemical dissolution of iron from the same sediments in buffered ascorbate-citrate solution (pH 7.5), ascorbic acid (pH 2), and 1 M HCl. The results confirm that ascorbate at near-neutral pH selectively reduces the reactive Fe(III) pool, while the acid extractants mobilize additional Fe(II) and less reactive Fe(III) mineral phases. Furthermore, the maximum concentrations of Fe(III) reducible by S. putrefaciens correlate linearly with the iron concentrations extracted by buffered ascorbate-citrate solution, but not with those of the acid extractions. However, on average, only 65% of the Fe(III) reduced in buffered ascorbate-citrate solution can be utilized by S. putrefaciens, probably due to physical inaccessibility of the remaining fraction of reactive Fe(III) to the cells. While the microbial and abiotic reaction kinetics further indicate that reduction by ascorbate at near-neutral pH most closely resembles microbial reduction of the sediment Fe(III) pool by S. putrefaciens, the results also highlight fundamental differences between chemical reductive dissolution and microbial utilization of mineral-bound ferric iron.

  18. The chemical biology of hydropersulfides (RSSH): Chemical stability, reactivity and redox roles.

    Science.gov (United States)

    Saund, Simran S; Sosa, Victor; Henriquez, Stephanie; Nguyen, Q Nhu N; Bianco, Christopher L; Soeda, Shuhei; Millikin, Robert; White, Corey; Le, Henry; Ono, Katsuhiko; Tantillo, Dean J; Kumagai, Yoshito; Akaike, Takaaki; Lin, Joseph; Fukuto, Jon M

    2015-12-15

    Recent reports indicate the ubiquitous prevalence of hydropersulfides (RSSH) in mammalian systems. The biological utility of these and related species is currently a matter of significant speculation. The function, lifetime and fate of hydropersulfides will be assuredly based on their chemical properties and reactivity. Thus, to serve as the basis for further mechanistic studies regarding hydropersulfide biology, some of the basic chemical properties/reactivity of hydropersulfides was studied. The nucleophilicity, electrophilicity and redox properties of hydropersulfides were examined under biological conditions. These studies indicate that hydropersulfides can be nucleophilic or electrophilic, depending on the pH (i.e. the protonation state) and can act as good one- and two-electron reductants. These diverse chemical properties in a single species make hydropersulfides chemically distinct from other, well-known sulfur containing biological species, giving them unique and potentially important biological function. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Reactive solute transport in physically and chemically heterogeneous porous media with multimodal reactive mineral facies: The Lagrangian approach

    CERN Document Server

    Soltanian, Mohamad Reza; Dai, Zhenxue; Huang, Chaocheng

    2014-01-01

    Physical and chemical heterogeneities have a large impact on reactive transport in porous media. Examples of heterogeneous attributes affecting reactive mass transport are the hydraulic conductivity (K), and the equilibrium sorption distribution coefficient (Kd). This paper uses the Deng et al. (2013) conceptual model for multimodal reactive mineral facies and a Lagrangian-based stochastic theory in order to analyze the reactive solute dispersion in three-dimensional anisotropic heterogeneous porous media with hierarchical organization of reactive minerals. An example based on real field data is used to illustrate the time evolution trends of reactive solute dispersion. The results show that the correlation between the hydraulic conductivity and the equilibrium sorption distribution coefficient does have a significant effect on reactive solute dispersion. The anisotropy ratio does not have a significant effect on reactive solute dispersion. Furthermore, through a sensitivity analysis we investigate the impact...

  20. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness.

    Science.gov (United States)

    Malek, Ali; Balawender, Robert

    2015-02-07

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor.

  1. To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

    Science.gov (United States)

    Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad

    2015-08-25

    Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with

  2. Hemoglobin (image)

    Science.gov (United States)

    Hemoglobin is the most important component of red blood cells. It is composed of a protein called ... exchanged for carbon dioxide. Abnormalities of an individual's hemoglobin value can indicate defects in the normal balance ...

  3. Chemical reactivity drives spatiotemporal organisation of bacterial metabolism.

    Science.gov (United States)

    de Lorenzo, Víctor; Sekowska, Agnieszka; Danchin, Antoine

    2015-01-01

    In this review, we examine how bacterial metabolism is shaped by chemical constraints acting on the material and dynamic layout of enzymatic networks and beyond. These are moulded not only for optimisation of given metabolic objectives (e.g. synthesis of a particular amino acid or nucleotide) but also for curbing the detrimental reactivity of chemical intermediates. Besides substrate channelling, toxicity is avoided by barriers to free diffusion (i.e. compartments) that separate otherwise incompatible reactions, along with ways for distinguishing damaging vs. harmless molecules. On the other hand, enzymes age and their operating lifetime must be tuned to upstream and downstream reactions. This time dependence of metabolic pathways creates time-linked information, learning and memory. These features suggest that the physical structure of existing biosystems, from operon assemblies to multicellular development may ultimately stem from the need to restrain chemical damage and limit the waste inherent to basic metabolic functions. This provides a new twist of our comprehension of fundamental biological processes in live systems as well as practical take-home lessons for the forward DNA-based engineering of novel biological objects. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permission@oup.com.

  4. Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory.

    Science.gov (United States)

    Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2017-05-31

    In this work we establish a new temperature dependent procedure within the grand canonical ensemble, to avoid the Dirac delta function exhibited by some of the second order chemical reactivity descriptors based on density functional theory, at a temperature of 0 K. Through the definition of a local chemical potential designed to integrate to the global temperature dependent electronic chemical potential, the local chemical hardness is expressed in terms of the derivative of this local chemical potential with respect to the average number of electrons. For the three-ground-states ensemble model, this local hardness contains a term that is equal to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba, which integrates to the global hardness given by the difference in the first ionization potential, I, and the electron affinity, A, at any temperature. However, in the present approach one finds an additional temperature-dependent term that introduces changes at the local level and integrates to zero. Additionally, a τ-hard dual descriptor and a τ-soft dual descriptor given in terms of the product of the global hardness and the global softness multiplied by the dual descriptor, respectively, are derived. Since all these reactivity indices are given by expressions composed of terms that correspond to products of the global properties multiplied by the electrophilic or nucleophilic Fukui functions, they may be useful for studying and comparing equivalent sites in different chemical environments.

  5. Studies on high chemical reactivity of nano-NaH

    Institute of Scientific and Technical Information of China (English)

    FAN Yinheng; ZOU Yunling; JIN Dan; WU Qiang; LIU Tong; XU Jie

    2007-01-01

    A comparison between the initial reaction rates of nanometric and commercial Nail has been studied in four test reactions: 1) hydrogenolysis of chlorobenzene; 2) selec-tive reduction of cinnamaldehyde to cinnamyl alcohol; 3)metallation of dimethyl sulfoxide; and 4) catalytic hydroge-nation ofolefins. The experimental results indicate that when Nail is used as a chemical reagent in the first three reactions,the initial reaction rates of nano-NaH is 230, 120 and 110 times higher than those of the commercial ones respectively,and it is in agreement with the difference in specific surface areas between these two forms of Nail. When Nail is used as a catalyst component together with Cp2TiCl2 in the fourth reaction, catalyst with nano-NaH gives extremely high activity in the hydrogenation of olefins, while the one with commercial Nail gives no activity at all even ifa large amount of the commercial Nail is used to make the total surface area equivalent to that of nano-NaH. Thus, it is evident that although large specific surface area is important for nano-Nail to be used as a catalyst component, high surface energy with surface defects seems to be more important. The largespecific surface and the activated surface of nano-NaH withhigh surface energy should be the main factors for thei rextremely high chemical reactivity, while whether the former or the latter one plays a leading role depends on the type of reactions involved.

  6. Assessment of the extended Koopmans' theorem for the chemical reactivity: Accurate computations of chemical potentials, chemical hardnesses, and electrophilicity indices.

    Science.gov (United States)

    Yildiz, Dilan; Bozkaya, Uğur

    2016-01-30

    The extended Koopmans' theorem (EKT) provides a straightforward way to compute ionization potentials and electron affinities from any level of theory. Although it is widely applied to ionization potentials, the EKT approach has not been applied to evaluation of the chemical reactivity. We present the first benchmarking study to investigate the performance of the EKT methods for predictions of chemical potentials (μ) (hence electronegativities), chemical hardnesses (η), and electrophilicity indices (ω). We assess the performance of the EKT approaches for post-Hartree-Fock methods, such as Møller-Plesset perturbation theory, the coupled-electron pair theory, and their orbital-optimized counterparts for the evaluation of the chemical reactivity. Especially, results of the orbital-optimized coupled-electron pair theory method (with the aug-cc-pVQZ basis set) for predictions of the chemical reactivity are very promising; the corresponding mean absolute errors are 0.16, 0.28, and 0.09 eV for μ, η, and ω, respectively. © 2015 Wiley Periodicals, Inc.

  7. Chemical reactivity in nucleophilic cycloaddition to C70: vibronic coupling density and vibronic coupling constants as reactivity indices.

    Science.gov (United States)

    Haruta, Naoki; Sato, Tohru; Tanaka, Kazuyoshi

    2012-11-02

    The chemical reactivity in nucleophilic cycloaddition to C70 is investigated on the basis of vibronic (electron-vibration) coupling density and vibronic coupling constants. Because the e1″ LUMOs of C70 are doubly degenerate and delocalized throughout the molecule, it is difficult to predict the regioselectivity by frontier orbital theory. It is found that vibronic coupling density analysis for the effective mode as a reaction mode illustrates the idea of a functional group embedded in the reactive sites. Furthermore, the vibronic coupling constants for localized stretching vibrational modes enable us to estimate the quantitative reactivity. These calculated results agree well with the experimental findings. The principle of chemical reactivity proposed by Parr and Yang is modified as follows: the preferred direction is the one for which the initial vibronic coupling density for a reaction mode of the isolated reactant is a minimum.

  8. Phthalides: Distribution in Nature, Chemical Reactivity, Synthesis, and Biological Activity.

    Science.gov (United States)

    León, Alejandra; Del-Ángel, Mayela; Ávila, José Luis; Delgado, Guillermo

    oxidation, reduction, addition, elimination, and cycloaddition reactions, and treatments with Lewis acids of (Z)-ligustilide have afforded linear dimers. Some intramolecular condensations and differentiated cyclizations of the dimeric phthalides have been carried out, providing evidences for the particular chemical reactivity of these compounds.Several structural modifications of phthalides have been carried out subjecting them to microbial transformations by different species of bacteria, fungi and algae, and these included resolutions of racemic mixtures and oxidations, among others.The [π4s + π2s] and [π2s + π2s] cycloadditions of (Z)-ligustilide for the synthesis of dimeric phthalides have been reported, and different approaches involving cyclizations, Alder-Rickert reactions, Sharpless asymmetric hydroxylations, or Grignard additions have been used for the synthesis of monomeric phthalides. The use of phthalides as building blocks for divergent oriented synthesis has been proven.Many of the naturally occurring phthalides display different biological activities including antibacterial, antifungal, insecticidal, cytotoxic, and anti-inflammatory effects, among many others, with a considerable recent research on the topic. In the case of compounds isolated from the Apiaceae, the bioactivities correlate with the traditional medicinal uses of the natural sources. Some monomeric phthalides have shown their ability to attenuate certain neurological diseases, including stroke, Alzheimer's and Parkinson's diseases.The present contribution covers the distribution of phthalides in nature and the findings in the structural diversity, chemical reactivity, biotransformations, syntheses, and bioactivity of natural and semisynthetic phthalides.

  9. Encoding of Fundamental Chemical Entities of Organic Reactivity Interest using chemical ontology and XML.

    Science.gov (United States)

    Durairaj, Vijayasarathi; Punnaivanam, Sankar

    2015-09-01

    Fundamental chemical entities are identified in the context of organic reactivity and classified as appropriate concept classes namely ElectronEntity, AtomEntity, AtomGroupEntity, FunctionalGroupEntity and MolecularEntity. The entity classes and their subclasses are organized into a chemical ontology named "ChemEnt" for the purpose of assertion, restriction and modification of properties through entity relations. Individual instances of entity classes are defined and encoded as a library of chemical entities in XML. The instances of entity classes are distinguished with a unique notation and identification values in order to map them with the ontology definitions. A model GUI named Entity Table is created to view graphical representations of all the entity instances. The detection of chemical entities in chemical structures is achieved through suitable algorithms. The possibility of asserting properties to the entities at different levels and the mechanism of property flow within the hierarchical entity levels is outlined. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Chemical reactivity of quinmerac herbicide through the Fukui function.

    Science.gov (United States)

    Mendoza-Huizar, Luis Humberto

    2014-01-01

    In the present work we have calculated DFT reactivity descriptors for quinmerac (7-chloro-3-methylquinoline-8-carboxylic acid) at the MP2/6-311++G(d,p)//B3LYP/6-311++G(2d,2p) level of theory to analyze its reactivity. Reactivity descriptors such as ionization energy, molecular hardness, electrophilicity, condensed Fukui function and total energies were calculated to predict changes in its reactivity. The Fukui function values predict that electrophilic and free radical attacks on quinmerac might cause aromatic substitutions, while nucleophilic attacks would cause cleavage of the C=N bond.

  11. Conservative or reactive? Mechanistic chemical perspectives on organic matter stability

    Science.gov (United States)

    Koch, Boris

    2016-04-01

    Carbon fixation by terrestrial and marine primary production has a fundamental seasonal effect on the atmospheric carbon content and it profoundly contributes to long-term carbon storage in form of organic matter (OM) in soils, water, and sediments. The efficacy of this sequestration process strongly depends on the degree of OM persistence. Therefore, one of the key issues in dissolved and particulate OM research is to assess the stability of reservoirs and to quantify their contribution to global carbon fluxes. Incubation experiments are helpful to assess OM stability during the first, early diagenetic turnover induced by sunlight or microbes. However, net carbon fluxes within the global carbon cycle also act on much longer time scales, which are not amenable in experiments. It is therefore critical to improve our mechanistic understanding to be able to assess potential future changes in the organic matter cycle. This session contribution highlights some achievements and open questions in the field. An improved mechanistic understanding of OM turnover particularly depends on the molecular characterization of biogeochemical processes and their kinetics: (i) in soils and sediments, aggregation/disaggregation of OM is primarily controlled by its molecular composition. Hence, the chemical composition determines the transfer of organic carbon from the large particulate to the small dissolved organic matter reservoir - an important substrate for microbial metabolism. (ii) In estuaries, dissolved organic carbon gradients usually suggest conservative behavior, whereas molecular-level studies reveal a substantial chemical modification of terrestrial DOM along the land-ocean interface. (iii) In the ocean, previous studies have shown that the recalcitrance of OM depends on bulk concentration and energy yield. However, ultrahigh resolution mass spectrometry in combination with radiocarbon analyses also emphasized that stability is tightly connected to molecular composition

  12. Effect of chemical reactivity on the detonation initiation in shock accelerated flow in a confined space

    Institute of Scientific and Technical Information of China (English)

    Yue-Jin Zhu; Gang Dong; Yi-Xin Liu; Bao-Chun Fan; Hua Jiang

    2013-01-01

    The interactions of a spherical flame with an incident shock wave and its reflected shock wave in a confined space were investigated using the three-dimensional reactive Navier-Stokes equations,with emphasis placed on the effect of chemical reactivity of mixture on the flame distortion and detonation initiation after the passage of the reflected shock wave.It is shown that the spatio-temporal characteristics of detonation initiation depend highly on the chemical reactivity of the mixture.When the chemical reactivity enhances,the flame can be severely distorted to form a reactive shock bifurcation structure with detonations initiating at different three-dimensional spatial locations.Moreover,the detonation initiation would occur earlier in a mixture of more enhanced reactivity.The results reveal that the detonations arise from hot spots in the unburned region which are initiated by the shock-detonation-transition mechanism.

  13. New compact-type latex photometric immunoassay system for hemoglobin and three acute inflammation markers: neutrophil count, C-reactive protein, and anti-streptolysin O.

    Science.gov (United States)

    Fukumori, Tatsuo; Ohta, Hironobu; Okubo, Akio; Hino, Masayuki; Ohta, Kensuke; Yamane, Takahisa; Tatsumi, Noriyuki

    2002-01-01

    A new compact-type latex photometric immunoassay system, SPOTCHEM IM SI-3510 (ARKRAY, Inc., Kyoto, Japan), which assays three kinds of inflammatory markers-neutrophil count (NPC), C-reactive protein (CRP), and anti-streptolysin O (ASO)-was evaluated. Hemoglobin (Hb), which is a good marker for anemia, can also be measured with it. NPC and CRP are measured using antibodies against neutrophilic elastase and CRP, purified streptolysin O was used for ASO determination, and Hb was measured by an azide-methemoglobin method. Whole blood, serum, and plasma specimens can be used as samples with this system. In this study, whole blood treated with dipotassium ethylenediamine tetraacetic acid was used for evaluation. Linearity and reproducibility were good for all of the items studied. Good correlations were observed between the results obtained by this system and those obtained by routine methods. Since NPC exhibited a high correlation with the routine white blood cell (WBC) counts, it was judged to be useful as a substitute for WBC counting. Since this system is small and easy to operate, and evaluation revealed reliable results, it was judged to be practical for small laboratories, and satellite testing in hospitals and physicians' office laboratories for patients suspected to have acute inflammation.

  14. Lunar Dust Chemical, Electrical, and Mechanical Reactivity: Simulation and Characterization

    Science.gov (United States)

    VanderWal, Randy L.

    2008-01-01

    Lunar dust is recognized to be a highly reactive material in its native state. Many, if not all Constellation systems will be affected by its adhesion, abrasion, and reactivity. A critical requirement to develop successful strategies for dealing with lunar dust and designing tolerant systems will be to produce similar material for ground-based testing.

  15. On the Inclusion of Inorganic Chemical Reactivity in High School Chemistry: The Reactivity Network.

    Science.gov (United States)

    Mellon, E. K.

    1989-01-01

    Reports the function of the Reactivity Network which is to translate reactivity data from the primary literature into some 30 reviews for high school teachers and curriculum developers and to disseminate that information nationwide. Discusses a needs assessment done for the project. (MVL)

  16. Modeling the reactivities of hydroxyl radical and ozone towards atmospheric organic chemicals using quantitative structure-reactivity relationship approaches.

    Science.gov (United States)

    Gupta, Shikha; Basant, Nikita; Mohan, Dinesh; Singh, Kunwar P

    2016-07-01

    The persistence and the removal of organic chemicals from the atmosphere are largely determined by their reactions with the OH radical and O3. Experimental determinations of the kinetic rate constants of OH and O3 with a large number of chemicals are tedious and resource intensive and development of computational approaches has widely been advocated. Recently, ensemble machine learning (EML) methods have emerged as unbiased tools to establish relationship between independent and dependent variables having a nonlinear dependence. In this study, EML-based, temperature-dependent quantitative structure-reactivity relationship (QSRR) models have been developed for predicting the kinetic rate constants for OH (kOH) and O3 (kO3) reactions with diverse chemicals. Structural diversity of chemicals was evaluated using a Tanimoto similarity index. The generalization and prediction abilities of the constructed models were established through rigorous internal and external validation performed employing statistical checks. In test data, the EML QSRR models yielded correlation (R (2)) of ≥0.91 between the measured and the predicted reactivities. The applicability domains of the constructed models were determined using methods based on descriptors range, Euclidean distance, leverage, and standardization approaches. The prediction accuracies for the higher reactivity compounds were relatively better than those of the low reactivity compounds. Proposed EML QSRR models performed well and outperformed the previous reports. The proposed QSRR models can make predictions of rate constants at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards OH radical and O3 in the atmosphere.

  17. The selective peptide reactivity of chemical respiratory allergens under competitive and non-competitive conditions.

    Science.gov (United States)

    Lalko, Jon F; Kimber, Ian; Dearman, Rebecca J; Api, Anne Marie; Gerberick, G Frank

    2013-01-01

    It is well established that certain chemicals cause respiratory allergy. In common with contact allergens, chemicals that induce sensitization of the respiratory tract must form stable associations with host proteins to elicit an immune response. Measurement of the reactivity of chemical allergens to single nucleophilic peptides is increasingly well-described, and standardized assays have been developed for use in hazard assessment. This study employed standard and modified peptide reactivity assays to investigate the selectivity of chemical respiratory allergens for individual amino acids under competitive and non-competitive conditions. The reactivity of 20 known chemical respiratory sensitizers (including diisocyanates, anhydrides, and reactive dyes) were evaluated for reactivity towards individual peptides containing cysteine, lysine, histidine, arginine, or tyrosine. Respiratory allergens exhibited the common ability to deplete both lysine and cysteine peptides; however, reactivity for histidine, arginine, and tyrosine varied between chemicals, indicating differences in relative binding affinity toward each nucleophile. To evaluate amino acid selectivity for cysteine and lysine under competitive conditions a modified assay was used in which reaction mixtures contained different relative concentrations of the target peptides. Under these reaction conditions, the binding preferences of reference respiratory and contact allergens (dinitrochlorobenzene, dinitrofluorobenzene) were evaluated. Discrete patterns of reactivity were observed showing various levels of competitive selectivity between the two allergen classes.

  18. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    NARCIS (Netherlands)

    Scheeren, H.A.

    2003-01-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large

  19. PREDICTION OF CHEMICAL REACTIVITY PARAMETERS AND PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS FROM MOLECULAR STRUCTURE USING SPARC

    Science.gov (United States)

    The computer program SPARC (SPARC Performs Automated Reasoning in Chemistry) has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms...

  20. PREDICTION OF CHEMICAL REACTIVITY PARAMETERS AND PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS FROM MOLECULAR STRUCTURE USING SPARC

    Science.gov (United States)

    The computer program SPARC (SPARC Performs Automated Reasoning in Chemistry) has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms...

  1. The relationship between periapical lesions and the serum levels of glycosylated hemoglobin and C-reactive protein in type 2 diabetic patients

    Science.gov (United States)

    Al-Zahrani, Mohammad S.; Abozor, Basel M.; Zawawi, Khalid H.

    2017-01-01

    Objectives: To investigate the relationship between the presence of periapical lesions (PL) and levels of glycosylated hemoglobin (HbA1c), and C-reactive protein (CRP) in patients with type 2 diabetes. Methods: This cross-sectional study was conducted at Ibn Sina National College for Medical Studies, Jeddah, Kingdom of Saudi Arabia, between September 2013 and February 2015. Medical and dental history and Sociodemographic data were obtained from participants. Dental and periodontal examinations were conducted and blood samples were obtained to determine levels of HbA1c and CRP. The presence of PL was recorded from panoramic and periapical radiographs. Descriptive statistics and multivariable linear and logistic regression models were used for data analyses. Results: One hundred patients were included; mean age was 48.9 ± 8.5 years. Of these patients, 14% had no PL, whereas 25% had one or 2 lesions, 32% had 3 or 4 lesions, and 29% had ≥5 PL. The mean HbA1c was 9.8% (± 2.5) mg/L and CRP was 6.9 mg/L (± 6.3). The presence of PL was significantly associated with a higher level of HbA1c independent of age, gender, probing depth, and plaque index (p=0.023). Individuals with PL were also more likely to have a high CRP level (>3 mg/L) independent of the previous covariates (odds ratio: 1.19; 95% confidence interval: 1.01-1.41). Conclusion: Periapical lesions are associated with a poorer glycemic control and a higher CRP level in type 2 diabetic patients. PMID:28042628

  2. Chemical reactivity of the compressed noble gas atoms and their reactivity dynamics during collisions with protons

    Indian Academy of Sciences (India)

    P K Chattaraj; B Maiti; U Sarkar

    2003-06-01

    Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study the dynamics of reactivity parameters during a collision between protons and He atoms in different electronic states for various projectile velocities and impact parameters. Dynamical variants of the principles of maximum hardness, minimum polarizability and maximum entropy are found to be operative.

  3. Models for risk assessment of reactive chemicals in aquatic toxicology

    NARCIS (Netherlands)

    Freidig, Andreas Peter

    2001-01-01

    A quantitative structure property relationship (QSPR) for a,b-unsaturated carboxylates (mainly acrylates and methacrylates) was established in chapter 2. Chemical reaction rate constants were measured for 12 different chemicals with three different nucleophiles, namely H 2 O, OH - and glutathione (G

  4. Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

    Science.gov (United States)

    Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

    2016-12-01

    In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ((1)H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Reactive skin decontamination lotion (RSDL) for the decontamination of chemical warfare agent (CWA) dermal exposure.

    Science.gov (United States)

    Schwartz, M D; Hurst, C G; Kirk, M A; Reedy, S J D; Braue, E H

    2012-08-01

    Rapid decontamination of the skin is the single most important action to prevent dermal absorption of chemical contaminants in persons exposed to chemical warfare agents (CWA) and toxic industrial chemicals (TICs) as a result of accidental or intentional release. Chemicals on the skin may be removed by mechanical means through the use of dry sorbents or water. Recent interest in decontamination systems which both partition contaminants away from the skin and actively neutralize the chemical has led to the development of several reactive decontamination solutions. This article will review the recently FDA-approved Reactive Skin Decontamination Lotion (RSDL) and will summarize the toxicity and efficacy studies conducted to date. Evidence of RSDL's superior performance against vesicant and organophosphorus chemical warfare agents compared to water, bleach, and dry sorbents, suggests that RSDL may have a role in mass human exposure chemical decontamination in both the military and civilian arenas.

  6. Hemoglobin electrophoresis

    Science.gov (United States)

    ... 12. Read More A1C test Anemia Hemoglobin Hemolytic anemia Sickle cell anemia Thalassemia Review Date 1/31/2016 Updated by: ... Anemia Blood Count Tests Blood Disorders Newborn Screening Sickle Cell Anemia Browse the Encyclopedia A.D.A.M., Inc. ...

  7. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity

    Science.gov (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  8. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity

    Science.gov (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  9. Chemical Reactivity as a Probe of Ionic-Liquid Surfaces

    Science.gov (United States)

    2009-04-30

    In practice, four ionic liquids have been investigated so far [EMIM] [Im], [ BMIM ] [Im], [PMIM] [Im] and [DMIM] [Im] (see Fig. 2 for definitions), with...N S CF3 O OS CF3 O O [Rmim] [Im] [EMIM] [Im] R = C2H5 [MMIM] [Im] R = CH3 [ BMIM ] [Im] R = C4H9 [PMIM] [Im] R = C5H11 [OMIM] [Im] R = C8H17 [DMIM... BMIM ] [Im] (B = butyl) and [PMIM] [Im] (P = pentyl) have also been measured and the relevant reactivity ratios are given in Table 1. Fig. 4

  10. Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate.

    Science.gov (United States)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi

    2016-03-21

    Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp(2) hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

  11. Hemoglobin C disease

    Science.gov (United States)

    Clinical hemoglobin C ... Hemoglobin C is an abnormal type of hemoglobin, the protein in red blood cells that carries oxygen. It is ... Americans. You are more likely to have hemoglobin C disease if someone in your family has had ...

  12. Reactivity of Dual-Use Decontaminants with Chemical Warfare Agents

    Science.gov (United States)

    2016-07-01

    decrease the logistical burden associated with transport and storage of decontaminants. The experiments in this study were focused on evaluating...propanediammonium dichloride, isopropanol, inert ingredients/water, hydrogen peroxide, diacetin Decontaminant formulated for chemical warfare agents F...potassium bisulfate, potassium sulfate, dipotassium peroxodisulfate, magnesium carbonate Acidic oxidative chemistry, used for VX laboratory waste

  13. Extension of the Dermal Sensitisation Threshold (DST) approach to incorporate chemicals classified as reactive.

    Science.gov (United States)

    Safford, Robert J; Api, Anne Marie; Roberts, David W; Lalko, Jon F

    2015-08-01

    The evaluation of chemicals for their skin sensitising potential is an essential step in ensuring the safety of ingredients in consumer products. Similar to the Threshold of Toxicological Concern, the Dermal Sensitisation Threshold (DST) has been demonstrated to provide effective risk assessments for skin sensitisation in cases where human exposure is low. The DST was originally developed based on a Local Lymph Node Assay (LLNA) dataset and applied to chemicals that were not considered to be directly reactive to skin proteins, and unlikely to initiate the first mechanistic steps leading to the induction of sensitisation. Here we have extended the DST concept to protein reactive chemicals. A probabilistic assessment of the original DST dataset was conducted and a threshold of 64 μg/cm(2) was derived. In our accompanying publication, a set of structural chemistry based rules was developed to proactively identify highly reactive and potentially highly potent materials which should be excluded from the DST approach. The DST and rule set were benchmarked against a test set of chemicals with LLNA/human data. It is concluded that by combining the reactive DST with knowledge of chemistry a threshold can be established below which there is no appreciable risk of sensitisation for protein-reactive chemicals.

  14. A Multiphilic Descriptor for Chemical Reactivity and Selectivity

    CERN Document Server

    Padmanabhan, J; Elango, M; Subramanian, V; Krishnamoorthy, B S; Gutierrez-Oliva, S; Toro-Labbe, A; Roy, D R; Chattaraj, P K

    2007-01-01

    In line with the local philicity concept proposed by Chattaraj et al. (Chattaraj, P. K.; Maiti, B.; Sarkar, U. J. Phys. Chem. A. 2003, 107, 4973) and a dual descriptor derived by Toro-Labbe and coworkers (Morell, C.; Grand, A.; Toro-Labbe, A. J. Phys. Chem. A. 2005, 109, 205), we propose a multiphilic descriptor. It is defined as the difference between nucleophilic (Wk+) and electrophilic (Wk-) condensed philicity functions. This descriptor is capable of simultaneously explaining the nucleophilicity and electrophilicity of the given atomic sites in the molecule. Variation of these quantities along the path of a soft reaction is also analyzed. Predictive ability of this descriptor has been successfully tested on the selected systems and reactions. Corresponding force profiles are also analyzed in some representative cases. Also, to study the intra- and intermolecular reactivities another related descriptor namely, the nucleophilicity excess (DelW-+) for a nucleophile, over the electrophilicity in it has been d...

  15. Reactive schedule modification in multipurpose batch chemical plants

    Energy Technology Data Exchange (ETDEWEB)

    Kanakamedala, K.B.; Reklaitis, G.V.; Venkatasubramanian, V. (Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering)

    1994-01-01

    A new scheme is described for reactive schedule modification in the face of unexpected deviations in processing times and unit availabilities of a multipurpose batch plant (MBP). Schedule modification is done using at least impact heuristic beam search which proceeds in two levels: creation of a decision tree which makes use of possible reroutings of the product that is causing a conflict, and heuristic pruning of the search space to contain the combinatorial complexity. The heuristic chooses a path among all possible reroutings for a product such that the impact of each decision on the rest of the schedule is kept as small as possible. This approach has been implemented and tested on a number of simulated deviations in a MBP case study with three products. The proposed least impact heuristic was found to perform better than the earliest finishing unit heuristic in all the cases considered.

  16. Accelerating Wave Function Convergence in Interactive Quantum Chemical Reactivity Studies

    CERN Document Server

    Mühlbach, Adrian H; Reiher, Markus

    2015-01-01

    The inherently high computational cost of iterative self-consistent-field (SCF) methods proves to be a critical issue delaying visual and haptic feedback in real-time quantum chemistry. In this work, we introduce two schemes for SCF acceleration. They provide a guess for the initial density matrix of the SCF procedure generated by extrapolation techniques. SCF optimizations then converge in fewer iterations, which decreases the execution time of the SCF optimization procedure. To benchmark the proposed propagation schemes, we developed a test bed for performing quantum chemical calculations on sequences of molecular structures mimicking real-time quantum chemical explorations. Explorations of a set of six model reactions employing the semi-empirical methods PM6 and DFTB3 in this testing environment showed that the proposed propagation schemes achieved speedups of up to thirty percent as a consequence of a reduced number of SCF iterations.

  17. Improved Understanding of In Situ Chemical Oxidation Soil Reactivity

    Science.gov (United States)

    2007-12-01

    This technique is dependent on measuring gamma radiation induced in the sample by irradiation with neutrons. The primary source of neutrons for...that TOC is related to NODmax (as indicated by Eq. 26) and its primary effects have been removed as part of the normalization. The parameter a...chemical remediation of contaminated sites. The presence of iron minerals (e.g., goethite, magnetite, and hematite ) or other transition metals (Mn

  18. Reactive formulations for a neutralization of toxic industrial chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Tucker, Mark D. (Albuqueruqe, NM); Betty, Rita G. (Rio Rancho, NM)

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  19. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    OpenAIRE

    H. A. Scheeren

    2003-01-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons ...

  20. Importance of asparagine on the conformational stability and chemical reactivity of selected anti-inflammatory peptides

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: csorico@comunidad.unam.mx [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz-Boca del Río, Universidad Veracruzana, C.P. 91700 Veracruz (Mexico); Campos-Fernández, Linda; Alvarado-Salazar, Andres [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), C.P. 09340 México, D.F. (Mexico)

    2015-08-18

    Highlights: • Asparagine plays an important role to anti-inflammatory effect of peptides. • The electron-donor substituent groups favor the formation of the hydrogen bonds, which contribute in the structural stability of peptides. • Chemical reactivity and the physicochemical features are crucial in the biological functions of peptides. - Abstract: Inflammatory response events are initiated by a complex series of molecular reactions that generate chemical intermediaries. The structure and properties of peptides and proteins are determined by the charge distribution of their side chains, which play an essential role in its electronic structure and physicochemical properties, hence on its biological functionality. The aim of this study was to analyze the effect of changing one central amino acid, such as substituting asparagine for aspartic acid, from Cys–Asn–Ser in aqueous solution, by assessing the conformational stability, physicochemical properties, chemical reactivity and their relationship with anti-inflammatory activity; employing quantum-chemical descriptors at the M06-2X/6-311+G(d,p) level. Our results suggest that asparagine plays a more critical role than aspartic acid in the structural stability, physicochemical features, and chemical reactivity of these tripeptides. Substituent groups in the side chain cause significant changes on the conformational stability and chemical reactivity, and consequently on their anti-inflammatory activity.

  1. Role of tip chemical reactivity on atom manipulation process in dynamic force microscopy.

    Science.gov (United States)

    Sugimoto, Yoshiaki; Yurtsever, Ayhan; Abe, Masayuki; Morita, Seizo; Ondráček, Martin; Pou, Pablo; Pérez, Ruben; Jelínek, Pavel

    2013-08-27

    The effect of tip chemical reactivity on the lateral manipulation of intrinsic Si adatoms toward a vacancy site on a Si(111)-(7 × 7) surface has been investigated by noncontact atomic force microscopy at room temperature. Here we measure the atom-hopping probabilities associated with different manipulation processes as a function of the tip-surface distance by means of constant height scans with chemically different types of tips. The interactions between different tips and Si atoms are evaluated by force spectroscopic measurements. Our results demonstrate that the ability to manipulate Si adatoms depends extremely on the chemical nature of the tip apex and is correlated with the maximal attractive force measured over Si adatoms. We rationalize the observed dependence of the atom manipulation process on tip-apex chemical reactivity by means of density functional theory calculations. The results of these calculations suggest that the ability to reduce the energy barrier associated with the Si adatom movement depends profoundly on tip chemical reactivity and that the level of energy barrier reduction is higher with tips that exhibit high chemical reactivity with Si adatoms. The results of this study provide a better way to control the efficiency of the atomic manipulation process for chemisorption systems.

  2. The alteration and investigation of c-peptide, glycosylated hemoglobin and sensitive C-reactive protein test of gestational diabetes mellitus%妊娠糖尿病患者C-P、HbAlc和hs-CRP的改变及意义

    Institute of Scientific and Technical Information of China (English)

    谢则金; 王厚照; 黄璐; 黄幼芳

    2011-01-01

    目的 探讨C肽(C-P)、糖化血红蛋白(HbAlc)和超敏C反应蛋白(hs-CRP)在妊娠糖尿病诊断中的临床意义.方法 对正常对照组36例、正常妊娠组50例及妊娠糖尿病组56例采用生化和化学发光免疫方法进行hs-CRP、HbAlc、C-P的测定.结果 妊娠糖尿病组hs-CRP、HbAlc和C-P结果与正常妊娠组相比均明显增高(P<0.01);C-P对妊娠糖尿病诊断的特异性高于HbAlc(P<0.05);阳性预测值为91.42%,也明显高于HbAlc(P<0.05);两者联合检测的结果中,联合检测的特异性和阳性预测值分别为98.84%和96.77%,明显高于两者单独检测的结果(Phemoglobin and sensitive C -reactive protein test in diagnosis of gestational diabetes mellitns.Methods: 36 cases health control, 56 cases of gestational diabetes mellitus and 50 cases of normal pregnant women were selected.C - peptide, glycosylated hemoglobin and sensitive C - reactive protein test were measured by biochemical and chemiluminescence immunoassay methods.Results: Compared with the control and the normal pregnant group,the values of glycosylated hemoglobin, C - peptide and sensitive C - reactive protein were higher apparently in the gestational diabetes mellitus group ( P <0.01 ).The specificity of c -peptide were significantly higher than glycosylated hemoglobin in the gestational diabetes mellitus; The specificity and the positive (98.84%and 96.77% ) predictive value of combined detection of aglycosylated hemoglobin and c - peptide were significantly higher than Single detection ( P <0.05 ).Conclusions: There were high value of c - peptide, glycosylated hemoglobin and sensitive C -reactive protein test in diagnosis of gestational diabetes mellitus; Combined detection of C - peptide, glycosylated

  3. Solution-phase synthesis of inorganic nanostructures by chemical transformation from reactive templates

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The solution-phase synthesis by chemical transformation from reactive templates has proved to be very effective in morphology-controlled synthesis of inorganic nanostructures. This review paper summarizes the recent progress in solution-phase synthesis of one-dimensional and hollow inorganic nanostructures via reactive templates, focusing on the approaches developed in our lab. The formation mechanisms based on reactive templates are discussed in depth to show the general concepts for the preparation processes. An outlook on the future development in this area is also presented.

  4. A tutorial for understanding chemical reactivity through the valence bond approach.

    Science.gov (United States)

    Usharani, Dandamudi; Lai, Wenzhen; Li, Chunsen; Chen, Hui; Danovich, David; Shaik, Sason

    2014-07-21

    This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight.

  5. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1997-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  7. Improvement of the chemical inhibition phenotyping assay by cross-reactivity correction.

    Science.gov (United States)

    Njuguna, Nicholas M; Umehara, Ken-Ichi; Huth, Felix; Schiller, Hilmar; Chibale, Kelly; Camenisch, Gian

    2016-12-01

    The fraction of an absorbed drug metabolized by the different hepatic cytochrome P450 (CYP) enzymes, relative to total hepatic CYP metabolism (fmCYP), can be estimated by measuring the inhibitory effects of presumably selective CYP inhibitors on the intrinsic metabolic clearance of a drug using human liver microsomes. However, the chemical inhibition data are often affected by cross-reactivities of the chemical inhibitors used in this assay. To overcome this drawback, the cross-reactivities exhibited by six chemical inhibitors (furafylline, montelukast, sulfaphenazole, ticlopidine, quinidine and ketoconazole) were quantified using specific CYP enzyme marker reactions. The determined cross-reactivities were used to correct the in vitro fmCYPs of nine marketed drugs. The corrected values were compared with reference data obtained by physiologically based pharmacokinetics simulation using the software SimCYP. Uncorrected in vitro fmCYPs of the nine drugs showed poor linear correlation with their reference data (R2=0.443). Correction by factoring in inhibitor cross-reactivities significantly improved the correlation (R2=0.736). Correcting in vitro chemical inhibition results for cross-reactivities appear to offer a straightforward and easily adoptable approach to provide improved fmCYP data for a drug.

  8. Chemical synthesis and biochemical reactivity of bacteriophage lambda PR promoter.

    OpenAIRE

    1983-01-01

    By a combination of chemical and enzymatic methods, a 75 base pair DNA duplex containing the sequence of the lambda PR promoter including the OR1 and OR2 cI repressor binding sites was synthesized. The solid support phosphite triester procedure (Caruthers, M. H. et al., Cold Spring Harbor Symposia on Quantitative Biology XLVII, in press) was used for the synthesis of oligonucleotides comprising the sequence. We report here an adaptation of the method of DNA synthesis in test tubes. Assembly o...

  9. Investigation of opening switch mechanisms based on chemically reactive plasmas

    Science.gov (United States)

    Lapatovich, W. P.; Piejak, R. B.; Proud, J. M.

    1985-11-01

    An investigation of discharge-induced chemical reactions resulting in high-density product vapors containing strongly attaching gases has been conducted to evaluate the feasibility and potential of such reactions in rapid opening plasma switches. This new concept of employing such reactions to limit and/or interrupt large currents on a microsecond time scale was studied in two element (electrodeless and electroded) devices and in three element (electroded) devices. Bimolecular and unimolecular reactions were considered. The plasma reaction between AlCl sub 3 and SiO sub 2 was studied. The electrical properties of one of the reaction products (SiCl sub 4) is reported.

  10. Chemical stability and in chemico reactivity of 24 fragrance ingredients of concern for skin sensitization risk assessment.

    Science.gov (United States)

    Avonto, Cristina; Wang, Mei; Chittiboyina, Amar G; Vukmanovic, Stanislav; Khan, Ikhlas A

    2017-09-16

    Twenty-four pure fragrance ingredients have been identified as potential concern for skin sensitization. Several of these compounds are chemically unstable and convert into reactive species upon exposure to air or light. In the present work, a systematic investigation of the correlation between chemical stability and reactivity has been undertaken. The compounds were subjected to forced photodegradation for three months and the chemical changes were studied with GC-MS. At the end of the stability study, two-thirds of the samples were found to be unstable. The generation of chemically reactive species was investigated using the in chemico HTS-DCYA assay. Eleven and fourteen compounds were chemically reactive before and after three months, respectively. A significant increase in reactivity upon degradation was found for isoeugenol, linalool, limonene, lyral, citronellol and geraniol; in the same conditions, the reactivity of hydroxycitronellal decreased. The non-reactive compounds α-isomethyl ionone, benzyl alcohol, amyl cinnamal and farnesol became reactive after photo-oxidative degradation. Overall, forced degradation resulted in four of non-reactive fragrance compounds to display in chemico thiol reactivity, while ten out of 24 compounds remained inactive. Chemical degradation thus not necessarily occurs with generation of reactive species. Non-chemical activation may be involved for the 10 stable unreactive compounds. Copyright © 2017. Published by Elsevier Ltd.

  11. Chemical Modification on Reactive Dye Adsorption Capacity of Castor Seeds

    Directory of Open Access Journals (Sweden)

    V. Dharmalingam

    2011-01-01

    Full Text Available Abstract: The roles played by four major functional groups (amine, carboxyl, azo, hydroxyl groups in the biomass of castor seeds in adsorption of seven dyes were investigated. These functional groups in castor seeds were chemically modified individually to determine their contribution to the adsorption of ionic dyes. The dyes used were remazol red B, procino yellow, fast green FCF, brilliant cresyl blue, methylene blue, neutral red, red-141. It was found that hydroxyl group inhibited the adsorption of anionic dyes but it was major functional group in the adsorption of cationic dyes, hydroxyl group was important functional group in the adsorption of all seven dyes and the effect of methylation of amino group was not significant on the adsorption of seven dyes.

  12. Understanding chemical reactivity for homo- and heterobifunctional protein cross-linking agents.

    Science.gov (United States)

    Chen, Fan; Nielsen, Simone; Zenobi, Renato

    2013-07-01

    Chemical cross-linking, combined with mass spectrometry, has been applied to map three-dimensional protein structures and protein-protein interactions. Proper choice of the cross-linking agent, including its reactive groups and spacer arm length, is of great importance. However, studies to understand the details of reactivity of the chemical cross-linkers with proteins are quite sparse. In this study, we investigated chemical cross-linking from the aspects of the protein structures and the cross-linking reagents involved, by using two structurally well-known proteins, glyceraldehyde 3-phosohate dehydrogenase and ribonuclease S. Chemical cross-linking reactivity was compared using a series of homo- and hetero-bifunctional cross-linkers, including bis(sulfosuccinimidyl) suberate, dissuccinimidyl suberate, bis(succinimidyl) penta (ethylene glycol), bis(succinimidyl) nona (ethylene glycol), m-maleimidobenzoyl-N-hydroxysulfosuccinimide ester, 2-pyridyldithiol-tetraoxaoctatriacontane-N-hydrosuccinimide and succinimidyl-[(N-maleimidopropionamido)-tetracosaethyleneglycol]ester. The protein structure itself, especially the distances between target amino acid residues, was found to be a determining factor for the cross-linking efficiency. Moreover, the reactive groups of the chemical cross-linker also play an important role; a higher cross-linking reaction efficiency was found for maleimides compared to 2-pyrimidyldithiols. The reaction between maleimides and sulfhydryl groups is more favorable than that between N-hydroxysuccinimide esters and amine groups, although cysteine residues are less abundant in proteins compared to lysine residues. Copyright © 2013 John Wiley & Sons, Ltd.

  13. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  14. Absorbent pads for Containment, Neutralization, and Clean-Up of Environmental Spills Containing Chemically-Reactive Agents

    Science.gov (United States)

    Davis, Dennis D. (Inventor)

    1997-01-01

    A pad for cleaning up liquid spills is described which contains a porous surface covering, and an absorbent interior containing chemically reactive reagents for neutralizing noxious chemicals within the spilled liquid. The porous surface and the absorbent component would normally consist of chemically resistant materials allowing tentative spill to pass. The absorbent interior which contains the neutralizing reagents can but is not required to be chemically resilient and conducts the liquid chemical spill towards the absorbent interior containing the chemically reactive reagents where the dangerous and undesirable chemicals within the chemical spill are then neutralized as well as removed from the premises.

  15. Electronic Structure of Pi Systems: Part III--Applications in Spectroscopy and Chemical Reactivity.

    Science.gov (United States)

    Fox, Marye Anne; Matsen, F. A.

    1985-01-01

    Shows that electronic structure diagrams make more accurate predictions of spectral properties and chemical reactivity for simple pi systems than do either Huckel molecular orbital or valence bond theory alone. Topics addressed include absorption and photoelectron spectra, spin density distribution in radicals, and several problems regarding…

  16. Test results of chemical reactivity test (CRT) analysis of structural materials and explosives

    Energy Technology Data Exchange (ETDEWEB)

    Back, P.S.; Barnhart, B.V.; Walters, R.R.; Haws, L.D.; Collins, L.W.

    1980-03-21

    The chemical reactivity test, CRT, is a procedure used to screen the compatibility of component structure materials with explosives. This report contains the results of CRT materials evaluations conducted at Mound Facility. Data about materials combinations are catalogued both under the name of the explosive and the nonexplosive.

  17. Self-Decontaminating Fibrous Materials Reactive toward Chemical Threats.

    Science.gov (United States)

    Bromberg, Lev; Su, Xiao; Martis, Vladimir; Zhang, Yunfei; Hatton, T Alan

    2016-07-13

    Polymers that possess highly nucleophilic pyrrolidinopyridine (Pyr) and primary amino (vinylamine, VAm) groups were prepared by free-radical copolymerization of N,N-diallylpyridin-4-amine (DAAP) and N-vinylformamide (NVF) followed by acidic hydrolysis of NVF into VAm. The resulting poly(DAAP-co-VAm-co-NVF) copolymers were water-soluble and reacted with water-dispersible polyurethane possessing a high content of unreacted isocyanate groups. Spray-coating of the nylon-cotton (NYCO), rayon, and poly(p-phenylene terephthalamide) (Kevlar 119) fibers pretreated with phosphoric acid resulted in covalent bonding of the polyurethane with the hydroxyl groups on the fiber surface. A second spray-coating of aqueous solutions of poly(DAAP-co-VAm-co-NVF) on the polyurethane-coated fiber enabled formation of urea linkages between unreacted isocyanate groups of the polyurethane layer and the amino groups of poly(DAAP-co-VAm-co-NVF). Fibers with poly(DAAP-co-VAm-co-NVF) attached were compared with fibers modified by adsorption of water-insoluble poly(butadiene-co-pyrrolidinopyridine) (polyBPP) in terms of the stability against polymer leaching in aqueous washing applications. While the fibers modified by attachment of poly(DAAP-co-VAm-co-NVF) exhibited negligible polymer leaching, over 65% of adsorbed polyBPP detached and leached from the fibers within 7 days. Rayon fibers modified by poly(DAAP-co-VAm-co-NVF) were tested for sorption of dimethyl methylphosphonate (DMMP) in the presence of moisture using dynamic vapor sorption technique. Capability of the fibers modified with poly(DAAP-co-VAm-co-NVF) to facilitate hydrolysis of the sorbed DMMP in the presence of moisture was uncovered. The self-decontaminating property of the modified fibers against chemical threats was tested using a CWA simulant diisopropylfluorophosphate (DFP) in aqueous media at pH 8.7. Fibers modified with poly(DAAP-co-VAm-co-NVF) facilitated hydrolysis of DFP with the half-lives up to an order of magnitude

  18. Chemical reactivity and biological activity of chalcones and other α,β-unsaturated carbonyl compounds.

    Science.gov (United States)

    Maydt, Daniela; De Spirt, Silke; Muschelknautz, Christian; Stahl, Wilhelm; Müller, Thomas J J

    2013-08-01

    Abstract 1. Chalcones are structural analogues of benzalacetophenone (BAP). Several derivatives have been identified in plants and anticarcinogenic and anti-inflammatory properties were attributed to the compounds, probably related to their direct antioxidant activity or stimulatory effects on the expression of endogenous defence enzymes like hemeoxygenase-1 (HO-1). HO-1 expression is triggered by the Nrf2-Keap1 signalling pathway, initiated by the addition of chalcones to thiol groups of Keap1 via Michael-type reaction. 2. The present study used a model system estimating the reactivity of different synthetic chalcones and other α,β-unsaturated carbonyl compounds with thiols and compared the chemical reactivity with the biological activity, measured by HO-1 expression in human dermal fibroblasts. 3. Chemical reactivity with the thiol group of N-acetylcysteine was determined with 5,5'-dithiobis-(2-nitrobenzoic acid) and followed chemical principles of structure-reactivity relationship. Most reactive were sulforaphane, dimethylfumarate, chalcone 3 ((2E)-1-phenyl-3-pyrimidin-2-ylprop-2-en-1-one) and chalcone 7 (1,3-diphenylprop-2-yn-1-one). This result demonstrates that α,β-unsaturated carbonyl derivatives react with thiols differently. All compounds were also biologically active; however, expression of HO-1 was not only related to the chemical reactivity but also to the lipophilicity of the molecules which likely affected transmembrane uptake. Most efficient inducers of HO-1 expression were BAP, 4-hydroxynonenal and chalcone 1 (4-[(1E)-3-oxo-3-phenylprop-1-en-1-yl]benzonitrile), chalcone 5 ((2E)-1-phenyl-3-[4-(trifluoromethyl)-phenyl]prop-2-en-1-one) and chalcone 7.

  19. Improving peroxidase-like activity of hemoglobin by recombining hemoglobin using chemically modified heme%修饰血红素提高血红蛋白类过氧化物酶活性

    Institute of Scientific and Technical Information of China (English)

    凌辉生; 李阳; 封琳; 李任强

    2011-01-01

    The phenol or 4-biphenylol was used to modify the heme. The modified hemin group was recombined with apo-hemoglobin to prepare novel artificial hemoglobin. Absorption spectral sean demonstrated that the artificial recombined hemoglobins with modified heme were obtained. Experimental resultsshowed that the peroxidase-like activity of modified hemoglobins was enhanced compared with that of native hemoglobin. And the enzymatic activity of modified hemoglobin with 4-biphenylol modified heme was as about 1.6 folds than that of the native hemoglobin.%利用苯酚或对羟基联苯时血红蛋白的血红素辅基进行化学修饰,将修饰后的血红素与脱辅基血红蛋白进行重组得到新的血红蛋白.以光吸收扫描分析修饰血红素和重组血红蛋白,证明新的重组血红蛋白构建成功.酶活力测定表明,修饰血红素得到的重组血红蛋白的类过氧化物酶活性都比天然血红蛋白的酶活力高,用对羟基联笨修饰血红素得到的重组血红蛋白的酶活提高明显,约是天然血红蛋白的1.6倍.

  20. Chemical Reactivity and Liquid/Nonliquid States of Secondary Organic Material.

    Science.gov (United States)

    Li, Yong Jie; Liu, Pengfei; Gong, Zhaoheng; Wang, Yan; Bateman, Adam P; Bergoend, Clara; Bertram, Allan K; Martin, Scot T

    2015-11-17

    The reactivity of secondary organic material (SOM) of variable viscosity, ranging from nonliquid to liquid physical states, was studied. The SOM, produced in aerosol form from terpenoid and aromatic precursor species, was reacted with ammonia at variable relative humidity (RH). The ammonium-to-organic mass ratio (MNH4+/MOrg) increased monotonically from reactivity limited by diffusion at low RH to one limited by other factors at higher RH. For the studied size distributions and reaction times, the transition corresponded to a diffusivity above 10-17.5 ± 0.5 m2 s-1. The threshold RH values for the transition were 90% for β-caryophyllene-derived SOM. The transition RH for reactivity differed in all cases from the transition RH of a nonliquid to a liquid state. For instance, for α-pinene-derived SOM the transition for chemical reactivity of 35-45% RH can be compared to the nonliquid to liquid transition of 65-90% RH. These differences imply that chemical transport models of atmospheric chemistry should not use the SOM liquid to nonliquid phase transition as one-to-one surrogates of SOM reactivity.

  1. Biochar and hydrochar reactivity assessed by chemical, physical and biological methods

    Science.gov (United States)

    Naisse, Christophe; Alexis, Marie; Wiedner, Katja; Glaser, Bruno; pozzi, Alessandro; Carcaillet, Christopher; Criscuoli, Irene; Miglietta, Franco; Rumpel, Cornelia

    2014-05-01

    Field application of biochar is intended to increase soil carbon (C) storage. The assessment of C storage potential of biochars lacks methods and standard materials. In this study, we compared the chemical reactivity of biochars and hydrochars and their potential mineralisation before and after physical weathering as one possibility to evaluate their environmental stability. We used biochars produced by gasification (GSs) and hydrochars produced by hydrothermal carbonisation (HTCs) produced from three different feedstocks as well as Holocene charcoals (150 and 2000 yr old). Their chemical reactivity was analysed after acid dichromate oxidation and their mineralisation potential after laboratory incubations before and after physical weathering. Our results showed that use of acid dichromate oxidation may allow for differentiation of the reactivity of modern biochars but that chemical reactivity of biochars is poorly suited to assess their environmental residence time because it may change with exposure time in soil. Physical weathering induced a carbon loss and increased biological stability of biochar, while reducing its positive priming effect on native soil organic matter. Model extrapolations based on our data showed that decadal C sequestration potential of GS and HTC is globally equivalent when all losses including those due to priming and physical weathering were taken into account. However, at century scale only GS may have the potential to increase soil C storage.

  2. Self-organised synthesis of Rh nanostructures with tunable chemical reactivity

    Directory of Open Access Journals (Sweden)

    Lizzit S

    2007-01-01

    Full Text Available AbstractNonequilibrium periodic nanostructures such as nanoscale ripples, mounds and rhomboidal pyramids formed on Rh(110 are particularly interesting as candidate model systems with enhanced catalytic reactivity, since they are endowed with steep facets running along nonequilibrium low-symmetry directions, exposing a high density of undercoordinated atoms. In this review we report on the formation of these novel nanostructured surfaces, a kinetic process which can be controlled by changing parameters such as temperature, sputtering ion flux and energy. The role of surface morphology with respect to chemical reactivity is investigated by analysing the carbon monoxide dissociation probability on the different nanostructured surfaces.

  3. Chemical modelling of Alkali Silica reaction: Influence of the reactive aggregate size distribution

    Energy Technology Data Exchange (ETDEWEB)

    Poyet, S. [CEA Saclay, DEN/DANS/DPC/SCCME/LECBA, F-91191 Gif Sur Yvette, (France); Sellier, A. [UPS, LMDC, INSA Toulouse, F-33077 Bordeaux 4, (France); Capra, B. [Oxand SA, F-77210 Avon (France); Foray, G. [Univ Lyon 1, L2MS, PETRA GC, F-69622 Villeurbanne (France); Torrenti, J.M. [IRSN, F-92262 Fontenay Aux Roses (France); Cognon, H. [EdF/DER Les Renardieres, F-77818 Moret Sur Loing (France); Bourdarot, E. [CIH Savoie Technolac, F-73373 Le Bourget du Lac (France)

    2007-07-01

    This article presents a new model which aims at predicting the expansion induced by Alkali Silica Reaction (ASR) and describing the chemical evolution of affected concretes. It is based on the description of the transport and reaction of alkalis and calcium ions within a Relative Elementary Volume (REV). It takes into account the influence of the reactive aggregate size grading on ASR, i.e. the effect of the simultaneous presence of different sized reactive aggregates within concrete. The constitutive equations are detailed and fitted using experimental results. Results from numerical simulations are presented and compared with experiments. (authors)

  4. Effect of discontinuities in Kohn-Sham-based chemical reactivity theory

    CERN Document Server

    Hellgren, M

    2012-01-01

    We provide a new derivation of a formula for the Fukui function of density-functional chemical reactivity theory which incorporates the discontinuities in the Kohn-Sham reference system. Orbital relaxations are described in terms of the exchange-correlation (XC) kernel, i.e., the derivative of the XC potential with respect to the density and it is shown that in order to correctly measure the reactivity toward a nucleophilic reagent a discontinuity of the XC kernel has to be taken into account. The importance of this finding is illustrated in model molecular systems.

  5. Chemical modification of peanut conglutin reduces IgE reactivity but not T cell reactivity in peanut-allergic patients.

    Science.gov (United States)

    van Hoffen, E; van der Kleij, H P M; den Hartog Jager, C F; van Doorn, W A; Knol, E F; Opstelten, D-J; Koppelman, S J; Knulst, A C

    2014-12-01

    Specific immunotherapy for peanut allergy is associated with significant side-effects. Chemically modified allergens may provide a safer alternative. This study aimed to analyse the immunogenicity and allergenicity of modified peanut conglutin. Native peanut conglutin and two modifications thereof were generated (RA and RAGA). Conglutin-specific T cell lines from 11 peanut-allergic patients were analysed for proliferation and cytokine production. Sera from 14 patients were analysed for IgE/IgG1/IgG4 binding by immunoblot and ELISA. IgE reactivity was analysed by direct and indirect basophil activation test (BAT), in presence and absence of patient plasma or CD32-blocking antibodies. T cell proliferation to RA was unchanged, and proliferation to RAGA was reduced compared to native conglutin. Cytokine profiles remained unchanged. IgE, IgG1 and IgG4 binding to RA and RAGA was significantly reduced. In the direct BAT, the relative potency of modified conglutin was decreased in 67% and increased/similar in 33% of the patients. In the indirect BAT, RA and RAGA were 10-100 times less potent than native conglutin. Addition of plasma to the indirect BAT increased the relative potency of modified conglutin in patients with high peanut-specific IgG levels. This was mediated via blocking of the response to native conglutin, most likely by soluble IgG, and not via CD32. Chemical modification of peanut conglutin by RA retains immunogenicity and reduces allergenicity and may be a promising approach for development of a curative treatment for peanut allergy. In a subgroup of patients, where the reactivity of native conglutin is already partially blocked by IgG, the effect of the modification of conglutin is less pronounced. © 2014 John Wiley & Sons Ltd.

  6. Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level

    Science.gov (United States)

    Szoszkiewicz, Robert; Garcia-Manyes, Sergi; Liang, Jian; Kuo, Tzu-Ling; Fernandez, Julio M.

    2010-03-01

    Mechanical force can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free-energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule AFM force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force-induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: Sergi Garcia-Manyes, Jian Liang, Robert Szoszkiewicz, Tzu-Ling Kuo and Julio M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

  7. The influence of zero-flux surface motion on chemical reactivity.

    Science.gov (United States)

    Morgenstern, Amanda; Morgenstern, Charles; Miorelli, Jonathan; Wilson, Tim; Eberhart, M E

    2016-02-21

    Visualizing and predicting the response of the electron density, ρ(r), to an external perturbation provides a portion of the insight necessary to understand chemical reactivity. One strategy used to portray electron response is the electron pushing formalism commonly utilized in organic chemistry, where electrons are pictured as flowing between atoms and bonds. Electron pushing is a powerful tool, but does not give a complete picture of electron response. We propose using the motion of zero-flux surfaces (ZFSs) in the gradient of the charge density, ∇ρ(r), as an adjunct to electron pushing. Here we derive an equation rooted in conceptual density functional theory showing that the movement of ZFSs contributes to energetic changes in a molecule undergoing a chemical reaction. Using a substituted acetylene, 1-iodo-2-fluoroethyne, as an example, we show the importance of both the boundary motion and the change in electron counts within the atomic basins of the quantum theory of atoms in molecules for chemical reactivity. This method can be extended to study the ZFS motion between smaller gradient bundles in ρ(r) in addition to larger atomic basins. Finally, we show that the behavior of ∇ρ(r) within atomic basins contains information about electron response and can be used to predict chemical reactivity.

  8. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

    Science.gov (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

    2015-07-23

    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  9. QSAR classification of metabolic activation of chemicals into covalently reactive species.

    Science.gov (United States)

    Liew, Chin Yee; Pan, Chuen; Tan, Andre; Ang, Ke Xin Magneline; Yap, Chun Wei

    2012-05-01

    Metabolic activation of chemicals into covalently reactive species might lead to toxicological consequences such as tissue necrosis, carcinogenicity, teratogenicity, or immune-mediated toxicities. Early prediction of this undesirable outcome can help in selecting candidates with increased chance of success, thus, reducing attrition at all stages of drug development. The ensemble modelling of mixed features was used for the development of a model to classify the metabolic activation of chemicals into covalently reactive species. The effects of the quality of base classifiers and performance measure for sorting were examined. An ensemble model of 13 naive Bayes classifiers was built from a diverse set of 1,479 compounds. The ensemble model was validated internally with five-fold cross validation and it has achieved sensitivity of 67.4% and specificity of 93.4% when tested on the training set. The final ensemble model was made available for public use.

  10. A Molecular Electron Density Theory Study of the Chemical Reactivity of Cis- and Trans-Resveratrol.

    Science.gov (United States)

    Frau, Juan; Muñoz, Francisco; Glossman-Mitnik, Daniel

    2016-12-01

    The chemical reactivity of resveratrol isomers with the potential to play a role as inhibitors of the nonenzymatic glycation of amino acids and proteins, both acting as antioxidants and as chelating agents for metallic ions such as Cu, Al and Fe, have been studied by resorting to the latest family of Minnesota density functionals. The chemical reactivity descriptors have been calculated through Molecular Electron Density Theory encompassing Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices, the dual descriptor f ( 2 ) ( r ) and the electrophilic and nucleophilic Parr functions. The validity of "Koopmans' theorem in DFT" has been assessed by means of a comparison between the descriptors calculated through vertical energy values and those arising from the HOMO and LUMO values.

  11. The chemical reactivity and structure of collagen studied by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wess, T.J.; Wess, L.; Miller, A. [Univ. of Stirling (United Kingdom)

    1994-12-31

    The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon.

  12. Shielding the chemical reactivity using graphene layers for controlling the surface properties of carbon materials.

    Science.gov (United States)

    Sedykh, A E; Gordeev, E G; Pentsak, E O; Ananikov, V P

    2016-02-14

    Graphene can efficiently shield chemical interactions and gradually decrease the binding to reactive defect areas. In the present study, we have used the observed graphene shielding effect to control the reactivity patterns on the carbon surface. The experimental findings show that a surface coating with a tiny carbon layer of 1-2 nm thickness is sufficient to shield the defect-mediated reactivity and create a surface with uniform binding ability. The shielding effect was directly observed using a combination of microscopy techniques and evaluated with computational modeling. The theoretical calculations indicate that a few graphene layers can drastically reduce the binding energy of the metal centers to the surface defects by 40-50 kcal mol(-1). The construction of large carbon areas with controlled surface reactivity is extremely difficult, which is a key limitation in many practical applications. Indeed, the developed approach provides a flexible and simple tool to change the reactivity patterns on large surface areas within a few minutes.

  13. Unorthodox chemistry for an unorthodox challenge:Exploration of new chemical reactivities for a sustainable future

    Institute of Scientific and Technical Information of China (English)

    LI Chao-Jun

    2012-01-01

    The sustainable development of our future represents an unorthodox challenge in sciences and technologies.The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemical productions with efficient utilization of resource and inherent prevention of waste will provide the foundation for the synthetic chemistry of our future.As part of this endeavor,we have explored metal-mediated reactions in water to minimize protection-deprotection and the use of organic solvents,catalytic nucleophilic additions via C-H reactions to avoid generation and use of stoichiometric organic halides and metal in water,and Cross-Dehydrogenative-Coupling (CDC) reactions to minimize overall transformation steps.

  14. Silicon-doping in carbon nanotubes: formation energies, electronic structures, and chemical reactivity.

    Science.gov (United States)

    Bian, Ruixin; Zhao, Jingxiang; Fu, Honggang

    2013-04-01

    By carrying out density functional theory (DFT) calculations, we have studied the effects of silicon (Si)-doping on the geometrical and electronic properties, as well as the chemical reactivity of carbon nanotubes (CNTs). It is found that the formation energies of these nanotubes increase with increasing tube diameters, indicating that the embedding of Si into narrower CNTs is more energetically favorable. For the given diameters, Si-doping in a (n, 0) CNT is slightly easier than that of in (n, n) CNT. Moreover, the doped CNTs with two Si atoms are easier to obtain than those with one Si atom. Due to the introduction of impurity states after Si-doping, the electronic properties of CNTs have been changed in different ways: upon Si-doping into zigzag CNTs, the band gap of nanotube is decreased, while the opening of band gap in armchair CNTs is found. To evaluate the chemical reactivity of Si-doped CNTs, the adsorption of NH3 and H2O on this kind of material is explored. The results show that N-H bond of NH3 and O-H bond of H2O can be easily split on the surface of doped CNTs. Of particular interest, the novel reactivity makes it feasible to use Si-doped CNT as a new type of splitter for NH3 and H2O bond, which is very important in chemical and biological processes. Future experimental studies are greatly desired to probe such interesting processes.

  15. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR

    Science.gov (United States)

    Vacchi, Isabella A.; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-01

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by

  16. Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse: Chapter 12

    Science.gov (United States)

    Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

    2009-01-01

    Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

  17. Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse

    Science.gov (United States)

    Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

    2009-01-01

    Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

  18. Hemoglobin Philly (β35 tyrosine→phenylalanine): studies in the molecular pathology of hemoglobin

    Science.gov (United States)

    Rieder, Ronald F.; Oski, Frank A.; Clegg, J. B.

    1969-01-01

    An abnormal unstable hemoglobin, hemoglobin Philly, was found in three members of a family, each of whom had evidence of a chronic hemolytic state. The presence of the mutant protein was suggested by the rapid appearance of inclusion bodies upon incubation of erythrocytes with brilliant cresyl blue and by the increased heat precipitability of the hemoglobin. However, no abnormal hemoglobin could be demonstrated by electrophoresis or column chromatography. Sulfhydryl titration of the hemolysates with p-mercuribenzoate indicated that there was an average of four reactive sulfhydryl groups per hemoglobin molecule instead of the usual two. The total number of hemoglobin sulfhydryl groups was normal; six groups were measured when denatured globin was reacted with 5,5′-dithiobis[2-nitrobenzoic acid]. This indicated that the increased sulfhydryl reactivity was due to an increased availability to p-mercuribenzoate of the usually unreactive hemoglobin cysteines at β112 and α104. After treatment for ½ hr with 4-5 moles of p-mercuribenzoate per mole of hemoglobin, electrophoresis revealed that 30-35% of the hemoglobin had been dissociated into α- and β-chains. Normal hemolysates revealed negligible splitting after 72 hr of similar treatment. The α- and β-chains of hemoglobin Philly were separated from the unsplit hemoglobin A by carboxymethyl cellulose chromatography. Fingerprint and amino acid analyses revealed that tyrosine β35 was replaced by phenylalanine. In hemoglobin Philly there is loss of the normal hydrogen bond between the tyrosine hydroxyl group and the carboxyl group of aspartic acid α126 at the α1β1 contact. This shifts the equilibrium from hemoglobin tetramers toward monomers, exposing the β112 and α104 cysteines. In the cell, precipitation of the unstable monomers may contribute to erythrocyte destruction. Images PMID:5822575

  19. Absorption and desorption mass transfer rates in chemically enhanced reactive systems. Part I : Chemical enhancement factors

    NARCIS (Netherlands)

    Hamborg, Espen S.; Versteeg, Geert F.

    2012-01-01

    The chemical enhancement factors have been measured in a controlled environment for absorption and desorption mass transfer processes in aqueous 2.0 M MDEA solutions at temperatures of 298.15, 313.15, and 333.15 K and the loading of CO2 ranging from 0 to 0.8 in a batch-operated stirred tank reactor.

  20. Chemical reactivity parameters (HSAB) applied to magma evolution and ore formation

    Science.gov (United States)

    Vigneresse, Jean-Louis

    2012-11-01

    Magmas are commonly described through the usual content of 10 major oxides. This requires a complex dimensional plot. Concepts of hard-soft acid-base (HSAB) interactions allow estimating chemical reactivity of elements, such as electronegativity, i.e. the chemical potential changed of sign, hardness and electrophilicity. For complex system, those values result from equalization methods, i.e. the equalization of the respective chemical potentials, or from ab-initio computations through density functional theory (DFT). They help to characterize silicate magmas by a single value describing their reactivity. Principles of minimum electrophilicity (mEP), maximum hardness (MHP) and minimum polarizability (mPP) indicate trends towards regions of higher stability. Those parameters are plotted within a fitness landscape diagram, highlighting toward which principle reactions trend. Major oxides, main minerals and magmas determine the respective fields in which evolve natural rocks. Three poles are identified, represented by silica and alkalis, whereas oxidation forms the third trend. Mantle-derived rocks show a large variation in electrophilicity compared to hardness. They present all characters of a closed chemical system, being simply described by the free Gibbs energy. Conversely, rocks contaminated within the continental crust show a large variation in hardness between a silica pole and an alkaline, defining two separate trends. The trends show the character of an open chemical system, requiring a Grand Potential description (i.e. taking into account the difference in chemical potential). The terms open and closed systems refer to thermodynamical description, implying contamination for the crust and recycling for the mantle. The specific role of alkalis contrasts with other cations, pointing to their behavior in modifying silicate polymer structures. A second application deals with the reactivity of the melt and its fluid phase. It leads to a better understanding on the

  1. CFD modeling of reactive pollutant dispersion in simplified urban configurations with different chemical mechanisms

    Science.gov (United States)

    Sanchez, Beatriz; Santiago, Jose-Luis; Martilli, Alberto; Palacios, Magdalena; Kirchner, Frank

    2016-09-01

    An accurate understanding of urban air quality requires considering a coupled behavior between the dispersion of reactive pollutants and atmospheric dynamics. Currently, urban air pollution is mostly dominated by traffic emission, where nitrogen oxides (NOx) and volatile organic compounds (VOCs) are the primary emitted pollutants. However, modeling reactive pollutants with a large set of chemical reactions, using a computational fluid dynamic (CFD) model, requires a large amount of computational (CPU) time. In this sense, the selection of the chemical reactions needed in different atmospheric conditions becomes essential in finding the best compromise between CPU time and accuracy. The purpose of this work is to assess the differences in NO and NO2 concentrations by considering three chemical approaches: (a) passive tracers (non-reactive), (b) the NOx-O3 photostationary state and (c) a reduced complex chemical mechanism based on 23 species and 25 reactions. The appraisal of the effects of chemical reactions focuses on studying the NO and NO2 dispersion in comparison with the tracer behavior within the street. In turn, the effect of including VOC reactions is also analyzed taking into account several VOC / NOx ratios of traffic emission. Given that the NO and NO2 dispersion can also be affected by atmospheric conditions, such as wind flow or the background concentration from season-dependent pollutants, in this work the influence of wind speeds and background O3 concentrations are studied. The results show that the presence of ozone in the street plays an important role in NO and NO2 concentrations. Therefore, greater differences linked to the chemical approach used are found with higher O3 concentrations and faster wind speeds. This bears relation to the vertical flux as a function of ambient wind speed since it increases the pollutant exchange between the street and the overlying air. This detailed study allows one to ascertain under which atmospheric conditions

  2. Selective adsorption of bovine hemoglobin on functional TiO2 nano-adsorbents: surface physic-chemical properties determined adsorption activity

    Science.gov (United States)

    Guo, Shiguang; Zhang, Jianghua; Shao, Mingxue; Zhang, Xia; Liu, Yufeng; Xu, Junli; Meng, Hao; Han, Yide

    2015-04-01

    Surface functionalized nanoparticles are efficient adsorbents which have shown good potential for protein separation. In this work, we chose two different types of organic molecules, oleic acid (OA) and 3-glycidoxypropyltrimethoxy silane (GPTMS), to functionalize the surface of TiO2 nanoparticles, and we studied the effects of this modification on their surface physicochemical properties in correlation with their selective adsorption of proteins. The results showed that the surface zeta potential and the surface water wettability of the modified TiO2 were significantly changed in comparison with the original TiO2 nanoparticles. The adsorption activities of bovine hemoglobin (BHb) and bovine serum albumin (BSA) on these functionalized TiO2 samples were investigated under different conditions, including pH values, contact time, ion strength, and initial protein concentration. In comparison with the non-specific adsorption of original TiO2, however, both the OA-TiO2 and GPTMS-TiO2 exhibited increased BHb adsorption and decreased BSA adsorption at the same time. Using a binary protein mixture as the adsorption object, a higher separation factor (SF) was obtained for OA-TiO2 under optimum conditions. The different adsorption activities of BHb and BSA on the modified TiO2 were correlated with different interactions at the protein/solid interface, and the chemical force as well as the electrostatic force played an important role in the selective adsorption process.

  3. Sampling reactive pathways with random walks in chemical space: Applications to molecular dissociation and catalysis

    Science.gov (United States)

    Habershon, Scott

    2015-09-01

    Automatically generating chemical reaction pathways is a significant computational challenge, particularly in the case where a given chemical system can exhibit multiple reactants and products, as well as multiple pathways connecting these. Here, we outline a computational approach to allow automated sampling of chemical reaction pathways, including sampling of different chemical species at the reaction end-points. The key features of this scheme are (i) introduction of a Hamiltonian which describes a reaction "string" connecting reactant and products, (ii) definition of reactant and product species as chemical connectivity graphs, and (iii) development of a scheme for updating the chemical graphs associated with the reaction end-points. By performing molecular dynamics sampling of the Hamiltonian describing the complete reaction pathway, we are able to sample multiple different paths in configuration space between given chemical products; by periodically modifying the connectivity graphs describing the chemical identities of the end-points we are also able to sample the allowed chemical space of the system. Overall, this scheme therefore provides a route to automated generation of a "roadmap" describing chemical reactivity. This approach is first applied to model dissociation pathways in formaldehyde, H2CO, as described by a parameterised potential energy surface (PES). A second application to the HCo(CO)3 catalyzed hydroformylation of ethene (oxo process), using density functional tight-binding to model the PES, demonstrates that our graph-based approach is capable of sampling the intermediate paths in the commonly accepted catalytic mechanism, as well as several secondary reactions. Further algorithmic improvements are suggested which will pave the way for treating complex multi-step reaction processes in a more efficient manner.

  4. Theoretical Approaches for Understanding the Interplay Between Stress and Chemical Reactivity.

    Science.gov (United States)

    Kochhar, Gurpaul S; Heverly-Coulson, Gavin S; Mosey, Nicholas J

    2015-01-01

    The use of mechanical stresses to induce chemical reactions has attracted significant interest in recent years. Computational modeling can play a significant role in developing a comprehensive understanding of the interplay between stresses and chemical reactivity. In this review, we discuss techniques for simulating chemical reactions occurring under mechanochemical conditions. The methods described are broadly divided into techniques that are appropriate for studying molecular mechanochemistry and those suited to modeling bulk mechanochemistry. In both cases, several different approaches are described and compared. Methods for examining molecular mechanochemistry are based on exploring the force-modified potential energy surface on which a molecule subjected to an external force moves. Meanwhile, it is suggested that condensed phase simulation methods typically used to study tribochemical reactions, i.e., those occurring in sliding contacts, can be adapted to study bulk mechanochemistry.

  5. Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries.

    Science.gov (United States)

    Giordano, Livia; Karayaylali, Pinar; Yu, Yang; Katayama, Yu; Maglia, Filippo; Lux, Simon; Shao-Horn, Yang

    2017-08-17

    Understanding electrochemical and chemical reactions at the electrode-electrolyte interface is of fundamental importance for the safety and cycle life of Li-ion batteries. Positive electrode materials such as layered transition metal oxides exhibit different degrees of chemical reactivity with commonly used carbonate-based electrolytes. Here we employed density functional theory methods to compare the energetics of four different chemical reactions between ethylene carbonate (EC) and layered (LixMO2) and rocksalt (MO) oxide surfaces. EC dissociation on layered oxides was found energetically more favorable than nucleophilic attack, electrophilic attack, and EC dissociation with oxygen extraction from the oxide surface. In addition, EC dissociation became energetically more favorable on the oxide surfaces with transition metal ions from left to right on the periodic table or by increasing transition metal valence in the oxides, where higher degree of EC dissociation was found as the Fermi level was lowered into the oxide O 2p band.

  6. Ultraviolet light photobiology of the protozoan Tetrahymena pyriformis and chemical reactivation of DNA damage

    Energy Technology Data Exchange (ETDEWEB)

    Wheeler, J.S.

    1988-01-01

    The tunable dye laser was developed in order to perform UV-B and UV-C (254-320 nm) action spectra studies on several different organisms. Using the laser, action spectra studies have been performed for Escherichia coli, Saccharomyces, Chlamydomonas, Caenorhabditis elegans, Paramecium, and Tetrahymena pyriformis. Studies generally indicate increasing LD{sub 50} values with increasing wavelength. Two notable findings were made: (1) The action spectra does not follow the DNA absorption spectra at 280, 290 and 295 nm; (2) The repair competent/repair defective sensitization factor does not remain constant throughout the wavelength region. In addition it was found that the repair defective strain of E. coli, Bs-1, showed an increase in survival with increasing UV irradiation, at certain dose levels. Further experiments were designed to better characterize the reactivation. Tetrahymena were exposed to UV-C and reactivated with methyl methanesulfonate (MMS) and 4-nitro quinoline oxide (4-NQO). In both cases survival was seen to increase after chemical exposure. Likewise, UV-C was found to reactivate chemical damage (MMS).

  7. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR.

    Science.gov (United States)

    Vacchi, Isabella A; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-14

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.

  8. Changes in the chemical reactivity of metals exposed to an inert gas glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Klemperer, D.F.; Williams, D.J. (Bristol Univ. (UK). Dept. of Physical Chemistry)

    1983-05-01

    From time to time the literature mentions curious effects on the chemical reactivity of metals due to inert gas ion bombardment: reactivity in corrosive environments is variously said to be inhibited or enhanced. Although there is no obvious explanation for such effects, some possible mechanisms have been suggested. Some simple experiments have been carried out to demonstrate that reactivity effects really do exist and to test such mechanisms. The results are qualitative because a glow discharge was used to implant the rare gas ions. Evaporated films of aluminium and nickel become amorphous after bombardment with xenon ions and the films resisted gaseous and liquid corrosion. On the other hand, aluminium foil bombarded with xenon ions in a Penning pump arrangement was attacked more heavily than unbombarded aluminium. Passivation is attributed to the known lack of reactivity of amorphous metals. Glassy materials appear to lack the normal routes of attack between their subsurface regions and the attacking medium. On the other hand, when a metal surface is heavily ion bombarded the surface is probably damaged to such an extent that the attacking medium gains physical access to the interior and corrosion proceeds rapidly.

  9. Ligand field effect at oxide-metal interface on the chemical reactivity of ultrathin oxide film surface.

    Science.gov (United States)

    Jung, Jaehoon; Shin, Hyung-Joon; Kim, Yousoo; Kawai, Maki

    2012-06-27

    Ultrathin oxide film is currently one of the paramount candidates for a heterogeneous catalyst because it provides an additional dimension, i.e., film thickness, to control chemical reactivity. Here, we demonstrate that the chemical reactivity of ultrathin MgO film grown on Ag(100) substrate for the dissociation of individual water molecules can be systematically controlled by interface dopants over the film thickness. Density functional theory calculations revealed that adhesion at the oxide-metal interface can be addressed by the ligand field effect and is linearly correlated with the chemical reactivity of the oxide film. In addition, our results indicate that the concentration of dopant at the interface can be controlled by tuning the drawing effect of oxide film. Our study provides not only profound insight into chemical reactivity control of ultrathin oxide film supported by a metal substrate but also an impetus for investigating ultrathin oxide films for a wider range of applications.

  10. Constitutive Relations for Reactive Transport Modeling: Effects of Chemical Reactions on Multi-Phase Flow Properties

    Science.gov (United States)

    Zhang, S.; Liu, H. H.; van Dijke, M. I.; Geiger, S.; Agar, S. M.

    2016-12-01

    The relationship between flow properties and chemical reactions is key to modeling subsurface reactive transport. This study develops closed-form equations to describe the effects of mineral precipitation and dissolution on multiphase flow properties (capillary pressure and relative permeabilities) of porous media. The model accounts for the fact that precipitation/dissolution only takes place in the water-filled part of pore space. The capillary tube concept was used to connect pore-scale changes to macroscopic hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and consequently in the pore-size distribution. The updated pore-size distribution is converted back to a new capillary pressure-water saturation relation from which the new relative permeabilities are calculated. Pore network modeling is conducted on a Berea sandstone to validate the new continuum-scale relations. The pore network modeling results are satisfactorily predicted by the new closed-form equations. Currently the effects of chemical reactions on flow properties are represented as a relation between permeability and porosity in reactive transport modeling. Porosity is updated after chemical calculations from the change of mineral volumes, then permeability change is calculated from the porosity change using an empirical permeability-porosity relation, most commonly the Carman-Kozeny relation, or the Verma-Pruess relation. To the best of our knowledge, there are no closed-form relations available yet for the effects of chemical reactions on multi-phase flow properties, and thus currently these effects cannot be accounted for in reactive transport modeling. This work presents new constitutive relations to represent how chemical reactions affect multi-phase flow properties on the continuum scale based on the conceptual model of parallel capillary tubes. The parameters in our new relations are either pre-existing input in a multi-phase flow

  11. Nitrous oxide production from reactive nitrification intermediates: a concerted action of biological and chemical processes

    Science.gov (United States)

    Brüggemann, Nicolas; Heil, Jannis; Liu, Shurong; Wei, Jing; Vereecken, Harry

    2017-04-01

    This contribution tries to open up a new perspective on biogeochemical N2O production processes, taking the term bio-geo-chemistry literally. What if a major part of N2O is produced from reactive intermediates of microbiological N turnover processes ("bio…") leaking out of the involved microorganisms into the soil ("…geo…") and then reacting chemically ("…chemistry") with the surrounding matrix? There are at least two major reactive N intermediates that might play a significant role in these coupled biological-chemical reactions, i.e. hydroxylamine (NH2OH) and nitrite (NO2-), both of which are produced during nitrification under oxic conditions, while NO2- is also produced during denitrification under anoxic conditions. Furthermore, NH2OH is assumed to be also a potential intermediate of DNRA and/or anammox. First, this contribution will summarize information about several chemical reactions involving NH2OH and NO2- leading to the formation of N2O. These abiotic reactions are: reactions of NO2- with reduced metal cations, nitrosation reactions of NO2- and soil organic matter (SOM), the reaction between NO2- and NH2OH, and the oxidation of NH2OH by oxidized metal ions. While these reactions can occur over a broad range of soil characteristics, they are ignored in most current N trace gas studies in favor of biological processes only. Disentangling microbiological from purely chemical N2O production is further complicated by the fact that the chemically formed N2O is either undiscernible from N2O produced during nitrification, or shows an intermediate 15N site preference between that of N2O from nitrification and denitrification, respectively. Results from experiments with live and sterilized soil samples, with artificial soil mixtures and with phenolic lignin decomposition model compounds will be presented that demonstrate the potential contribution of these abiotic processes to soil N trace gas emissions, given a substantial leakage rate of these reactive

  12. Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca$^+$ ions

    CERN Document Server

    Chang, Yuan-Pin; Küpper, Jochen; Rösch, Daniel; Wild, Dieter; Willitsch, Stefan

    2013-01-01

    Many molecules exhibit multiple rotational isomers (conformers) that interconvert thermally and are difficult to isolate. Consequently, a precise characterization of their role in chemical reactions has proven challenging. We have probed the reactivity of specific conformers using an experimental technique based on their spatial separation in a molecular beam by electrostatic deflection. The separated conformers react with a target of Coulomb-crystallized ions in a trap. In the reaction of Ca$^+$ with 3-aminophenol, we find a twofold larger rate constant for the \\textit{cis}- compared to the \\textit{trans}-conformer (differentiated by the O-H bond orientation). This result is explained by conformer-specific differences in the long-range ion-molecule interaction potentials. Our approach demonstrates the possibility of controlling reactivity through selection of conformational states.

  13. XCHEM-1D: A Heat Transfer/Chemical Kinetics Computer Program for multilayered reactive materials

    Energy Technology Data Exchange (ETDEWEB)

    Gross, R.J.; Baer, M.R.; Hobbs, M.L.

    1993-10-01

    An eXplosive CHEMical kinetics code, XCHEM, has been developed to solve the reactive diffusion equations associated with thermal ignition of energetic materials. This method-of-lines code uses stiff numerical methods and adaptive meshing to resolve relevant combustion physics. Solution accuracy is maintained between multilayered materials consisting of blends of reactive components and/or inert materials. Phase change and variable properties are included in one-dimensional slab, cylindrical and spherical geometries. Temperature-dependent thermal properties have been incorporated and the modification of thermal conductivities to include decomposition effects are estimated using solid/gas volume fractions determined by species fractions. Gas transport properties, including high pressure corrections, have also been included. Time varying temperature, heat flux, convective and thermal radiation boundary conditions, and layer to layer contact resistances have also been implemented.

  14. Optical and Chemical Properties of Mixed-valent Rhenium Oxide Films Synthesized by Reactive DC Magnetron Sputtering

    Science.gov (United States)

    2015-04-03

    AFRL-RX-WP-JA-2015-0178 OPTICAL AND CHEMICAL PROPERTIES OF MIXED- VALENT RHENIUM OXIDE FILMS SYNTHESIZED BY REACTIVE DC MAGNETRON...To) 06 May 2010 – 16 March 2015 4. TITLE AND SUBTITLE OPTICAL AND CHEMICAL PROPERTIES OF MIXED-VALENT RHENIUM OXIDE FILMS SYNTHESIZED BY REACTIVE ...DC MAGNETRON SPUTTERING (POSTPRINT) 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 62102F 6. AUTHOR(S) (see

  15. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  16. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    Energy Technology Data Exchange (ETDEWEB)

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.

    1997-07-01

    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  17. Modeling and analysis of time-dependent processes in a chemically reactive mixture

    Science.gov (United States)

    Ramos, M. P.; Ribeiro, C.; Soares, A. J.

    2017-08-01

    In this paper, we study the propagation of sound waves and the dynamics of local wave disturbances induced by spontaneous internal fluctuations in a reactive mixture. We consider a non-diffusive, non-heat conducting and non-viscous mixture described by an Eulerian set of evolution equations. The model is derived from the kinetic theory in a hydrodynamic regime of a fast chemical reaction. The reactive source terms are explicitly computed from the kinetic theory and are built in the model in a proper way. For both time-dependent problems, we first derive the appropriate dispersion relation, which retains the main effects of the chemical process, and then investigate the influence of the chemical reaction on the properties of interest in the problems studied here. We complete our study by developing a rather detailed analysis using the Hydrogen-Chlorine system as reference. Several numerical computations are included illustrating the behavior of the phase velocity and attenuation coefficient in a low-frequency regime and describing the spectrum of the eigenmodes in the small wavenumber limit.

  18. The chemical and mechanical behaviors of polymer / reactive metal systems under high strain rates

    Science.gov (United States)

    Shen, Yubin

    As one category of energetic materials, impact-initiated reactive materials are able to release a high amount of stored chemical energy under high strain rate impact loading, and are used extensively in civil and military applications. In general, polymers are introduced as binder materials to trap the reactive metal powders inside, and also act as an oxidizing agent for the metal ingredient. Since critical attention has been paid on the metal / metal reaction, only a few types of polymer / reactive metal interactions have been studied in the literature. With the higher requirement of materials resistant to different thermal and mechanical environments, the understanding and characterization of polymer / reactive metal interactions are in great demand. In this study, PTFE (Polytetrafluoroethylene) 7A / Ti (Titanium) composites were studied under high strain rates by utilizing the Taylor impact and SHPB tests. Taylor impact tests with different impact velocities, sample dimensions and sample configurations were conducted on the composite, equipped with a high-speed camera for tracking transient images during the sudden process. SHPB and Instron tests were carried out to obtain the stress vs. strain curves of the composite under a wide range of strain rates, the result of which were also utilized for fitting the constitutive relations of the composite based on the modified Johnson-Cook strength model. Thermal analyses by DTA tests under different flow rates accompanied with XRD identification were conducted to study the reaction mechanism between PTFE 7A and Ti when only heat was provided. Numerical simulations on Taylor impact tests and microstructural deformations were also performed to validate the constitutive model built for the composite system, and to investigate the possible reaction mechanism between two components. The results obtained from the high strain rate tests, thermal analyses and numerical simulations were combined to provide a systematic study on

  19. Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification

    Indian Academy of Sciences (India)

    DEVENDRA P MISHRA; ANCHAL SRIVASTAVA; R K SHUKLA

    2017-07-01

    This paper describes the spectroscopic ($_{1}\\rm{H}$ and $_{13}\\rm{C NMR}$, FT-IR and UV–Visible), chemical, nonlinear optical and thermodynamic properties of D-Myo-Inositol using quantum chemical technique and its experimental verification. The structural parameters of the compound are determined from the optimized geometry by B3LYP method with $6-311++G(d,p)$ basis set. It was found that the optimized parameters thus obtained are almost in agreement with the experimental ones. A detailed interpretation of the infrared spectra of D-Myo-Inositol is also reported in the present work. After optimization, the proton and carbon NMR chemical shifts of the studied compound are calculated using GIAO and 6-311++G(d,p) basis set. The search of organic materials with improved charge transfer properties requires precise quantum chemical calculations of space-charge density distribution, state and transition dipole moments and HOMO–LUMO states. The nature of the transitions in the observed UV–Visible spectrum of the compound has been studied by the time-dependent density functional theory (TD-DFT). The global reactivity descriptors like chemical potential, electronegativity, hardness, softness and electrophilicity index, have been calculated using DFT. The thermodynamic calculation related to the title compound was also performed at $B3LYP/6-311++G(d,p)$ level of theory. The standard statistical thermodynamic functions like heat capacity at constant pressure, entropy and enthalpy change were obtained from the theoretical harmonic frequencies of the optimized molecule. It is observed that the values of heat capacity, entropy and enthalpy increase with increase intemperature from 100 to 1000 K, which is attributed to the enhancement of molecular vibration with the increase in temperature.

  20. Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification

    Science.gov (United States)

    Mishra, Devendra P.; Srivastava, Anchal; Shukla, R. K.

    2017-07-01

    This paper describes the spectroscopic (^1H and ^{13}C NMR, FT-IR and UV-Visible), chemical, nonlinear optical and thermodynamic properties of D-Myo-Inositol using quantum chemical technique and its experimental verification. The structural parameters of the compound are determined from the optimized geometry by B3LYP method with 6 {-}311{+}{+}G(d,p) basis set. It was found that the optimized parameters thus obtained are almost in agreement with the experimental ones. A detailed interpretation of the infrared spectra of D-Myo-Inositol is also reported in the present work. After optimization, the proton and carbon NMR chemical shifts of the studied compound are calculated using GIAO and 6 {-}311{+}{+}G(d,p) basis set. The search of organic materials with improved charge transfer properties requires precise quantum chemical calculations of space-charge density distribution, state and transition dipole moments and HOMO-LUMO states. The nature of the transitions in the observed UV-Visible spectrum of the compound has been studied by the time-dependent density functional theory (TD-DFT). The global reactivity descriptors like chemical potential, electronegativity, hardness, softness and electrophilicity index, have been calculated using DFT. The thermodynamic calculation related to the title compound was also performed at B3LYP/ 6 {-}311{+}{+}G(d,p) level of theory. The standard statistical thermodynamic functions like heat capacity at constant pressure, entropy and enthalpy change were obtained from the theoretical harmonic frequencies of the optimized molecule. It is observed that the values of heat capacity, entropy and enthalpy increase with increase in temperature from 100 to 1000 K, which is attributed to the enhancement of molecular vibration with the increase in temperature.

  1. Computational Nutraceutics: Chemical Reactivity Properties of the Flavonoid Naringin by Means of Conceptual DFT

    Directory of Open Access Journals (Sweden)

    Jorge Ignacio Martínez-Araya

    2013-01-01

    Full Text Available The M06 family of density functionals has been assessed for the calculation of the molecular structure and properties of the Naringin molecule. The chemical reactivity descriptors have been calculated through Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices and the dual descriptor f(2(r. A comparison between the descriptors calculated through vertical energy values and those arising from the Koopmans' theorem approximation has been performed in order to check for the validity of the last procedure.

  2. Chemical Reactivity Testing for the National Spent Nuclear Fuel Program. Quality Assurance Project Plan

    Energy Technology Data Exchange (ETDEWEB)

    Newsom, H.C.

    1999-01-24

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of Work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, QA-101PD, revision 1, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted.

  3. Predicting Chemical Reactivity from the Charge Density through Gradient Bundle Analysis: Moving beyond Fukui Functions.

    Science.gov (United States)

    Morgenstern, Amanda; Wilson, Timothy R; Eberhart, M E

    2017-06-08

    Predicting chemical reactivity is a major goal of chemistry. Toward this end, atom condensed Fukui functions of conceptual density functional theory have been used to predict which atom is most likely to undergo electrophilic or nucleophilic attack, providing regioselectivity information. We show that the most probable regions for electrophilic attack within each atom can be predicted through analysis of gradient bundle volumes, a property that depends only on the charge density of the neutral molecules. We also introduce gradient bundle condensed Fukui functions to compare the stereoselectivity information obtained from gradient bundle volume analysis. We demonstrate this method using the test set of molecular fluorine, oxygen, nitrogen, carbon monoxide, and hydrogen cyanide.

  4. The role of charge transfer in the stability and reactivity of chemical systems from experimental findings.

    Science.gov (United States)

    Falcinelli, S; Candori, P; Pirani, F; Vecchiocattivi, F

    2017-03-08

    A variety of phenomena, of apparently different natures, are described within a unifying picture, by properly isolating the role of charge/electron transfer as an interaction component triggering chemical reactivity. This basic quantity is isolated by analyzing, with advanced theoretical methods developed by our group, experimental findings characterized with different techniques, such as double photo-ionization spectra, scattering cross sections and auto-ionization reaction probabilities. Suitable rationalization of such phenomena appears to be crucial for modeling the selectivity of basic elementary processes occurring in systems at increasing complexity of fundamental/applied interest, such as plasmas, flames, interstellar media, planetary atmospheres and biological environments.

  5. Atomistic Simulations of Chemical Reactivity of TATB Under Thermal and Shock Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Manaa, M R; Reed, E J; Fried, L E

    2009-09-23

    The study of chemical transformations that occur at the reactive shock front of energetic materials provides important information for the development of predictive models at the grain-and continuum scales. A major shortcoming of current high explosives models is the lack of chemical kinetics data of the reacting explosive in the high pressure and temperature regimes. In the absence of experimental data, long-time scale atomistic molecular dynamics simulations with reactive chemistry become a viable recourse to provide an insight into the decomposition mechanism of explosives, and to obtain effective reaction rate laws. These rates can then be incorporated into thermo-chemical-hydro codes (such as Cheetah linked to ALE3D) for accurate description of the grain and macro scales dynamics of reacting explosives. In this talk, I will present quantum simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals under thermal decomposition (high density and temperature) and shock compression conditions. This is the first time that condensed phase quantum methods have been used to study the chemistry of insensitive high explosives. We used the quantum-based, self-consistent charge density functional tight binding method (SCC{_}DFTB) to calculate the interatomic forces for reliable predictions of chemical reactions, and to examine electronic properties at detonation conditions for a relatively long time-scale on the order of several hundreds of picoseconds. For thermal decomposition of TATB, we conducted constant volume-temperature simulations, ranging from 0.35 to 2 nanoseconds, at {rho} = 2.87 g/cm{sup 3} at T = 3500, 3000, 2500, and 1500 K, and {rho} = 2.9 g/cm{sup 3} and 2.72 g/cm{sup 3}, at T = 3000 K. We also simulated crystal TATB's reactivity under steady overdriven shock compression using the multi-scale shock technique. We conducted shock simulations with specified shock speeds of 8, 9, and 10 km/s for up to 0.43 ns duration, enabling us to track the

  6. Chemical modification of cotton fabrics for improving utilization of reactive dyes.

    Science.gov (United States)

    Fang, Long; Zhang, Xiaodong; Sun, Deshuai

    2013-01-02

    The cotton fabric was chemically modified with the acrylamide through Michael addition reaction and Hoffman degradation reaction. And the optimum chemical modification conditions were determined. The molecular structure of the modified cotton fabric was identified by Fourier transform infrared spectroscopy (FTIR). The structures of both the raw and modified cotton fabrics were investigated by X-ray diffraction and scanning electronic microscopy. The raw and modified cotton fabrics were dyed using commercial reactive dyes with vinyl-sulfone groups. The results showed that the total dye utilization of modified cotton fabrics in the salt-free dyeing was higher than that of raw cotton fabrics in the conventional dyeing. And the color fastness properties and tear strength of modified fabrics were both satisfactory.

  7. Chemically Reactive Solute Distribution in a Steady MHD Boundary Layer Flow over a Stretching Surface

    Directory of Open Access Journals (Sweden)

    M.S Uddin

    2011-01-01

    Full Text Available The paper is concerned to find the distribution of the chemically reactant solute in the MHD flow of an electrically conducting viscous incompressible fluid over a stretching surface. The first order chemical reaction and the variable solute distribution along the surface are taken into consideration. The governing partial differential equations along with appropriate boundary conditions for flow field and reactive solute are transformed into a set of non-linear self-similar ordinary differential equations by using scaling group of transformations. An exact analytic solution is obtained for the velocity field. Using this velocity field, we obtain numerical solution for the reactant concentration field. It reveals from the study that the values of concentration profile enhances with the increase of the magnetic field and decreases with increase of Schmidt number as well as the reaction rate parameter. Most importantly, when the solute distribution along the surface increases then the concentration profile decreases.

  8. Interactions between ingredients in IMX-101: Reactive Chemical Processes Control Insensitive Munitions Properties

    Energy Technology Data Exchange (ETDEWEB)

    Maharrey, Sean P.; Wiese-Smith, Deneille; Highley, Aaron M.; Behrens, Richard,; Kay, Jeffrey J

    2014-03-01

    Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS) measurements have been conducted on a new Insensitive Munitions (IM) formulation. IMX-101 is the first explosive to be fully IM qualified under new NATO STANAG guidelines for fielded munitions. The formulation uses dinitroanisole (DNAN) as a new melt cast material to replace TNT, and shows excellent IM performance when formulated with other energetic ingredients. The scope of this work is to explain this superior IM performance by investigating the reactive processes occurring in the material when subjected to a well-controlled thermal environment. The dominant reactive processes observed were a series of complex chemical interactions between the three main ingredients (DNAN, NQ, and NTO) that occurs well below the onset of the normal decomposition process of any of the individual ingredients. This process shifts the thermal response of the formulations to a much lower temperature, where the kinetically controlled reaction processes are much slower. This low temperature shift has the effect of allowing the reactions to consume the reactive solids (NQ, NTO) well before the reaction rates increase and reach thermal runaway, resulting in a relatively benign response to the external stimuli. The main findings on the interaction processes are presented.

  9. Human hemoglobin genetics

    Energy Technology Data Exchange (ETDEWEB)

    Honig, G.R.; Adams, J.G.

    1986-01-01

    This book contains the following 10 chapters: Introduction; The Human Hemoglobins; The Human Globin Genes; Hemoglobin Synthesis and Globin Gene Expression; The Globin Gene Mutations - A. Mechanisms and Classification; The Globin Gene Mutations - B. Their Phenotypes and Clinical Expression; The Genetics of the Human Globin Gene Loci: Formal Genetics and Gene Linkage; The Geographic Distribution of Globin Gene Variation; Labortory Identification, Screening, Education, and Counseling for Abnormal Hemoglobins and Thalassemias; and Approaches to the Treatment of the Hemoglobin Disorders.

  10. Theoretical studies of chemical reactivity of metabolically activated forms of aromatic amines toward DNA.

    Science.gov (United States)

    Shamovsky, Igor; Ripa, Lena; Blomberg, Niklas; Eriksson, Leif A; Hansen, Peter; Mee, Christine; Tyrchan, Christian; O'Donovan, Mike; Sjö, Peter

    2012-10-15

    The metabolism of aromatic and heteroaromatic amines (ArNH₂) results in nitrenium ions (ArNH⁺) that modify nucleobases of DNA, primarily deoxyguanosine (dG), by forming dG-C8 adducts. The activated amine nitrogen in ArNH⁺ reacts with the C8 of dG, which gives rise to mutations in DNA. For the most mutagenic ArNH₂, including the majority of known genotoxic carcinogens, the stability of ArNH⁺ is of intermediate magnitude. To understand the origin of this observation as well as the specificity of reactions of ArNH⁺ with guanines in DNA, we investigated the chemical reactivity of the metabolically activated forms of ArNH₂, that is, ArNHOH and ArNHOAc, toward 9-methylguanine by DFT calculations. The chemical reactivity of these forms is determined by the rate constants of two consecutive reactions leading to cationic guanine intermediates. The formation of ArNH⁺ accelerates with resonance stabilization of ArNH⁺, whereas the formed ArNH⁺ reacts with guanine derivatives with the constant diffusion-limited rate until the reaction slows down when ArNH⁺ is about 20 kcal/mol more stable than PhNH⁺. At this point, ArNHOH and ArNHOAc show maximum reactivity. The lowest activation energy of the reaction of ArNH⁺ with 9-methylguanine corresponds to the charge-transfer π-stacked transition state (π-TS) that leads to the direct formation of the C8 intermediate. The predicted activation barriers of this reaction match the observed absolute rate constants for a number of ArNH⁺. We demonstrate that the mutagenic potency of ArNH₂ correlates with the rate of formation and the chemical reactivity of the metabolically activated forms toward the C8 atom of dG. On the basis of geometric consideration of the π-TS complex made of genotoxic compounds with long aromatic systems, we propose that precovalent intercalation in DNA is not an essential step in the genotoxicity pathway of ArNH₂. The mechanism-based reasoning suggests rational design strategies to

  11. The influence of condensed tannin structure on rate of microbial mineralization and reactivity to chemical assays.

    Science.gov (United States)

    Norris, Charlotte E; Preston, Caroline M; Hogg, Karen E; Titus, Brian D

    2011-03-01

    We examined how tannin structure influences reactivity in tannin assays and carbon and nitrogen mineralization. Condensed tannins from the foliage of ten tree and shrub species and from pecan shells (Carya illinoensis) had different proportions of: (a) epicatechin (cis) and catechin (trans) isomers, (b) procyanidin (PC) and prodelphinidin (PD) monomers, and (c) different chain lengths. The response of each tannin to several widely used tannin assays was determined. Although there was some variation in response to proanthocyanidin (butanol/HCl) and Folin Ciocalteu assays, we did not deduce any predictable relationship between tannin structure and response to either assay. There was little variation in protein precipitation among the different tannins. To assess biological activity, six of the tannins were incubated with forest humus for 22 days. We determined that, while PC-based tannins remained at least partly extractable for the duration of the incubation, tannins with a high proportion of PD subunits rapidly became unextractable from soil. There was a positive correlation between net nitrogen mineralization and cis chemical structure. Carbon mineralization was enhanced initially by the addition of tannins to humus, but after 22 days, a negative correlation between the proportion of cis subunits and respiration was determined. Overall, we were not able to demonstrate consistent effects of structure on either microbial mineralization or reactivity to chemical assays; such relationships remain elusive.

  12. Differences in the chemical reactivity of individual molecules of an enzyme

    Science.gov (United States)

    Xue, Qifeng; Yeung, Edward S.

    1995-02-01

    MUCH attention has been focused recently on the detection and physical characterization of individual molecules1-11. Using such methods to study the chemical properties, such as reactivity, of single molecules offers the potential to investigate how these might vary from molecule to molecule, and for individual molecules as a function of time. The complex structures of biomolecules such as enzymes make them particularly attractive targets for studying how subtle changes or differences at the molecular level might influence chemical reactivity. We have shown previously12,13 that very small (zeptomole) amounts of enzymes can be studied using a fluorescence microassay; single enzyme molecules have also been detected in oil-dispersed droplets by fluorescence microscopy14,15. Here we report the observation of reactions of individual molecules of lactate dehydrogenase (LDH-1), which produces NADH from lactate and nicotinamide adenine dinucleotide (NAD+). When they are present at very low concentrations in a narrow capillary, each enzyme molecule produces a discrete zone of NADH; these can be manipulated electrophoretically and monitored by fluorescence spectroscopy. We find that the activity of individual electrophoretically pure enzyme molecules can vary by up to a factor of four, and that these activities remain unchanged over a two-hour period. We suggest that the origin of the activity differences may lie in the presence of several stable forms of the enzyme.

  13. Peptide reactivity assay using spectrophotometric method for high-throughput screening of skin sensitization potential of chemical haptens.

    Science.gov (United States)

    Jeong, Yun Hyeok; An, Susun; Shin, Kyeho; Lee, Tae Ryong

    2013-02-01

    Haptens must react with cellular proteins to be recognized by antigen presenting cells. Therefore, monitoring reactivity of chemicals with peptide/protein has been considered an in vitro skin sensitization testing method. The reactivity of peptides with chemicals (peptide reactivity) has usually been monitored by chromatographic methods like HPLC or LC/MS, which are robust tools for monitoring common chemical reactions but are rather expensive and time consuming. Here, we examined the possibility of using spectrophotometric methods to monitor peptide reactivity. Two synthetic peptides, Ac-RWAACAA and Ac-RWAAKAA, were reacted with 48 chemicals (34 sensitizers and 14 non-sensitizers). Peptide reactivity was measured by monitoring unreacted peptides with UV-Vis spectrophotometer using 5,5'-dithiobis-2-nitrobenzoic acid as a detection reagent for the free thiol group of cysteine-containing peptide or fluorometer using fluorescamine™ as a detection reagent for the free amine group of lysine-containing peptide. Chemicals were categorized as sensitizers when they induced more than 10% depletion of cysteine-containing peptide or 20% depletion of lysine-containing peptide. The sensitivity, specificity, and accuracy of this method were 82.4%, 85.7%, and 83.3%, respectively. These results demonstrate that spectrophotometric methods can be easy, fast, and high-throughput screening tools for the prediction of the skin sensitization potential of chemical haptens. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Chemical reactivity and skin sensitization potential for benzaldehydes: can Schiff base formation explain everything?

    Science.gov (United States)

    Natsch, Andreas; Gfeller, Hans; Haupt, Tina; Brunner, Gerhard

    2012-10-15

    Skin sensitizers chemically modify skin proteins rendering them immunogenic. Sensitizing chemicals have been divided into applicability domains according to their suspected reaction mechanism. The widely accepted Schiff base applicability domain covers aldehydes and ketones, and detailed structure-activity-modeling for this chemical group was presented. While Schiff base formation is the obvious reaction pathway for these chemicals, the in silico work was followed up by limited experimental work. It remains unclear whether hydrolytically labile Schiff bases can form sufficiently stable epitopes to trigger an immune response in the living organism with an excess of water being present. Here, we performed experimental studies on benzaldehydes of highly differing skin sensitization potential. Schiff base formation toward butylamine was evaluated in acetonitrile, and a detailed SAR study is presented. o-Hydroxybenzaldehydes such as salicylaldehyde and the oakmoss allergens atranol and chloratranol have a high propensity to form Schiff bases. The reactivity is highly reduced in p-hydroxy benzaldehydes such as the nonsensitizing vanillin with an intermediate reactivity for p-alkyl and p-methoxy-benzaldehydes. The work was followed up under more physiological conditions in the peptide reactivity assay with a lysine-containing heptapeptide. Under these conditions, Schiff base formation was only observable for the strong sensitizers atranol and chloratranol and for salicylaldehyde. Trapping experiments with NaBH₃CN showed that Schiff base formation occurred under these conditions also for some less sensitizing aldehydes, but the reaction is not favored in the absence of in situ reduction. Surprisingly, the Schiff bases of some weaker sensitizers apparently may react further to form stable peptide adducts. These were identified as the amides between the lysine residues and the corresponding acids. Adduct formation was paralleled by oxidative deamination of the parent

  15. Biological and chemical reactivity and phosphorus forms of buffalo manure compost, vermicompost and their mixture with biochar.

    Science.gov (United States)

    Ngo, Phuong-Thi; Rumpel, Cornelia; Ngo, Quoc-Anh; Alexis, Marie; Velásquez Vargas, Gabriela; Mora Gil, Maria de la Luz; Dang, Dinh-Kim; Jouquet, Pascal

    2013-11-01

    This study characterized the carbon and phosphorus composition of buffalo manure, its compost and vermicompost and investigated if presence of bamboo biochar has an effect on their chemical and biological reactivity. The four substrates were characterized for chemical and biochemical composition and P forms. The biological stability of the four substrates and their mixtures were determined during an incubation experiment. Their chemical reactivity was analyzed after acid dichromate oxidation. Biological reactivity of these substrates was related to their soluble organic matter content, which decreased in the order buffalo manure>compost>vermicompost. Phosphorus was labile in all organic substrates and composting transformed organic P into plant available P. The presence of biochar led to a protection of organic matter against chemical oxidation and changed their susceptibility to biological degradation, suggesting that biochar could increase the carbon sequestration potential of compost, vermicompost and manure, when applied in mixture.

  16. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    T. F. Lyon

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  17. Symptoms from masked acrolein exposure suggest altered trigeminal reactivity in chemical intolerance.

    Science.gov (United States)

    Claeson, Anna-Sara; Andersson, Linus

    2017-05-01

    Chemical intolerance (CI) is a widespread occupational and public health problem characterized by symptoms that reportedly result from low-levels of chemical exposure. The mechanisms behind CI are unknown, however modifications of the chemical senses (rather than toxic processes) have been suggested as key components. The aim of this study was to investigate whether individuals with self-reported CI report more sensory irritation during masked acrolein exposure compared to controls without CI. Individuals with CI (n=18) and controls without CI (n=19) were exposed in an exposure chamber. Each participant took part in two exposure conditions - one with heptane (the masking compound), and one with heptane and acrolein at a dose below previously reported sensory irritation thresholds. The exposures lasted for 60min. Symptoms and confidence ratings were measured continuously throughout the exposure as were measurements of electrodermal activity and self-reported tear-film break-up time. Participants were blind to exposure condition. Individuals with CI, compared with controls reported greater sensory irritation in the eyes, nose and throat when exposed to acrolein masked with heptane. There was no difference during exposure to heptane. Masked exposure to acrolein at a concentration below the previously reported detection threshold is perceived as more irritating by individuals with CI compared with controls. The results indicate that there is altered trigeminal reactivity in those with CI compared to controls. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Preparation of Reactive Oligo(p-Phenylene Vinylene) Materials for Spatial Profiling of the Chemical Reactivity of Intracellular Compartments.

    Science.gov (United States)

    Nie, Chenyao; Li, Shengliang; Wang, Bing; Liu, Libing; Hu, Rong; Chen, Hui; Lv, Fengting; Dai, Zhihui; Wang, Shu

    2016-05-01

    An oligo(p-phenylene vinylene) derivative (OPV-pfp) functionalized with pentafluorophenol active ester is designed and synthesized. The high reactivity of OPV-pfp with biological small molecules or macromolecules containing amino groups under physiological conditions leads to spectral changes of OPV-pfp; thus, spatial reactivity discrimination for different subcellular structures inside cells is realized by triggering and imaging the fluorescence signal change of the OPV-pfp. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Reactive species and DNA damage in chronic inflammation: reconciling chemical mechanisms and biological fates.

    Science.gov (United States)

    Lonkar, Pallavi; Dedon, Peter C

    2011-05-01

    Chronic inflammation has long been recognized as a risk factor for many human cancers. One mechanistic link between inflammation and cancer involves the generation of nitric oxide, superoxide and other reactive oxygen and nitrogen species by macrophages and neutrophils that infiltrate sites of inflammation. Although pathologically high levels of these reactive species cause damage to biological molecules, including DNA, nitric oxide at lower levels plays important physiological roles in cell signaling and apoptosis. This raises the question of inflammation-induced imbalances in physiological and pathological pathways mediated by chemical mediators of inflammation. At pathological levels, the damage sustained by nucleic acids represents the full spectrum of chemistries and likely plays an important role in carcinogenesis. This suggests that DNA damage products could serve as biomarkers of inflammation and oxidative stress in clinically accessible compartments such as blood and urine. However, recent studies of the biotransformation of DNA damage products before excretion point to a weakness in our understanding of the biological fates of the DNA lesions and thus to a limitation in the use of DNA lesions as biomarkers. This review will address these and other issues surrounding inflammation-mediated DNA damage on the road to cancer.

  20. The chemical reactivity of the Martian soil and implications for future missions

    Science.gov (United States)

    Zent, Aaron P.; Mckay, Christopher P.

    1994-01-01

    Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

  1. The chemical reactivity of the Martian soil and implications for future missions

    Science.gov (United States)

    Zent, Aaron P.; Mckay, Christopher P.

    1994-01-01

    Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

  2. Reactive Ion Etching as Cleaning Method Post Chemical Mechanical Polishing for Phase Change Memory Device

    Institute of Scientific and Technical Information of China (English)

    ZHONG Min; SONG Zhi-Tang; LIU Bo; FENG Song-Lin; CHEN Bomy

    2008-01-01

    In order to improve nano-scale phase change memory performance,a super-clean interface should be obtained after chemical mechanical polishing (CMP) of Ge2Sb2Te5 phase change films.We use reactive ion etching (RIE) as the cleaning method.The cleaning effect is analysed by scanning electron microscopy and an energy dispersive spectrometer.The results show that particle residue on the surface has been removed.Meanwhile,Ge2 Sb2 Te5 material stoichiometric content ratios are unchanged.After the top electrode is deposited,currentvoltage characteristics test demonstrates that the set threshold voltage is reduced from 13 V to 2.7V and the threshold current from 0.1 mA to 0.025 mA.Furthermore,we analyse the RIE cleaning principle and compare it with the ultrasonic method.

  3. Basic and Reactive Dyes Sorption Enhancement of Rice Hull through Chemical Modification

    Directory of Open Access Journals (Sweden)

    Siew-Teng Ong

    2010-01-01

    Full Text Available Problem statement: Many studies have been conducted on the removal of either anionic or cationic dyes. However, as a mixture of dyes does commonly exist together in wastewater, therefore it is of great interest to have a material that can remove both types of dyes. Approach: To prepare an inexpensive and efficient sorbent by chemically modifying rice hull for the removal of both basic and reactive dyes. Different chemical modifications were performed on rice hull and a comparison study on the uptake of dyes was carried out. Optimization study was carried out on most promising modified rice hull. Surface morphology of modified rice hull was examined and the functional groups present were determined using FTIR. Results: From the results, it appeared that by using EDA modified rice hull, an appreciable amount of both dyes could be sorbed. Varying the EDA/NRH ratios and heating temperatures affected the uptake of BB3 and RO16. The investigated sorbents were non-porous materials, due to the absence of pores and cavities. Sorption-desorption study showed that a complete recovery of BB3 can be obtained using high concentrations of H2SO4 and HCl but the desorption experiments of RO16 using NH3 and NaOH were not successful. Conclusion: The modification of rice hull with EDA under the optimum conditions (in a ratio of 1.00 g of NRH to 0.02 mole of EDA in a well stirred water bath at 80°C for 2 h resulted in the formation of a sorbent (MRH that could be used successfully to remove Both Basic (BB3 and Reactive dyes (RO16.

  4. Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

    Science.gov (United States)

    Hung, Ching-Cheh

    1994-01-01

    Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

  5. Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

    Directory of Open Access Journals (Sweden)

    J. Rinne

    2012-06-01

    Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

  6. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    Science.gov (United States)

    Scheeren, H. A.

    2003-09-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of

  7. Global chemical reactivity parameters for several chiral beta-blockers from the Density Functional Theory viewpoint.

    Science.gov (United States)

    Talmaciu, Mona Maria; Bodoki, Ede; Oprean, Radu

    2016-01-01

    Beta-adrenergic antagonists have been established as first line treatment in the medical management of hypertension, acute coronary syndrome and other cardiovascular diseases, as well as for the prevention of initial episodes of gastrointestinal bleeding in patients with cirrhosis and esophageal varices, glaucoma, and have recently become the main form of treatment of infantile hemangiomas. The aim of the present study is to calculate for 14 beta-blockers several quantum chemical descriptors in order to interpret various molecular properties such as electronic structure, conformation, reactivity, in the interest of determining how such descriptors could have an impact on our understanding of the experimental observations and describing various aspects of chemical binding of beta-blockers in terms of these descriptors. The 2D chemical structures of the beta-blockers (14 molecules with one stereogenic center) were cleaned in 3D, their geometry was preoptimized using the software MOPAC2012, by PM6 method, and then further refined using standard settings in MOE; HOMO and LUMO descriptors were calculated using semi-empirical molecular orbital methods AM1, MNDO and PM3, for the lowest energy conformers and the quantum chemical descriptors (HLG, electronegativity, chemical potential, hardness and softness, electrophilicity) were then calculated. According to HOMO-LUMO gap and the chemical hardness the most stable compounds are alprenolol, bisoprolol and esmolol. The softness values calculated for the study molecules revolve around 0.100. Propranolol, sotalol and timolol have among the highest electrophilicity index of the studied beta-blocker molecules. Results obtained from calculations showed that acebutolol, atenolol, timolol and sotalol have the highest values for the electronegativity index. The future aim is to determine whether it is possible to find a valid correlation between these descriptors and the physicochemical behavior of the molecules from this class. The

  8. The Hemoglobin E Thalassemias

    Science.gov (United States)

    Fucharoen, Suthat; Weatherall, David J.

    2012-01-01

    Hemoglobin E (HbE) is an extremely common structural hemoglobin variant that occurs at high frequencies throughout many Asian countries. It is a β-hemoglobin variant, which is produced at a slightly reduced rate and hence has the phenotype of a mild form of β thalassemia. Its interactions with different forms of α thalassemia result in a wide variety of clinical disorders, whereas its coinheritance with β thalassemia, a condition called hemoglobin E β thalassemia, is by far the most common severe form of β thalassemia in Asia and, globally, comprises approximately 50% of the clinically severe β-thalassemia disorders. PMID:22908199

  9. Local and linear chemical reactivity response functions at finite temperature in density functional theory.

    Science.gov (United States)

    Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2015-12-28

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

  10. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Franco-Pérez, Marco, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340 (Mexico); Ayers, Paul W., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Gázquez, José L., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340 (Mexico); Vela, Alberto, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Departamento de Química, Centro de Investigación y de Estudios Avanzados (Cinvestav), Av. Instituto Politécnico Nacional 2508, México, D.F. 07360 (Mexico)

    2015-12-28

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

  11. Accelerating moderately stiff chemical kinetics in reactive-flow simulations using GPUs

    CERN Document Server

    Niemeyer, Kyle E

    2014-01-01

    The chemical kinetics ODEs arising from operator-split reactive-flow simulations were solved on GPUs using explicit integration algorithms. Nonstiff chemical kinetics of a hydrogen oxidation mechanism (9 species and 38 irreversible reactions) were computed using the explicit fifth-order Runge-Kutta-Cash-Karp method, and the GPU-accelerated version performed faster than single- and six-core CPU versions by factors of 126 and 25, respectively, for 524,288 ODEs. Moderately stiff kinetics, represented with mechanisms for hydrogen/carbon-monoxide (13 species and 54 irreversible reactions) and methane (53 species and 634 irreversible reactions) oxidation, were computed using the stabilized explicit second-order Runge-Kutta-Chebyshev (RKC) algorithm. The GPU-based RKC implementation demonstrated an increase in performance of nearly 59 and 10 times, for problem sizes consisting of 262,144 ODEs and larger, than the single- and six-core CPU-based RKC algorithms using the hydrogen/carbon-monoxide mechanism. With the met...

  12. Reactive chemical transport in ground-water hydrology: Challenges to mathematical modeling

    Energy Technology Data Exchange (ETDEWEB)

    Narasimhan, T.N.; Apps, J.A.

    1990-07-01

    For a long time, earth scientists have qualitatively recognized that mineral assemblages in soils and rocks conform to established principles of chemistry. In the early 1960's geochemists began systematizing this knowledge by developing quantitative thermodynamic models based on equilibrium considerations. These models have since been coupled with advective-dispersive-diffusive transport models, already developed by ground-water hydrologists. Spurred by a need for handling difficult environmental issues related to ground-water contamination, these models are being improved, refined and applied to realistic problems of interest. There is little doubt that these models will play an important role in solving important problems of engineering as well as science over the coming years. Even as these models are being used practically, there is scope for their improvement and many challenges lie ahead. In addition to improving the conceptual basis of the governing equations, much remains to be done to incorporate kinetic processes and biological mediation into extant chemical equilibrium models. Much also remains to be learned about the limits to which model predictability can be reasonably taken. The purpose of this paper is to broadly assess the current status of knowledge in modeling reactive chemical transport and to identify the challenges that lie ahead.

  13. Dynamics and Kinetics Study of "In-Water" Chemical Reactions by Enhanced Sampling of Reactive Trajectories.

    Science.gov (United States)

    Zhang, Jun; Yang, Y Isaac; Yang, Lijiang; Gao, Yi Qin

    2015-11-12

    High potential energy barriers and engagement of solvent coordinates set challenges for in silico studies of chemical reactions, and one is quite commonly limited to study reactions along predefined reaction coordinate(s). A systematic protocol, QM/MM MD simulations using enhanced sampling of reactive trajectories (ESoRT), is established to quantitatively study chemical transitions in complex systems. A number of trajectories for Claisen rearrangement in water and toluene were collected and analyzed, respectively. Evidence was found that the bond making and breaking during this reaction are concerted processes in solutions, preferentially through a chairlike configuration. Water plays an important dynamic role that helps stabilize the transition sate, and the dipole-dipole interaction between water and the solute also lowers the transition barrier. The calculated rate coefficient is consistent with the experimental measurement. Compared with water, the reaction pathway in toluene is "narrower" and the reaction rate is slower by almost three orders of magnitude due to the absence of proper interactions to stabilize the transition state. This study suggests that the "in-water" nature of the Claisen rearrangement in aqueous solution influences its thermodynamics, kinetics, as well as dynamics.

  14. Flow of Chemically Reactive non-Newtonian Fluids in Twin-Screw Extruders

    Science.gov (United States)

    Zhu, Weimin; Jaluria, Yogesh

    1998-11-01

    Many applications of twin-screw extruders are found in the processing of food, plastics, pharmaceutical materials and other highly viscous materials. In reactive extrusion, complex interactions in which the flow pattern, and the heat and mass transfer are affected by viscous dissipation, reaction energy, convection, residence time distribution and rheology of the materials may occur. The fluid flow, heat transfer and chemical reactions in a fully intermeshing, corotating and self wiping twin screw extruder were investigated numerically by using the finite volume method. The screw channel of a twin screw extruder are approximated as translation (parabolic) domain and intermeshing (elliptic) domain. The full governing equations were solved to determine the velocity components in the three coordinate directions. The energy equation is coupled with the equations of motion through viscosity. The Residence Time Distribution (RTD), was obtained by using a particle tracking method. The flow field, temperature field, pressure as well as RTD and chemical conversion were obtained by numerical simulation and the results yielded agreement with experimental measurements and expected physical characteristic of the process.

  15. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Sudarjanto, Gatut [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller-Lehmann, Beatrice [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller, Jurg [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia)]. E-mail: j.keller@awmc.uq.edu.au

    2006-11-02

    The integrated chemical-biological degradation combining advanced oxidation by UV/H{sub 2}O{sub 2} followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H{sub 2}O{sub 2}/L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required.

  16. Multidimensional fully-coupled thermal/chemical/mechanical response of reactive materials

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, M.L.; Baer, M.R.

    1995-11-01

    A summary of multidimensional modeling is presented which describes coupled thermals chemical and mechanical response of reactive and nonreactive materials. This modeling addresses cookoff of energetic material (EM) prior to the onset of ignition. Cookoff, lasting from seconds to days, sensitizes the EM whereupon combustion of confined, degraded material determines the level of violence. Such processes are dynamic, occurring over time scales of millisecond to microsecond, and thus more amenable for shock physics analysis. This work provides preignition state estimates such as the amount of decomposition, morphological changes, and quasistatic stress states for subsequent dynamic analysis. To demonstrate a fully-coupled thermal/chemical/quasistatic mechanical capability, several example simulations have been performed: (1) the one-dimensional time-to-explosion experiments, (2) the Naval Air Weapon Center`s (NAWC) small scale cookoff bomb, (3) a small hot cell experiment and (4) a rigid, highly porous, closed-cell polyurethane foam. Predictions compared adequately to available data. Deficiencies in the model and future directions are discussed.

  17. Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Sibener, Steven J. [University of Chicago, IL (United States)

    2014-03-11

    This research program explored the efficacy of using molecular-level manipulation, imaging and scanning tunneling spectroscopy in conjunction with supersonic molecular beam gas-surface scattering to significantly enhance our understanding of chemical processes occurring on well-characterized interfaces. One program focus was on the spatially-resolved emergent behavior of complex reaction systems as a function of the local geometry and density of adsorbate-substrate systems under reaction conditions. Another focus was on elucidating the emergent electronic and related reactivity characteristics of intentionally constructed single and multicomponent atom- and nanoparticle-based materials. We also examined emergent chirality and self-organization in adsorbed molecular systems where collective interactions between adsorbates and the supporting interface lead to spatial symmetry breaking. In many of these studies we combined the advantages of scanning tunneling (STM) and atomic force (AFM) imaging, scanning tunneling local electronic spectroscopy (STS), and reactive supersonic molecular beams to elucidate precise details of interfacial reactivity that had not been observed by more traditional surface science methods. Using these methods, it was possible to examine, for example, the differential reactivity of molecules adsorbed at different bonding sites in conjunction with how reactivity is modified by the local configuration of nearby adsorbates. At the core of this effort was the goal of significantly extending our understanding of interfacial atomic-scale interactions to create, with intent, molecular assemblies and materials with advanced chemical and physical properties. This ambitious program addressed several key topics in DOE Grand Challenge Science, including emergent chemical and physical properties in condensed phase systems, novel uses of chemical imaging, and the development of advanced reactivity concepts in combustion and catalysis including carbon

  18. The designability of protein switches by chemical rescue of structure: mechanisms of inactivation and reactivation

    Science.gov (United States)

    Xia, Yan; DiPrimio, Nina; Keppel, Theodore R.; Vo, Binh; Fraser, Keith; Battaile, Kevin P.; Egan, Chet; Bystroff, Christopher; Lovell, Scott; Weis, David D.; Anderson, J. Christopher; Karanicolas, John

    2014-01-01

    The ability to selectively activate function of particular proteins via pharmacological agents is a longstanding goal in chemical biology. Recently, we reported an approach for designing a de novo allosteric effector site directly into the catalytic domain of an enzyme. This approach is distinct from traditional chemical rescue of enzymes in that it relies on disruption and restoration of structure, rather than active site chemistry, as a means to achieve modulate function. However, rationally identifying analogous de novo binding sites in other enzymes represents a key challenge for extending this approach to introduce allosteric control into other enzymes. Here we show that mutation sites leading to protein inactivation via tryptophan-to-glycine substitution and allowing (partial) reactivation by the subsequent addition of indole are remarkably frequent. Through a suite of methods including a cell-based reporter assay, computational structure prediction and energetic analysis, fluorescence studies, enzymology, pulse proteolysis, x-ray crystallography and hydrogen-deuterium mass spectrometry we find that these switchable proteins are most commonly modulated indirectly, through control of protein stability. Addition of indole in these cases rescues activity not by reverting a discrete conformational change, as we had observed in the sole previously reported example, but rather rescues activity by restoring protein stability. This important finding will dramatically impact the design of future switches and sensors built by this approach, since evaluating stability differences associated with cavity-forming mutations is a far more tractable task than predicting allosteric conformational changes. By analogy to natural signaling systems, the insights from this study further raise the exciting prospect of modulating stability to design optimal recognition properties into future de novo switches and sensors built through chemical rescue of structure. PMID:24313858

  19. Controls on the surface chemical reactivity of volcanic ash investigated with probe gases

    Science.gov (United States)

    Maters, Elena C.; Delmelle, Pierre; Rossi, Michel J.; Ayris, Paul M.; Bernard, Alain

    2016-09-01

    Increasing recognition that volcanic ash emissions can have significant impacts on the natural and human environment calls for a better understanding of ash chemical reactivity as mediated by its surface characteristics. However, previous studies of ash surface properties have relied on techniques that lack the sensitivity required to adequately investigate them. Here we characterise at the molecular monolayer scale the surfaces of ash erupted from Eyjafjallajökull, Tungurahua, Pinatubo and Chaitén volcanoes. Interrogation of the ash with four probe gases, trimethylamine (TMA; N(CH3)3), trifluoroacetic acid (TFA; CF3COOH), hydroxylamine (HA; NH2OH) and ozone (O3), reveals the abundances of acid-base and redox sites on ash surfaces. Measurements on aluminosilicate glass powders, as compositional proxies for the primary constituent of volcanic ash, are also conducted. We attribute the greater proportion of acidic and oxidised sites on ash relative to glass surfaces, evidenced by comparison of TMA/TFA and HA/O3 uptake ratios, in part to ash interaction with volcanic gases and condensates (e.g., H2O, SO2, H2SO4, HCl, HF) during the eruption. The strong influence of ash surface processing in the eruption plume and/or cloud is further supported by particular abundances of oxidised and reduced sites on the ash samples resulting from specific characteristics of their eruptions of origin. Intense interaction with water vapour may result in a higher fraction of oxidised sites on ash produced by phreatomagmatic than by magmatic activity. This study constitutes the first quantification of ash chemical properties at the molecular monolayer scale, and is an important step towards better understanding the factors that govern the role of ash as a chemical agent within atmospheric, terrestrial, aquatic or biotic systems.

  20. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan [ORNL; Yeh, Gour-Tsyh [University of Central Florida, Orlando; Parker, Jack C [ORNL; Brooks, Scott C [ORNL; Pace, Molly [ORNL; Kim, Young Jin [ORNL; Jardine, Philip M [ORNL; Watson, David B [ORNL

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  1. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C.; Pace, Molly N.; Kim, Young-Jin; Jardine, Philip M.; Watson, David B.

    2007-06-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M- NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  2. Chemical thermodynamics as a predictive tool in the reactive metal brazing of ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Wang, G. [Edison Welding Inst., Columbus, OH (United States); Lannutti, J.J. [Ohio State Univ., Columbus, OH (United States)

    1995-06-01

    Thermodynamics have long been applied to the understanding of the reactive wetting phenomena in metal-ceramic joining. The authors postulate the existence of a ``solvent effect`` due to the interaction between the reactive element addition and the brazing alloy. This effect plays a significant role in reactive wetting. By taking this effect into account, more realistic reactivities of different reactive element additions into a given brazing base alloy are predicted. Irreversible thermodynamics are also used to characterize the driving forces for reactive metal-ceramic joining.

  3. Chemical thermodynamics as a predictive tool in the reactive metal brazing of ceramics

    Science.gov (United States)

    Wang, G.; Lannutti, J. J.

    1995-06-01

    Thermodynamics have long been applied to our understanding of the reactive wetting phenomena in metal-ceramic joining. We postulate the existence of a “solvent effect” due to the interaction between the reactive element addition and the brazing alloy. This effect plays a significant role in reactive wetting. By taking this effect into account, more realistic reactivities of different reactive element additions into a given brazing base alloy are predicted. Irreversible thermodynamics are also used to characterize the driving forces for reactive metal-ceramic joining.

  4. Hemoglobin E disease and glycosylated hemoglobin

    OpenAIRE

    Niharika Yedla; Mohammad Shafi Kuchay; Ambrish Mithal

    2015-01-01

    Glycosylated hemoglobin (HbA1C) is a routinely measured parameter to monitor long-term glycemic control in people with diabetes mellitus. The presence of hemoglobin (Hb) variants can affect the accuracy of HbA1C methods. Hb E variant is the most common Hb variant in South-east Asia and North-east India. In the presence of Hb E, HbA1C may not be detectable by ion-exchange chromatography (high-pressure liquid chromatography), but may be estimated by immunoassay technique and boronate affinity c...

  5. Chemical exposure-response relationship between air pollutants and reactive oxygen species in the human respiratory tract

    OpenAIRE

    Lakey, Pascale S. J.; Thomas Berkemeier; Haijie Tong; Arangio, Andrea M.; Kurt Lucas; Ulrich Pöschl; Manabu Shiraiwa

    2016-01-01

    Air pollution can cause oxidative stress and adverse health effects such as asthma and other respiratory diseases, but the underlying chemical processes are not well characterized. Here we present chemical exposure-response relations between ambient concentrations of air pollutants and the production rates and concentrations of reactive oxygen species (ROS) in the epithelial lining fluid (ELF) of the human respiratory tract. In highly polluted environments, fine particulate matter (PM2.5) con...

  6. The synergistic effect of chemical carcinogens enhances Epstein-Barr virus reactivation and tumor progression of nasopharyngeal carcinoma cells.

    Directory of Open Access Journals (Sweden)

    Chih-Yeu Fang

    Full Text Available Seroepidemiological studies imply a correlation between Epstein-Barr virus (EBV reactivation and the development of nasopharyngeal carcinoma (NPC. N-nitroso compounds, phorbols, and butyrates are chemicals found in food and herb samples collected from NPC high-risk areas. These chemicals have been reported to be risk factors contributing to the development of NPC, however, the underlying mechanism is not fully understood. We have demonstrated previously that low dose N-methyl-N'-nitro-N-nitrosoguanidine (MNNG, 0.1 µg/ml had a synergistic effect with 12-O-tetradecanoylphorbol-13-acetate (TPA and sodium butyrate (SB in enhancing EBV reactivation and genome instability in NPC cells harboring EBV. Considering that residents in NPC high-risk areas may contact regularly with these chemical carcinogens, it is vital to elucidate the relation between chemicals and EBV and their contributions to the carcinogenesis of NPC. In this study, we constructed a cell culture model to show that genome instability, alterations of cancer hallmark gene expression, and tumorigenicity were increased after recurrent EBV reactivation in NPC cells following combined treatment of TPA/SB and MNNG. NPC cells latently infected with EBV, NA, and the corresponding EBV-negative cell, NPC-TW01, were periodically treated with MNNG, TPA/SB, or TPA/SB combined with MNNG. With chemically-induced recurrent reactivation of EBV, the degree of genome instability was significantly enhanced in NA cells treated with a combination of TPA/SB and MNNG than those treated individually. The Matrigel invasiveness, as well as the tumorigenicity in mouse, was also enhanced in NA cells after recurrent EBV reactivation. Expression profile analysis by microarray indicates that many carcinogenesis-related genes were altered after recurrent EBV reactivation, and several aberrations observed in cell lines correspond to alterations in NPC lesions. These results indicate that cooperation between chemical

  7. Visualizing the enhanced chemical reactivity of mesoporous ceria; simulating templated crystallization in silica scaffolds at the atomic level.

    Science.gov (United States)

    Sayle, Thi X T; Sayle, Dean C

    2014-03-12

    Unique physical, chemical, and mechanical properties can be engineered into functional nanomaterials via structural control. However, as the hierarchical structural complexity of a nanomaterial increases, so do the challenges associated with generating atomistic models, which are sufficiently realistic that they can be interrogated to reliably predict properties and processes. The structural complexity of a functional nanomaterial necessarily emanates during synthesis. Accordingly, to capture such complexity, we have simulated each step in the synthetic protocol. Specifically, atomistic models of mesoporous ceria were generated by simulating the infusion and confined crystallization of ceria in a mesoporous silica scaffold. After removing the scaffold, the chemical reactivity of the templated mesoporous ceria was calculated and predicted to be more reactive compared to mesoporous ceria generated without template; visual "reactivity fingerprints" are presented. The strategy affords a general method for generating atomistic models, with hierarchical structural complexity, which can be used to predict a variety of properties and processes enabling the nanoscale design of functional materials.

  8. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    Energy Technology Data Exchange (ETDEWEB)

    Hamaguchi, Satoshi [Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2013-07-11

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

  9. Colloidal stability and chemical reactivity of complex colloids containing Fe3+

    NARCIS (Netherlands)

    van Leeuwen, Y.M.|info:eu-repo/dai/nl/314850139; Velikov, K. P.; Kegel, W.K.|info:eu-repo/dai/nl/113729464

    2014-01-01

    The reactivity of iron contained within insoluble colloidal metal-pyrophosphate salts was determined and compared to the reactivity of a soluble iron salt (FeCl3). As a model system for the reactivity of iron in food products, the formation of an iron–polyphenol complex was followed with

  10. Towards hemerythrin-based blood substitutes: Comparative performance to hemoglobin on human leukocytes and umbilical vein endothelial cells

    Indian Academy of Sciences (India)

    Eva Fischer-Fodor; Augustin Mot; Florina Deac; Mariann Arkosi; Radu Silaghi-Dumitrescu

    2011-06-01

    Hemerythrin is a dioxygen-carrying protein whose oxidative/nitrosative stress-related reactivity is lower than that of hemoglobin, which may warrant investigation of hemerythrin as raw material for artificial oxygen carriers (‘blood substitutes’). We report here the first biological tests for hemerythrin and its chemical derivatives, comparing their performance with that of a representative competitor, glutaraldehyde-polymerized bovine hemoglobin. Hemerythrin (native or derivatized) exhibits a proliferative effect on human umbilical vein endothelial cell (HUVEC) cultures, as opposed to a slight inhibitory effect of hemoglobin. A similar positive effect is displayed on human lymphocytes by glutaraldehyde-polymerized hemerythrin, but not by native or polyethylene glycol-derivatized hemerythrin.

  11. Hemoglobins, programmed cell death and somatic embryogenesis.

    Science.gov (United States)

    Hill, Robert D; Huang, Shuanglong; Stasolla, Claudio

    2013-10-01

    Programmed cell death (PCD) is a universal process in all multicellular organisms. It is a critical component in a diverse number of processes ranging from growth and differentiation to response to stress. Somatic embryogenesis is one such process where PCD is significantly involved. Nitric oxide is increasingly being recognized as playing a significant role in regulating PCD in both mammalian and plant systems. Plant hemoglobins scavenge NO, and evidence is accumulating that events that modify NO levels in plants also affect hemoglobin expression. Here, we review the process of PCD, describing the involvement of NO and plant hemoglobins in the process. NO is an effector of cell death in both plants and vertebrates, triggering the cascade of events leading to targeted cell death that is a part of an organism's response to stress or to tissue differentiation and development. Expression of specific hemoglobins can alter this response in plants by scavenging the NO, thus, interrupting the death process. Somatic embryogenesis is used as a model system to demonstrate how cell-specific expression of different classes of hemoglobins can alter the embryogenic process, affecting hormone synthesis, cell metabolite levels and genes associated with PCD and embryogenic competence. We propose that plant hemoglobins influence somatic embryogenesis and PCD through cell-specific expression of a distinct plant hemoglobin. It is based on the premise that both embryogenic competence and PCD are strongly influenced by cellular NO levels. Increases in cellular NO levels result in elevated Zn(2+) and reactive-oxygen species associated with PCD, but they also result in decreased expression of MYC2, a transcription factor that is a negative effector of indoleacetic acid synthesis, a hormone that positively influences embryogenic competence. Cell-specific hemoglobin expression reduces NO levels as a result of NO scavenging, resulting in cell survival.

  12. Reactive molecular dynamics simulation and chemical kinetic modeling of pyrolysis and combustion of n-dodecane

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Quan-De [College of Chemistry, Sichuan University, Chengdu (China); Wang, Jing-Bo; Li, Juan-Qin; Tan, Ning-Xin; Li, Xiang-Yuan [College of Chemical Engineering, Sichuan University, Chengdu (China)

    2011-02-15

    The initiation mechanisms and kinetics of pyrolysis and combustion of n-dodecane are investigated by using the reactive molecular dynamics (ReaxFF MD) simulation and chemical kinetic modeling. From ReaxFF MD simulations, we find the initiation mechanisms of pyrolysis of n-dodecane are mainly through two pathways, (1) the cleavage of C-C bond to form smaller hydrocarbon radicals, and (2) the dehydrogenation reaction to form an H radical and the corresponding n-C{sub 12}H{sub 25} radical. Another pathway is the H-abstraction reactions by small radicals including H, CH{sub 3}, and C{sub 2}H{sub 5}, which are the products after the initiation reaction of n-dodecane pyrolysis. ReaxFF MD simulations lead to reasonable Arrhenius parameters compared with experimental results based on first-order kinetic analysis of n-dodecane pyrolysis. The density/pressure effects on the pyrolysis of n-dodecane are also analyzed. By appropriate mapping of the length and time from macroscopic kinetic modeling to ReaxFF MD, a simple comparison of the conversion of n-dodecane from ReaxFF MD simulations and that from kinetic modeling is performed. In addition, the oxidation of n-dodecane is studied by ReaxFF MD simulations. We find that formaldehyde molecule is an important intermediate in the oxidation of n-dodecane, which has been confirmed by kinetic modeling, and ReaxFF leads to reasonable reaction pathways for the oxidation of n-dodecane. These results indicate that ReaxFF MD simulations can give an atomistic description of the initiation mechanism and product distributions of pyrolysis and combustion for hydrocarbon fuels, and can be further used to provide molecular based robust kinetic reaction mechanism for chemical kinetic modeling of hydrocarbon fuels. (author)

  13. Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

    Directory of Open Access Journals (Sweden)

    Christelle Pau Ping Wong

    2015-10-01

    Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

  14. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  15. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan

    2015-12-30

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  16. Chemical reactivity testing for the National Spent Nuclear Fuel Program. Revision 2

    Energy Technology Data Exchange (ETDEWEB)

    Koester, L.W.

    2000-02-08

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, Y60-101PD, Quality Program Description, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted. The project consists of conducting three separate series of related experiments, ''Passivation of Uranium Hydride Powder With Oxygen and Water'', '''Passivation of Uranium Hydride Powder with Surface Characterization'', and ''Electrochemical Measure of Uranium Hydride Corrosion Rate''.

  17. Chemical Reactivity Probes for Assessing Abiotic Natural Attenuation by Reducing Iron Minerals.

    Science.gov (United States)

    Fan, Dimin; Bradley, Miranda J; Hinkle, Adrian W; Johnson, Richard L; Tratnyek, Paul G

    2016-02-16

    Increasing recognition that abiotic natural attenuation (NA) of chlorinated solvents can be important has created demand for improved methods to characterize the redox properties of the aquifer materials that are responsible for abiotic NA. This study explores one promising approach: using chemical reactivity probes (CRPs) to characterize the thermodynamic and kinetic aspects of contaminant reduction by reducing iron minerals. Assays of thermodynamic CRPs were developed to determine the reduction potentials (ECRP) of suspended minerals by spectrophotometric determination of equilibrium CRP speciation and calculations using the Nernst equation. ECRP varied as expected with mineral type, mineral loading, and Fe(II) concentration. Comparison of ECRP with reduction potentials measured potentiometrically using a Pt electrode (EPt) showed that ECRP was 100-150 mV more negative than EPt. When EPt was measured with small additions of CRPs, the systematic difference between EPt and ECRP was eliminated, suggesting that these CRPs are effective mediators of electron transfer between mineral and electrode surfaces. Model contaminants (4-chloronitrobenzene, 2-chloroacetophenone, and carbon tetrachloride) were used as kinetic CRPs. The reduction rate constants of kinetic CRPs correlated well with the ECRP for mineral suspensions. Using the rate constants compiled from literature for contaminants and relative mineral reduction potentials based on ECRP measurements, qualitatively consistent trends were obtained, suggesting that CRP-based assays may be useful for estimating abiotic NA rates of contaminants in groundwater.

  18. Chemical reactivity predictions: use of data mining techniques for analyzing regioselective azidolysis of epoxides.

    Science.gov (United States)

    Borghini, Alice; Crotti, Paolo; Pietra, Daniele; Favero, Lucilla; Bianucci, Anna Maria

    2010-11-15

    Azidolysis of epoxides followed by reduction of the intermediate azido alcohols constitutes a valuable synthetic tool for the construction of beta-amino alcohols, an important chemical functionality occurring in many biologically active compounds of natural origin. However, depending on conditions under which the azidolysis is carried out, two regioisomeric products can be formed, as a consequence of the nucleophilic attack on both the oxirane carbon atoms. In this work, predictive models for quantitative structure-reactivity relationships were developed by means of multiple linear regression, k-nearest neighbor, locally weighted regression, and Gaussian Process regression algorithms. The specific nature of the problem at hand required the creation of appropriate new descriptors, able to properly reflect the most relevant features of molecular moieties directly involved in the opening process. The models so obtained are able to predict the regioselectivity of the azidolysis of epoxides promoted by sodium azide, in the presence of lithium perchlorate, on the basis of steric hindrance, and charge distribution of the substituents directly attached to the oxirane ring.

  19. Investigation of the Reactivity of Oligodeoxynucleotides with Glyoxal and KMnO4 Chemical Probes by Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Parr, Carol; Pierce, Sarah E.; Smith, Suncerae I.; Brodbelt, Jennifer S.

    2010-01-01

    The reactions of two well-known chemical probes, glyoxal and potassium permanganate (KMnO4), with oligodeoxynucleotides were monitored by electrospray ionization (ESI) mass spectrometry to evaluate the influence of the sequence of DNA, its secondary structure, and interactions with associated ligands on the reactivity of the two probes. Glyoxal, a guanine-reactive probe, incorporated a mass shift of 58 Da, and potassium permanganate (KMnO4) is a thymine-reactive probe that resulted in a mass shift of 34 Da. The reactions depended on the accessibility of the nucleobases, and the peak abundances of the adducts in the ESI-mass spectra were used to quantify the extent of the chemical probe reactions. In this study, both mixed-base sequences were studied as well as control sequences in which one reactive site was located at the terminus or center of the oligodeoxynucleotide while the surrounding bases were a second, different nucleobase. In addition, the reactions of the chemical probes with non-covalent complexes formed between DNA and either actinomycin D or ethidium bromide, both known to interact with single strand DNA, were evaluated. PMID:21743793

  20. Characterization of the chemical reactivity and nephrotoxicity of N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide, a potential reactive metabolite of trichloroethylene.

    Science.gov (United States)

    Irving, Roy M; Pinkerton, Marie E; Elfarra, Adnan A

    2013-02-15

    N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NA-DCVC) has been detected in the urine of humans exposed to trichloroethylene and its related sulfoxide, N-acetyl-S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (NA-DCVCS), has been detected as hemoglobin adducts in blood of rats dosed with S-(1,2-dichlorovinyl)-L-cysteine (DCVC) or S-(1,2-dichlorovinyl)-L-cysteine sulfoxide (DCVCS). Because the in vivo nephrotoxicity of NA-DCVCS was unknown, in this study, male Sprague-Dawley rats were dosed (i.p.) with 230 μmol/kg b.w. NA-DCVCS or its potential precursors, DCVCS or NA-DCVC. At 24 h post treatment, rats given NA-DCVC or NA-DCVCS exhibited kidney lesions and effects on renal function distinct from those caused by DCVCS. NA-DCVC and NA-DCVCS primarily affected the cortico-medullary proximal tubules (S(2)-S(3) segments) while DCVCS primarily affected the outer cortical proximal tubules (S(1)-S(2) segments). When NA-DCVCS or DCVCS was incubated with GSH in phosphate buffer pH 7.4 at 37°C, the corresponding glutathione conjugates were detected, but NA-DCVC was not reactive with GSH. Because NA-DCVCS exhibited a longer half-life than DCVCS and addition of rat liver cytosol enhanced GSH conjugate formation, catalysis of GSH conjugate formation by the liver could explain the lower toxicity of NA-DCVCS in comparison with DCVCS. Collectively, these results provide clear evidence that NA-DCVCS formation could play a significant role in DCVC, NA-DCVC, and trichloroethylene nephrotoxicity. They also suggest a role for hepatic metabolism in the mechanism of NA-DCVC nephrotoxicity.

  1. Minimizing the risk of chemically reactive metabolite formation of new drug candidates: implications for preclinical drug design.

    Science.gov (United States)

    Brink, Andreas; Pähler, Axel; Funk, Christoph; Schuler, Franz; Schadt, Simone

    2016-11-27

    Many pharmaceutical companies aim to reduce reactive metabolite formation by chemical modification at early stages of drug discovery. A practice often applied is the detection of stable trapping products of electrophilic intermediates with nucleophilic trapping reagents to guide rational structure-based drug design. This contribution delineates this strategy to minimize the potential for reactive metabolite formation of clinical candidates during preclinical drug optimization, exemplified by the experience at Roche over the past decade. For the majority of research programs it was possible to proceed with compounds optimized for reduced covalent binding potential. Such optimized candidates are expected to have a higher likelihood of succeeding throughout the development processes, resulting in safer drugs.

  2. The Clinical Value of Glycosylated Hemoglobin and High Sensitivity C-Reactive Protein in Microangiopathy of Type 2 Diabete%2型糖尿病患者糖化血红蛋白和超敏C反应蛋白在微血管病变中的临床价值

    Institute of Scientific and Technical Information of China (English)

    钟淑萍; 王兴木

    2011-01-01

    Objective To discuss the clinical value of glycosylated hemoglohin and high sensitivity C - reactive protein in microangiopatby of type 2 diabete.Methods Analysator was applied to detect peripheral blood glycosylated hemoglobin and high sensitivity C - reactive protein of the 172 patienta with type 2 diabete more 10 years and 50 controls.Results Peripheral blood glycosylated hemoglobin and high sensitivity C - reactive protein of the patients with type 2 diabete were significantly higher than the contruls( P < 0.05 ) .Peripheral blood glycosylated hemoglobin and high sensitivity C - reactive protein of the patients with diabetic microangiopathy were significantly higher than the NDMA ( P < 0.05 ) .Peripheral blood glycosylated hemoglohin and high sensitivity C - reactive protein of the patients with diabetic nephropathy and diabetic retinopathy were significantly higher than those with only one symptom ( P <0.05) , but the difference in peripheral blood glycosylated hemoglobin and high sensitivity C - reactive protein between diabetic nephropathy group and the diabetic retinopathy group was not statistically significant ( P > 0.05 ) .For peripheral blood glycosylated hemoglobin to diagnose DMA , the sensibility was 93.9% , the positive predictive value was 83.7 % , negative predictive value was 68.0% , the reliability was 81.4% .For peripheral blood high sensitivity C - reactive protein to diagnose DMA, the specificity was 97.6% , the positive predictive value was 97.6% .Conclusion To detect peripheral blood glycosylated hemoglobin and high sensitivity C - reactive protein was helpful for the diagnoaia of type 2 diabete and diabetic microangiopathy.HbAlc, hs - CRP levela were associated with the progress of diabetic microvascular disease.%目的 探讨糖化血红蛋白(HbA1c)和超敏C反应蛋白(hs-CRP)在糖尿病微血管病变中的临床价值.方法 采用生化分析仪测定172例2型糖尿病病史超过10 年的患者[其中41

  3. Hemoglobin E disease and glycosylated hemoglobin

    Directory of Open Access Journals (Sweden)

    Niharika Yedla

    2015-01-01

    Full Text Available Glycosylated hemoglobin (HbA1C is a routinely measured parameter to monitor long-term glycemic control in people with diabetes mellitus. The presence of hemoglobin (Hb variants can affect the accuracy of HbA1C methods. Hb E variant is the most common Hb variant in South-east Asia and North-east India. In the presence of Hb E, HbA1C may not be detectable by ion-exchange chromatography (high-pressure liquid chromatography, but may be estimated by immunoassay technique and boronate affinity chromatography. However, the result may be underestimated when correlated with plasma glucose and serum fructosamine levels. Clinicians should be aware of this limitation of HbA1C estimation in patients with Hb E and other Hb variants.

  4. Chemical reactivity of CVC and CVD SiC with UO{sub 2} at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Chinthaka M., E-mail: silvagw@ornl.gov [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Katoh, Yutai [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Voit, Stewart L. [Fusion and Materials for Nuclear Systems Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Snead, Lance L. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2015-05-15

    Two types of silicon carbide (SiC) synthesized using two different vapor deposition processes were embedded in UO{sub 2} pellets and evaluated for their potential chemical reaction with UO{sub 2}. While minor reactivity between chemical-vapor-composited (CVC) SiC and UO{sub 2} was observed at comparatively low temperatures of 1100 and 1300 °C, chemical-vapor-deposited (CVD) SiC did not show any such reactivity. However, both CVD and CVC SiCs showed some reaction with UO{sub 2} at a higher temperature (1500 °C). Elemental maps supported by phase maps obtained using electron backscatter diffraction indicated that CVC SiC was more reactive than CVD SiC at 1500 °C. Furthermore, this investigation indicated the formation of uranium carbides and uranium silicide chemical phases such as UC, USi{sub 2}, and U{sub 3}Si{sub 2} as a result of SiC reaction with UO{sub 2}.

  5. Computational nanochemistry report on the oxicams--conceptual DFT indices and chemical reactivity.

    Science.gov (United States)

    Martínez-Araya, Jorge Ignacio; Salgado-Morán, Guillermo; Glossman-Mitnik, Daniel

    2013-05-30

    A density functional theory study of eight oxicams was carried out in order to determine their global and local reactivities. These types of reactivities were measured by means of global and local reactivity descriptors coming from the conceptual density functional theory. Net electrophilicity as a global reactivity descriptor and local hypersoftness as a local reactivity descriptor were the used tools to distinguish reactivity and selectivity among these oxicams. Globally, isoxicam presents the highest electron donating capacity; meanwhile, the highest electron accepting capacity is exhibited by droxicam. Locally, two oxicams present neither nucleophilic nor electrophilic relevant reactivity in their peripheral pyridine ring, droxicam and tenoxicam, so that their more reactive zones are found on the respective fused rings. Oxicams have been divided into two subgroups in order to facilitate the local analysis of reactivity. One group is characterized because their most important condensed values for local hypersoftnes are well-separated: 4-meloxicam, lornoxicam, meloxicam, and normeloxicam. Meanwhile, the opposite situation is found in droxicam, isoxicam, piroxicam, and tenoxicam. As a whole, the nucleophilic characteristic noticeably predominates in these eight oxicams instead of an electrophilic behavior, thus meaning a greater tendency to donate electrons rather than withdrawing them; a consequence of this behavior implies a favorable interaction with a hypothetical receptor bearing one or more electron acceptor functional groups rather than electron donor functional groups; this would imply a maximization of this interaction from the covalent point of view.

  6. Evaluation of a High-Throughput Peptide Reactivity Format Assay for Assessment of the Skin Sensitization Potential of Chemicals

    Science.gov (United States)

    Wong, Chin Lin; Lam, Ai-Leen; Smith, Maree T.; Ghassabian, Sussan

    2016-01-01

    The direct peptide reactivity assay (DPRA) is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate, and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium, and high concentrations) and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme, and non-sensitizers) with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF), cysteine- (Ac-RFAACAA), and lysine- (Ac-RFAAKAA) containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7%) and glass (47.3%) vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2, 4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further highlight

  7. Phylogeny of Echinoderm Hemoglobins.

    Directory of Open Access Journals (Sweden)

    Ana B Christensen

    Full Text Available Recent genomic information has revealed that neuroglobin and cytoglobin are the two principal lineages of vertebrate hemoglobins, with the latter encompassing the familiar myoglobin and α-globin/β-globin tetramer hemoglobin, and several minor groups. In contrast, very little is known about hemoglobins in echinoderms, a phylum of exclusively marine organisms closely related to vertebrates, beyond the presence of coelomic hemoglobins in sea cucumbers and brittle stars. We identified about 50 hemoglobins in sea urchin, starfish and sea cucumber genomes and transcriptomes, and used Bayesian inference to carry out a molecular phylogenetic analysis of their relationship to vertebrate sequences, specifically, to assess the hypothesis that the neuroglobin and cytoglobin lineages are also present in echinoderms.The genome of the sea urchin Strongylocentrotus purpuratus encodes several hemoglobins, including a unique chimeric 14-domain globin, 2 androglobin isoforms and a unique single androglobin domain protein. Other strongylocentrotid genomes appear to have similar repertoires of globin genes. We carried out molecular phylogenetic analyses of 52 hemoglobins identified in sea urchin, brittle star and sea cucumber genomes and transcriptomes, using different multiple sequence alignment methods coupled with Bayesian and maximum likelihood approaches. The results demonstrate that there are two major globin lineages in echinoderms, which are related to the vertebrate neuroglobin and cytoglobin lineages. Furthermore, the brittle star and sea cucumber coelomic hemoglobins appear to have evolved independently from the cytoglobin lineage, similar to the evolution of erythroid oxygen binding globins in cyclostomes and vertebrates.The presence of echinoderm globins related to the vertebrate neuroglobin and cytoglobin lineages suggests that the split between neuroglobins and cytoglobins occurred in the deuterostome ancestor shared by echinoderms and vertebrates.

  8. Charge transfer effects on the chemical reactivity of PdxCu1-x nanoalloys

    Science.gov (United States)

    Castegnaro, M. V.; Gorgeski, A.; Balke, B.; Alves, M. C. M.; Morais, J.

    2015-12-01

    This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process between Pd and Cu and its dependency on the nanoalloy composition. Additionally, it was verified that alloying was able to change the NP's reactivity towards oxidation and reduction. Indeed, the higher the amount of Pd in the nanoalloy, less oxidized are both the Pd and the Cu atoms in the as-prepared samples. Also, in situ XANES experiments during thermal treatment under a reducing atmosphere showed that the temperature required for a complete reduction of the nanoalloys depends on their composition. These results envisage the control at the atomic level of novel catalytic properties of such nanoalloys.This work reports on the synthesis and characterization of PdxCu1-x (x = 0.7, 0.5 and 0.3) nanoalloys obtained via an eco-friendly chemical reduction method based on ascorbic acid and trisodium citrate. The average size of the quasi-spherical nanoparticles (NPs) obtained by this method was about 4 nm, as observed by TEM. The colloids containing different NPs were then supported on carbon in order to produce powder samples (PdxCu1-x/C) whose electronic and structural properties were probed by different techniques. XRD analysis indicated the formation of crystalline PdCu alloys with a nanoscaled crystallite size. Core-level XPS results provided a fingerprint of a charge transfer process

  9. Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

    Science.gov (United States)

    Weishaar, J.L.; Aiken, G.R.; Bergamaschi, B.A.; Fram, M.S.; Fujii, R.; Mopper, K.

    2003-01-01

    Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

  10. Colloidal stability and chemical reactivity of complex colloids containing Fe³⁺.

    Science.gov (United States)

    van Leeuwen, Y M; Velikov, K P; Kegel, W K

    2014-07-15

    The reactivity of iron contained within insoluble colloidal metal-pyrophosphate salts was determined and compared to the reactivity of a soluble iron salt (FeCl3). As a model system for the reactivity of iron in food products, the formation of an iron-polyphenol complex was followed with spectrophotometry. Three types of systems were prepared and their colloidal stability and reactivity studied: Fe(3+) pyrophosphate, protein-coated Fe(3+) pyrophosphate and mixed-metal pyrophosphates containing Fe(3+) and a second cation M. The additional cation used was either monovalent (sodium) or divalent (M(2+)). It was found that: (i) incorporating iron in a colloidal salt reduced its reactivity compared to free Fe(3+) ions; (ii) coating the particles with a layer of hydrophobic protein (zein) increased stability and further decreased the reactivity. Finally, the most surprising result was that (iii) a mixed system containing more Fe(3+) than M actually increased the reactivity of the contained iron, while the reverse, a system containing excess M, inhibited the reactivity completely.

  11. An Experiment with Manifold Purposes: The Chemical Reactivity of Crystal Defects upon Crystal Dissolution.

    Science.gov (United States)

    Lazzarini, Annaluisa Fantola; Lazzarini, Ennio

    1983-01-01

    Background information and procedures are provided for an experiment designed to introduce (1) crystal defects and their reactivity upon crystal dissolution; (2) hydrates electron and its reactivity; (3) application of radiochemical method of analysis; and (4) the technique of competitive kinetics. Suggested readings and additional experiments are…

  12. Analysis of chemical reactivity of aminocyclopyrachlor herbicide through the Fukui function

    Directory of Open Access Journals (Sweden)

    Mendoza-Huizar Luis Humberto

    2015-01-01

    Full Text Available We have calculated global and local DFT reactivity descriptors for aminocyclopyrachlor herbicide at the MP2/6-311++G (2d,2p level of theory in the aqueous phase. Global reactivity descriptors such as ionization energy, molecular hardness, electrophilicity, and total energies were calculated to evaluate the aminocyclopyrachlor reactivity. Local reactivity was evaluated through the Fukui function. Our results suggest that the cationic and dipolar forms of aminocyclopyrachlor exhibit similar global reactivity and they are susceptible to deamination and decarboxylation. Also, the opening of the ring might become factible through free radical attacks to the neutral form, while a similar process is caused by nucleophilic attacks on the anionic form.

  13. Prediction of the Chapman–Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics

    OpenAIRE

    Guo, Dezhou; Zybin, Sergey V.; An, Qi; Goddard, William A.; Huang, Fenglei

    2016-01-01

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman–Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ s...

  14. The reactivation of tabun-inhibited mutant AChE with Ortho-7: steered molecular dynamics and quantum chemical studies.

    Science.gov (United States)

    Lo, Rabindranath; Chandar, Nellore Bhanu; Ghosh, Shibaji; Ganguly, Bishwajit

    2016-04-01

    A highly toxic nerve agent, tabun, can inhibit acetylcholinesterase (AChE) at cholinergic sites, which leads to serious cardiovascular complications, respiratory compromise and death. We have examined the structural features of the tabun-conjugated AChE complex with an oxime reactivator, Ortho-7, to provide a strategy for designing new and efficient reactivators. Mutation of mAChE within the choline binding site by Y337A and F338A and its interaction with Ortho-7 has been investigated using steered molecular dynamics (SMD) and quantum chemical methods. The overall study shows that after mutagenesis (Y337A), the reactivator can approach more freely towards the phosphorylated active site of serine without any significant steric hindrance in the presence of tabun compared to the wild type and double mutant. Furthermore, the poor binding of Ortho-7 with the peripheral residues of mAChE in the case of the single mutant compared to that of the wild-type and double mutant (Y337A/F338A) can contribute to better efficacy in the former case. Ortho-7 has formed a greater number of hydrogen bonds with the active site surrounding residues His447 and Phe295 in the case of the single mutant (Y337A), and that stabilizes the drug molecule for an effective reactivation process. The DFT M05-2X/6-31+G(d) level of theory shows that the binding energy of Ortho-7 with the single mutant (Y337A) is energetically more preferred (-19.8 kcal mol(-1)) than the wild-type (-8.1 kcal mol(-1)) and double mutant (Y337A/F338A) (-16.0 kcal mol(-1)). The study reveals that both the orientation of the oxime reactivator for nucleophilic attack and the stabilization of the reactivator at the active site would be crucial for the design of an efficient reactivator.

  15. THE RENAL HANDLING OF HEMOGLOBIN

    Science.gov (United States)

    Bunn, H. Franklin; Esham, William T.; Bull, Robert W.

    1969-01-01

    The glomerular filtration of hemoglobin (α2β2) was studied under conditions in which its dissociation into αβ dimers was experimentally altered. Rats receiving hemoglobin treated with the sulfhydryl reagent bis(N-maleimidomethyl) ether (BME) showed a much lower renal excretion and prolonged plasma survival as compared with animals injected with untreated hemoglobin. Plasma disappearance was also prolonged in dogs receiving BME hemoglobin. Gel filtration data indicated that under physiological conditions, BME hemoglobin had impaired subunit dissociation. In addition, BME hemoglobin showed a very high oxygen affinity and a decreased rate of auto-oxidation. Glomerular filtration was enhanced under conditions which favor the dissociation of hemoglobin into dimers. Cat hemoglobin, which forms subunits much more extensively than canine hemoglobin, was excreted more readily by the rat kidney. The renal uptake of 59Fe hemoglobin injected intra-arterially into rabbits varied inversely with the concentration of the injected dose. PMID:5778789

  16. Characterization of Dimethylsulfoxide / Glycerol Mixtures: A Binary Solvent System for the Study of "Friction-Dependent" Chemical Reactivity

    CERN Document Server

    Angulo, Gonzalo; Gerecke, Mario; Grampp, Günter; Jeannerat, Damien; Milkiewicz, Jadwiga; Mitrev, Yavor; Radzewicz, Czesław; Rosspeintner, Arnulf; Vauthey, Eric; Wnuk, Paweł

    2016-01-01

    The properties of binary mixtures of dimethylsulfoxide and glycerol, measured by several techniques, are reported. Special attention is given to those properties contributing or affecting chemical reactions. In this respect the investigated mixture behaves as a relatively simple solvent and it is especially well suited for studies on the influence of viscosity in chemical reactivity. This is due to the relative invariance of the dielectric properties of the mixture. However, special caution must be taken with specific solvation, as the hydrogen-bonding properties of the solvent changes with the molar fraction of glycerol.

  17. Characterization of dimethylsulfoxide/glycerol mixtures: a binary solvent system for the study of "friction-dependent" chemical reactivity.

    Science.gov (United States)

    Angulo, Gonzalo; Brucka, Marta; Gerecke, Mario; Grampp, Günter; Jeannerat, Damien; Milkiewicz, Jadwiga; Mitrev, Yavor; Radzewicz, Czesław; Rosspeintner, Arnulf; Vauthey, Eric; Wnuk, Paweł

    2016-07-21

    The properties of binary mixtures of dimethylsulfoxide and glycerol, measured using several techniques, are reported. Special attention is given to those properties contributing or affecting chemical reactions. In this respect the investigated mixture behaves as a relatively simple solvent and it is especially well suited for studies on the influence of viscosity on chemical reactivity. This is due to the relative invariance of the dielectric properties of the mixture. However, special caution must be taken with specific solvation, as the hydrogen-bonding properties of the solvent change with the molar fraction of glycerol.

  18. Determining Chemical Reactivity Driving Biological Activity from SMILES Transformations: The Bonding Mechanism of Anti-HIV Pyrimidines

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz

    2013-07-01

    Full Text Available Assessing the molecular mechanism of a chemical-biological interaction and bonding stands as the ultimate goal of any modern quantitative structure-activity relationship (QSAR study. To this end the present work employs the main chemical reactivity structural descriptors (electronegativity, chemical hardness, chemical power, electrophilicity to unfold the variational QSAR though their min-max correspondence principles as applied to the Simplified Molecular Input Line Entry System (SMILES transformation of selected uracil derivatives with anti-HIV potential with the aim of establishing the main stages whereby the given compounds may inhibit HIV infection. The bonding can be completely described by explicitly considering by means of basic indices and chemical reactivity principles two forms of SMILES structures of the pyrimidines, the Longest SMILES Molecular Chain (LoSMoC and the Branching SMILES (BraS, respectively, as the effective forms involved in the anti-HIV activity mechanism and according to the present work, also necessary intermediates in molecular pathways targeting/docking biological sites of interest.

  19. Determining chemical reactivity driving biological activity from SMILES transformations: the bonding mechanism of anti-HIV pyrimidines.

    Science.gov (United States)

    Putz, Mihai V; Dudaş, Nicoleta A

    2013-07-30

    Assessing the molecular mechanism of a chemical-biological interaction and bonding stands as the ultimate goal of any modern quantitative structure-activity relationship (QSAR) study. To this end the present work employs the main chemical reactivity structural descriptors (electronegativity, chemical hardness, chemical power, electrophilicity) to unfold the variational QSAR though their min-max correspondence principles as applied to the Simplified Molecular Input Line Entry System (SMILES) transformation of selected uracil derivatives with anti-HIV potential with the aim of establishing the main stages whereby the given compounds may inhibit HIV infection. The bonding can be completely described by explicitly considering by means of basic indices and chemical reactivity principles two forms of SMILES structures of the pyrimidines, the Longest SMILES Molecular Chain (LoSMoC) and the Branching SMILES (BraS), respectively, as the effective forms involved in the anti-HIV activity mechanism and according to the present work, also necessary intermediates in molecular pathways targeting/docking biological sites of interest.

  20. Amyloid Fibrils from Hemoglobin

    Directory of Open Access Journals (Sweden)

    Nadishka Jayawardena

    2017-04-01

    Full Text Available Amyloid fibrils are a class of insoluble protein nanofibers that are formed via the self-assembly of a wide range of peptides and proteins. They are increasingly exploited for a broad range of applications in bionanotechnology, such as biosensing and drug delivery, as nanowires, hydrogels, and thin films. Amyloid fibrils have been prepared from many proteins, but there has been no definitive characterization of amyloid fibrils from hemoglobin to date. Here, nanofiber formation was carried out under denaturing conditions using solutions of apo-hemoglobin extracted from bovine waste blood. A characteristic amyloid fibril morphology was confirmed by transmission electron microscopy (TEM and atomic force microscopy (AFM, with mean fibril dimensions of approximately 5 nm diameter and up to several microns in length. The thioflavin T assay confirmed the presence of β-sheet structures in apo-hemoglobin fibrils, and X-ray fiber diffraction showed the characteristic amyloid cross-β quaternary structure. Apo-hemoglobin nanofibers demonstrated high stability over a range of temperatures (−20 to 80 °C and pHs (2–10, and were stable in the presence of organic solvents and trypsin, confirming their potential as nanomaterials with versatile applications. This study conclusively demonstrates the formation of amyloid fibrils from hemoglobin for the first time, and also introduces a cost-effective method for amyloid fibril manufacture using meat industry by-products.

  1. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  2. Location change method for imaging chemical reactivity and catalysis with single-molecule and -particle fluorescence microscopy.

    Science.gov (United States)

    Blum, S A

    2014-08-21

    In the last eight years, it has become possible to image chemical reactivity at the single-molecule and -particle level with fluorescence microscopy. This Perspective describes one of the imaging techniques that enabled this state-of-the-art application: imaging by the location change of molecules and particles. In this method, the microscope and experiment are configured to produce a signal when an individual molecule or particle changes location or changes mobility concurrently with a chemical change. This imaging technique has enabled observation of single chemical reactions and unraveled mechanisms of complex chemical and physical processes in transition metal and polymerization systems. This Perspective has three major goals: (1) to unify studies of different chemical processes or of different chemical questions, which, in spite of these differences, employ a similar microscopy detection method, (2) to explain the technique to nonexperts and those who might be interested in joining this nascent field, and (3) to highlight unique information available through this cross-disciplinary technique and the value this information has for chemical reaction development generally and catalysis specifically. To this end, application of the location change method to the investigation of polymerization reactions with radical initiators and separately with metal catalysts, and to ligand exchange reactions at platinum complexes are described.

  3. Chemical exposure-response relationship between air pollutants and reactive oxygen species in the human respiratory tract

    Science.gov (United States)

    Lakey, Pascale S. J.; Berkemeier, Thomas; Tong, Haijie; Arangio, Andrea M.; Lucas, Kurt; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-09-01

    Air pollution can cause oxidative stress and adverse health effects such as asthma and other respiratory diseases, but the underlying chemical processes are not well characterized. Here we present chemical exposure-response relations between ambient concentrations of air pollutants and the production rates and concentrations of reactive oxygen species (ROS) in the epithelial lining fluid (ELF) of the human respiratory tract. In highly polluted environments, fine particulate matter (PM2.5) containing redox-active transition metals, quinones, and secondary organic aerosols can increase ROS concentrations in the ELF to levels characteristic for respiratory diseases. Ambient ozone readily saturates the ELF and can enhance oxidative stress by depleting antioxidants and surfactants. Chemical exposure-response relations provide a quantitative basis for assessing the relative importance of specific air pollutants in different regions of the world, showing that aerosol-induced epithelial ROS levels in polluted megacity air can be several orders of magnitude higher than in pristine rainforest air.

  4. Surface reactivity and layer analysis of chemisorbed reaction films in the surface-chemical environment of alkyl octadecenoates

    Indian Academy of Sciences (India)

    R B Choudhary; O N Anand; O S Tyagi

    2009-05-01

    Studies on surface reactivity of substrate iron (Fe-particles) were made in the tribo-chemical environment of alkyl octadecenoates. Two alkyl octadecenoates namely ethyl octadecenoate and methyl 12-hydroxy octadecenoate, slightly different in their chemical nature, were taken for preparing the chemisorbed reaction films (CRF) at the temperature 100 ± 5°C. The reaction products collected in the composite (amorphous) phase were isolated into three different solvent-soluble fractions (sub-layer films) using polar solvents of increasing polar strength. The FTIR analysis of these films showed that these were primarily organic in nature and were composed of alkyl and/or aryl hydroxy ethers, unsaturated hydroxy ketones, and aromatic structures chemically linked with iron surface. These reaction films also contained large amount of iron (Fe). Further, these film fractions also showed varying thermal behaviour during thermal decomposition in the temperature range of 50-800°C when thermally evaluated in the nitrogen environment.

  5. Two-phase reactive transport of an oil-soluble chemical: an NMR study

    NARCIS (Netherlands)

    Castelijns, H.J.

    2007-01-01

    An oil-soluble chemical (OSC) is a chemical substance which is soluble and chemically inert in oil, but reacts with water to form a gel. Application of an OSC can be found in oil- and gas production. An increased water production, which usually occurs in mature oil fields, can be remedied by

  6. Two-phase reactive transport of an oil-soluble chemical: an NMR study

    NARCIS (Netherlands)

    Castelijns, H.J.

    2007-01-01

    An oil-soluble chemical (OSC) is a chemical substance which is soluble and chemically inert in oil, but reacts with water to form a gel. Application of an OSC can be found in oil- and gas production. An increased water production, which usually occurs in mature oil fields, can be remedied by injecti

  7. Two-phase reactive transport of an oil-soluble chemical: an NMR study

    NARCIS (Netherlands)

    Castelijns, H.J.

    2007-01-01

    An oil-soluble chemical (OSC) is a chemical substance which is soluble and chemically inert in oil, but reacts with water to form a gel. Application of an OSC can be found in oil- and gas production. An increased water production, which usually occurs in mature oil fields, can be remedied by injecti

  8. Evaluation of a high-throughput peptide reactivity format assay for assessment of the skin sensitization potential of chemicals

    Directory of Open Access Journals (Sweden)

    Chin Lin eWong

    2016-03-01

    Full Text Available The direct peptide reactivity assay (DPRA is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium and high concentrations and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme and non-sensitizers with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF, cysteine- (Ac-RFAACAA and lysine- (Ac-RFAAKAA containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7% and glass (47.3% vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2,4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further

  9. Spectroscopic link between adsorption site occupation and local surface chemical reactivity

    DEFF Research Database (Denmark)

    Baraldi, A.; Lizzit, S.; Comelli, G.;

    2004-01-01

    In this Letter we show that sequences of adsorbate-induced shifts of surface core level (SCL) x-ray photoelectron spectra contain profound information on surface changes of electronic structure and reactivity. Energy shifts and intensity changes of time-lapsed spectral components follow simple...... rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface...... reactivity....

  10. Fluctuations in reactive networks subject to extrinsic noise studied in the framework of the Chemical Langevin Equation

    CERN Document Server

    Berthoumieux, Hélène

    2016-01-01

    Theoretical and experimental studies have shown that the fluctuations of in vivo systems break the fluctuation-dissipation theorem. One can thus ask what information is contained in the correlation functions of protein concentrations and how they relate to the response of the reactive network to a perturbation. Answers to these questions are of prime importance to extract meaningful parameters from the in vivo fluorescence correlation spectroscopy data. In this paper we study the fluctuations of the concentration of a reactive species involved in a cyclic network that is in a non-equilibrium steady state perturbed by a noisy force, taking into account both the breaking of detailed balance and extrinsic noises. Using a generic model for the network and the extrinsic noise, we derive a Chemical Langevin Equation that describes the dynamics of the system, we determine the expressions of the correlation functions of the concentrations, estimate the deviation of the fluctuation-dissipation theorem and the range of...

  11. Rice (Oryza) hemoglobins

    Science.gov (United States)

    Hemoglobins (Hbs) corresponding to non-symbiotic (nsHb) and truncated (tHb) Hbs have been identified in rice (Oryza). This review discusses the major findings from the current studies on rice Hbs. At the molecular level, a family of the nshb genes, consisting of hb1, hb2, hb3, hb4 and hb5, and a sin...

  12. Methyl Salicylate: A Reactive Chemical Warfare Agent Surrogate to Detect Reaction with Hypochlorite (POSTPRINT)

    Science.gov (United States)

    2011-05-01

    acid (Fisher Scientific, Fair Lawn, NJ) was diluted to 1.0 M in water purified by reverse osmosis . Methods. Reactions were initially examined by...reactivity of hypochlorite neutralizants delivered onto a substrate is strongly diffusion limited, an observation likely to be useful as a

  13. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  14. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  15. Reactivity boundaries for chemical reactions associated with higher-index and multiple saddles.

    Science.gov (United States)

    Nagahata, Yutaka; Teramoto, Hiroshi; Li, Chun-Biu; Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2013-10-01

    Reactivity boundaries that divide the origin and destination of trajectories are of crucial importance to reveal the mechanism of reactions, which was recently found to exist robustly even at high energies for index 1 saddles [Phys. Rev. Lett. 105, 048304 (2010)]. Here we revisit the concept of the reactivity boundary and propose a more general definition that can involve a single reaction associated with a bottleneck composed of higher-index saddles and/or several saddle points with different indices, where the normal form theory, based on expansion around a single stationary point, does not work. We numerically demonstrate the reactivity boundary by using a reduced model system of the H(5)(+) cation where the proton exchange reaction takes place through a bottleneck composed of two index 2 saddle points and two index 1 saddle points. The cross section of the reactivity boundary in the reactant region of the phase space reveals which initial conditions are effective in making the reaction happen and thus sheds light on the reaction mechanism.

  16. Supercharging SpyCatcher toward an intrinsically disordered protein with stimuli-responsive chemical reactivity.

    Science.gov (United States)

    Cao, Yang; Liu, Dong; Zhang, Wen-Bin

    2017-08-03

    We report a supercharged, intrinsically disordered protein, SpyCatcher(-), possessing stimuli-responsive reactivity toward SpyTag with tunable yields ranging from 4% to 98% depending on pH, temperature, ionic strength, etc. The CD and NMR studies reveal that the reaction occurs through a folded intermediate formed probably via a different mechanism from that of SpyCatcher.

  17. Supra-molecular structure and chemical reactivity of cellulose I studied using CP/MAS (sup)13 C-NMR

    CSIR Research Space (South Africa)

    Chunilall, Viren

    2013-08-01

    Full Text Available medium, provided the original work is properly cited. Supra-Molecular Structure and Chemical Reactivity of Cellulose I Studied Using CP/MAS 13C-NMR Viren Chunilall, Tamara Bush and Per Tomas Larsson Additional information is available at the end... of Cellulose I Studied Using CP/MAS 13C-NMR 71 1.1.2. Dissolving pulp The unbleached pulp that results after acid bi-sulphite pulping is used as raw material for dissolving pulp production. Lignin and hemicelluloses in the unbleached pulp are considered...

  18. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  19. Forced chromatin looping raises fetal hemoglobin in adult sickle cells to higher levels than pharmacologic inducers.

    Science.gov (United States)

    Breda, Laura; Motta, Irene; Lourenco, Silvia; Gemmo, Chiara; Deng, Wulan; Rupon, Jeremy W; Abdulmalik, Osheiza Y; Manwani, Deepa; Blobel, Gerd A; Rivella, Stefano

    2016-08-25

    Overcoming the silencing of the fetal γ-globin gene has been a long-standing goal in the treatment of sickle cell disease (SCD). The major transcriptional enhancer of the β-globin locus, called the locus control region (LCR), dynamically interacts with the developmental stage-appropriate β-type globin genes via chromatin looping, a process requiring the protein Ldb1. In adult erythroid cells, the LCR can be redirected from the adult β- to the fetal γ-globin promoter by tethering Ldb1 to the human γ-globin promoter with custom-designed zinc finger (ZF) proteins (ZF-Ldb1), leading to reactivation of γ-globin gene expression. To compare this approach to pharmacologic reactivation of fetal hemoglobin (HbF), hematopoietic cells from patients with SCD were treated with a lentivirus expressing the ZF-Ldb1 or with chemical HbF inducers. The HbF increase in cells treated with ZF-Ldb1 was more than double that observed with decitabine and pomalidomide; butyrate had an intermediate effect whereas tranylcypromine and hydroxyurea showed relatively low HbF reactivation. ZF-Ldb1 showed comparatively little toxicity, and reduced sickle hemoglobin (HbS) synthesis as well as sickling of SCD erythroid cells under hypoxic conditions. The efficacy and low cytotoxicity of lentiviral-mediated ZF-Ldb1 gene transfer compared with the drug regimens support its therapeutic potential for the treatment of SCD.

  20. Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

    Indian Academy of Sciences (India)

    Francisco Méndez; María De L Romero; José L Gazquez

    2005-09-01

    The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiHF4- and SiHF$^{1-}_{5-n}$. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiHF$^{1-}_{5-n}$, and hard nucleophiles with SiHF4-.

  1. Hemoglobin interacting proteins and implications of spectrin hemoglobin interaction.

    Science.gov (United States)

    Basu, Avik; Chakrabarti, Abhijit

    2015-10-14

    In this report we have analyzed interacting partners of hemoglobin inside erythrocyte and sought possible implications of hemoglobin-spectrin interaction. Our list of identified cytosolic hemoglobin interacting proteins includes redox regulators like peroxiredoxin-2, Cu-Zn superoxide dismutase, catalase, aldehyde dehydrogenase-1, flavin reductase and chaperones like HSP70, α-hemoglobin stabilizing protein. Others include metabolic enzymes like carbonic anhydrase-1, selenium binding protein-1, purine nucleoside phosphorylase and nucleoside diphosphate kinase. Additionally, various membrane proteins like α and β spectrin, ankyrin, band3, protein4.1, actin and glyceraldehyde 3 phosphate dehydrogenase have been shown to interact with hemoglobin. Our result indicates that major membrane skeleton protein spectrin, that also has a chaperone like activity, helps to fold the unstable alpha-globin chains in vitro. Taken together our results could provide insight into a protein network evolved around hemoglobin molecule inside erythrocyte that may add a new perspective in understanding the hemoglobin function and homeostasis.

  2. Chemical Cleaning of Metal Surfaces in Vacuum Systems by Exposure to Reactive Gases.

    Science.gov (United States)

    1987-11-10

    Phys. Letters 39 (1976) 113. 196. P.E. Luscher , Surface Sci. 66 (1977) 167. 197. M. Housley and C.A. King, Surface Sci. 62 (1977) 81, 93. 193. M.K. Debe... Physics and Astronomy Barrows Hall University of Maine Orono, ME 04469 ............... November 10, 1987 Reproduction in whole or in part is permitted...Exposure to Reactive Gases M. Grunze*, H. Ruppender and 0. Elshazly Laboratory for Surface Science and Technology and Department of Physics and

  3. Control of Convective Dissolution by Chemical Reactions: General Classification and Application to CO2 Dissolution in Reactive Aqueous Solutions

    Science.gov (United States)

    Loodts, V.; Thomas, C.; Rongy, L.; De Wit, A.

    2014-09-01

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO2 in aqueous solutions by a classical acid-base reaction.

  4. Antimicrobial properties of hemoglobin.

    Science.gov (United States)

    Sheshadri, Preethi; Abraham, Jayanthi

    2012-12-01

    Hemoglobin consists of a heme containing component and a globin unit. It exists as a tetramer with 2 α subunits and 2 β subunits in adults and with 2 α subunits and 2 γ chains in infants. On proteolytic cleavage, hemoglobin breaks down to produce many biologically active compounds, among which are hemocidins, those which exhibit antimicrobial property. The generation of these peptides does not depend on the blood group, Rhesus factor, age and sex of the healthy donors. The microbicidal activity has been observed against a variety of gram positive and Gram-negative bacteria, and against filamentous fungi, yeast and even certain parasites. The discovery of hemocidins opens a new field for research into the details of the peptides acting as second line of defence in boosting the innate immune system of the organisms.

  5. Hemoglobin oxidative stress

    Energy Technology Data Exchange (ETDEWEB)

    Croci, S.; Ortalli, I.; Pedrazzi, G. [University of Parma, Istituto di Scienze Fisiche, INFM-Udr Parma (Italy); Passeri, G. [University of Parma, Dipartimento di Medicina Interna e Scienze Biomediche (Italy); Piccolo, P. [University of Parma, Istituto di Clinica chirurgica Generale, Toracica e Vascolare (Italy)

    2000-07-15

    Venous blood obtained from healthy donors and from patients suffering from breast cancer have been treated with acetylphenylhydrazine (APH) for different time. Moessbauer spectra of the packed red cells have been recorded and compared. The largest difference occurs after 50 min of treatment with APH where the patient samples show a broad spectral pattern indicating an advanced hemoglobin oxidation. These results may have some relevance in early cancer diagnosis.

  6. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    Science.gov (United States)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  7. Chemical weathering rates in deep-sea sediments: Comparison of multicomponent reactive transport models and estimates based on 234U

    Science.gov (United States)

    Maher, K.; Steefel, C. I.; Depaolo, D. J.

    2004-12-01

    Chemical weathering rates in natural systems are typically much slower than expected based on experiments and theory. There are several possible explanations. However, because it has been difficult to determine what effects in particular reduce the rates in specific settings, natural rates remain difficult to predict. Silicate-rich deep-sea sediments provide an ideal in-situ laboratory for investigating weathering rates because certain potentially important factors, such as advective transport through heterogeneous media, limitations on the availability of reactive surface area due to low porosity and/or cementation, unsaturated flow conditions, and seasonal variations in fluid flux and temperature, do not occur in this setting. Geochemical profiles from Site 984 in the North Atlantic are modeled using a multi-component reactive transport model (CRUNCH) to determine in-situ rates of plagioclase dissolution and other diagenetic processes, including sulfate reduction and anaerobic methane oxidation. Various possible processes which might contribute to slower rates in the field are considered, including the effect of mineral saturation state, secondary precipitation of clays, inhibition by dissolved aluminum, and the availability of reactive surface area. The reactive transport model includes an isotopic solid-solution formulation that tracks the isotopic composition of precipitating (calcite) and dissolving (plagioclase and calcite) phases, thus allowing the determination of plagioclase dissolution rates. The rate constants for plagioclase determined by geochemical transport modeling of major element profiles are within the same range determined from U-series calculations and suggest that natural weathering rates for this system are on the order of 10-17.5 to 10-17.7 mol/m2/sec assuming estimates of reactive surface area are correct, several orders of magnitude slower than laboratory-derived rates. The slow plagioclase rates are most likely due to the fact that

  8. Programmable Thermal Dissociation of Reactive Gaseous Mercury, a Potential Approach to Chemical Speciation: Results from a Field Study§

    Directory of Open Access Journals (Sweden)

    Cheryl Tatum Ernest

    2014-08-01

    Full Text Available Programmable Thermal Dissociation (PTD has been used to investigate the chemical speciation of Reactive Gaseous Mercury (RGM, Hg2+. RGM was collected on denuders and analyzed using PTD. The technique was tested in a field campaign at a coal-fired power plant in Pensacola, Florida. Stack gas samples were collected from ducts located after the electrostatic precipitator and prior to entering the stack. An airship was used to sample from the stack plume, downwind of the stack exit. The PTD profiles from these samples were compared with PTD profiles of HgCl2. Comparison of stack and in-plume samples suggest that the chemical speciation are the same and that it is possible to track a specific chemical form of RGM from the stack and follow its evolution in the stack plume. Comparison of the measured plume RGM with the amount calculated from in-stack measurements and the measured plume dilution suggest that the stack and plume RGM concentrations are consistent with dilution. The PTD profiles of the stack and plume samples are consistent with HgCl2 being the chemical form of the sampled RGM. Comparison with literature PTD profiles of reference mercury compounds suggests no other likely candidates for the speciation of RGM.

  9. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  10. Heavy Grignard Reagents: Synthesis, Physical and Structural Properties, Chemical Behavior, and Reactivity.

    Science.gov (United States)

    Westerhausen, Matthias; Koch, Alexander; Görls, Helmar; Krieck, Sven

    2017-01-31

    The Grignard reaction offers a straight forward atom-economic synthesis of organomagnesium halides, which undergo redistribution reactions (Schlenk equilibrium) yielding diorganylmagnesium and magnesium dihalides. The homologous organocalcium complexes (heavy Grignard reagents) gained interest only quite recently owing to several reasons. The discrepancy between the inertness of this heavy alkaline earth metal and the enormous reactivity of its organometallics hampered a vast and timely development after the first investigation more than 100 years ago. In this overview the synthesis of organocalcium reagents is described as is the durability in ethereal solvents. Aryl-, alkenyl-, and alkylcalcium halides are prepared by direct synthesis. Characteristic structural features and NMR parameters are discussed. Ligand redistribution reactions can be performed by addition of potassium tert-butanolate to ethereal solutions of arylcalcium iodides yielding soluble diarylcalcium, whereas sparingly soluble potassium iodide and calcium bis(tert-butanolate) precipitate. Furthermore, reactivity studies with respect to metalation and addition to unsaturated organic compounds and metal-based Lewis acids, leading to the formation of heterobimetallic complexes, are presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Correlated Electrochemical and Optical Detection Reveals the Chemical Reactivity of Individual Silver Nanoparticles.

    Science.gov (United States)

    Brasiliense, Vitor; Patel, Anisha N; Martinez-Marrades, Ariadna; Shi, Jian; Chen, Yong; Combellas, Catherine; Tessier, Gilles; Kanoufi, Frédéric

    2016-03-16

    Electrochemical (EC) impacts of single nanoparticles (NPs) on an ultramicroelectrode are coupled with optics to identify chemical processes at the level of individual NPs. While the EC signals characterize the charge transfer process, the optical monitoring gives a complementary picture of the transport and chemical transformation of the NPs. This is illustrated in the case of electrodissolution of Ag NPs. In the simplest case, the optically monitored dissolution of individual NPs is synchronized with individual EC spikes. Optics then validates in situ the concept of EC nanoimpacts for sizing and counting of NPs. Chemical complexity is introduced by using a precipitating agent, SCN(-), which tunes the overall electrodissolution kinetics. Particularly, the charge transfer and dissolution steps occur sequentially as the synchronicity between the EC and optical signals is lost. This demonstrates the level of complexity that can be revealed from such electrochemistry/optics coupling.

  12. Subcritical crack growth in a chemically reactive environment-implications for caprock integrity for CO2 storage

    Science.gov (United States)

    Fan, Z.; Eichhubl, P.; Callahan, O. A.; Major, J. R.; Chen, X.

    2015-12-01

    Seal integrity of cap-rock is a critical constraint on the long term performance of CO2 containment site. During fluid migration, the coupled geochemical reaction of minerals and geomechanical deformation of rock matrix may affect the seal integrity. The potential leakage of injected CO2 from cap-rock through preexisting fractures/faults represents a major concern associated with geological storage of CO2. To address the fundamental question of CO2 leakage through subcritical growth of fractures driven by chemically reactive fluid across caprocks, we build a Dugdale cohesive model. Ahead of the physical crack tip, a narrow band of cohesive zone is assumed to exist with the upper and lower cohesive surfaces held by the cohesive traction. In the vicinity of the crack tip, minerals dissolve due to the acidic environment and migrate from the physical crack tip into the cohesive zone causing damage of rock matrix in the form of a reduction of cohesive traction.Focusing on the dissolution of calcite and following the stress corrosion theory, we assume the degradation of cohesive traction is linearly proportional to the concentration of Ca2+whose evolution follows the reactive diffusion equation. Using a critical crack opening displacement criterion, the subcritical propagation behavior of crack due to stress corrosion is captured and the rate-limiting effects including the chemical reactions to produce the Ca2+ and the transport of minerals along the newly generated fracture cohesive zone are incorporated. Subcritical crack growth rate under different chemical environment conditions is examined and compared with the experimental fracture mechanics testing.

  13. Topological analysis (BCP) of vibrational spectroscopic studies, docking, RDG, DSSC, Fukui functions and chemical reactivity of 2-methylphenylacetic acid.

    Science.gov (United States)

    Kavimani, M; Balachandran, V; Narayana, B; Vanasundari, K; Revathi, B

    2017-09-07

    Experimental FT-IR and FT-Raman spectra of 2-methylphenylacetic acid (MPA) were recorded and theoretical values are also analyzed. The non-linear optical (NLO) properties were evaluated by determination of first (5.5053×10(-30) e.s.u.) and second hyper-polarizabilities (7.6833×10(-36) e.s.u.) of the title compound. The Multiwfn package is used to find the weak non-covalent interaction (Van der Wall interaction) and strong repulsion (steric effect) of the molecule and examined by reduced density gradient. The molecular electrostatic potential (MEP) analysis used to find the most reactive sites for the electrophilic and nucleophilic attack. The chemical activity (electronegativity, hardness, chemical softness and chemical potential) of the title compound was predicted with the help of HOMO-LUMO energy values. The natural bond orbital (NBO) has been analyzed the stability of the molecule arising from the hyper-conjugative interaction. DSSCs were discussed in structural modifications that improve the electron injection efficiency of the title compound (MPA). The Fukui functions are calculated in order to get information associated with the local reactivity properties of the title compound. The binding sites of the two receptors were reported by molecular docking field and active site bond distance is same 1.9Å. The inhibitor of the title compound forms a stable complex with 1QYV and 2H1K proteins at the binding energies are -5.38 and -5.85 (∆G in kcal/mol). Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Facile Interfacial Electron Transfer of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Chunhai Fan

    2005-12-01

    Full Text Available Abstract: We herein describe a method of depositing hemoglobin (Hb and sulfonated polyaniline (SPAN on GC electrodes that facilitate interfacial protein electron transfer. Well-defined, reproducible, chemically reversible peaks of Hb and SPAN can be obtained in our experiments. We also observed enhanced peroxidase activity of Hb in SPAN films. These results clearly showed that SPAN worked as molecular wires and effectively exchanged electrons between Hb and electrodes.Mediated by Conjugated Polymers

  15. Development of a QSAR for worst case estimates of acute toxicity of chemically reactive compounds

    NARCIS (Netherlands)

    Freidig, A.P.; Dekkers, S.; Verwei, M.; Zvinavashe, E.; Bessems, J.G.M.; Sandt, J.J.M. van de

    2007-01-01

    Future EU legislations enforce a fast hazard and risk assessment of thousands of existing chemicals. If conducted by means of present data requirements, this assessment will use a huge number of test animals and will be neither cost nor time effective. The purpose of the current research was to

  16. Development of a QSAR for worst case estimates of acute toxicity of chemically reactive compounds

    NARCIS (Netherlands)

    Freidig, A.P.; Dekkers, S.; Verwei, M.; Zvinavashe, E.; Bessems, J.G.M.; Sandt, J.J.M. van de

    2007-01-01

    Future EU legislations enforce a fast hazard and risk assessment of thousands of existing chemicals. If conducted by means of present data requirements, this assessment will use a huge number of test animals and will be neither cost nor time effective. The purpose of the current research was to deve

  17. Hemoglobin Drift after Cardiac Surgery

    Science.gov (United States)

    George, Timothy J.; Beaty, Claude A.; Kilic, Arman; Haggerty, Kara A.; Frank, Steven M.; Savage, William J.; Whitman, Glenn J.

    2013-01-01

    Introduction Recent literature suggests that a restrictive approach to red blood cell transfusions is associated with improved outcomes in cardiac surgery (CS) patients. Even in the absence of bleeding, intravascular fluid shifts cause hemoglobin levels to drift postoperatively, possibly confounding the decision to transfuse. We undertook this study to define the natural progression of hemoglobin levels in postoperative CS patients. Methods We included all CS patients from 10/10-03/11 who did not receive a postoperative transfusion. Primary stratification was by intraoperative transfusion status. Change in hemoglobin was evaluated relative to the initial postoperative hemoglobin. Maximal drift was defined as the maximum minus the minimum hemoglobin for a given hospitalization. Final drift was defined as the difference between initial and discharge hemoglobin. Results Our final cohort included 199 patients, 71(36%) received an intraoperative transfusion while 128(64%) did not. The average initial and final hemoglobin for all patients were 11.0±1.4g/dL and 9.9±1.3g/dL, respectively, an final drift of 1.1±1.4g/dL. The maximal drift was 1.8±1.1g/dL and was similar regardless of intraoperative transfusion status(p=0.9). Although all patients’ hemoglobin initially dropped, 79% of patients reached a nadir and experienced a mean recovery of 0.7±0.7g/dL by discharge. On multivariable analysis, increasing CPB time was significantly associated with total hemoglobin drift(Coefficient/hour: 0.3[0.1–0.5]g/dL, p=0.02). Conclusions In this first report of hemoglobin drift following CS, although all postoperative patients experienced downward hemoglobin drift, 79% of patients exhibited hemoglobin recovery prior to discharge. Physicians should consider the eventual upward hemoglobin drift prior to administering red cell transfusions. PMID:22609121

  18. Chemical reactivity of hydrogen, nitrogen, and oxygen atoms at temperatures below 100 k

    Science.gov (United States)

    Mcgee, H. A., Jr.

    1973-01-01

    The synthesis of unusual compounds by techniques employing cryogenic cooling to retard their very extreme reactivity was investigated. Examples of such species that were studied are diimide (N2H2), cyclobutadiene (C4H4), cyclopropanone (C3H4O), oxirene (C2H2O), and many others. Special purpose cryogenically cooled inlet arrangements were designed such that the analyses incurred no warm-up of the cold, and frequently explosively unstable, compounds. Controlled energy electron impact techniques were used to measure critical potentials and to develop the molecular energetics and thermodynamics of these molecules and to gain some insight into their kinetic characteristics as well. Three and four carbon strained ring molecules were studied. Several reactions of oxygen and hydrogen atoms with simple molecules of H, N, C, and O in hard quench configurations were studied. And the quench stabilization of BH3 was explored as a model system in cryochemistry.

  19. Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen.

    Science.gov (United States)

    Morinaka, Yuta; Zhang, Rui; Sato, Satoru; Nikawa, Hidefumi; Kato, Tatsuhisa; Furukawa, Ko; Yamada, Michio; Maeda, Yutaka; Murata, Michihisa; Wakamiya, Atsushi; Nagase, Shigeru; Akasaka, Takeshi; Murata, Yasujiro

    2017-06-01

    To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C60 and C70 fullerenes. Among the studied endofullerenes, H2 @C70 was able to encapsulate an additional nitrogen atom within the fullerene cage under radiofrequency plasma conditions. The product was analyzed by ESR spectroscopy and mass spectrometry in solution, which revealed that the nitrogen atom with a quartet ground state does not react but weakly interact with the H2 molecule, thus demonstrating the utility of such fullerenes as "nanoflasks". © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials.

  1. A Graph Theoretical and Topological Approach to Chemical Structure, Reactivity, and Dynamics

    Science.gov (United States)

    1988-10-01

    chirality polynomial of the regular icosahedron, a problem previously assumed to be intractable. 2 7 Professor King has also expanded, extended, and...algebra to determine polynomials for the description of chirality observations. 6 0 This review presents a critical analysis of the limitations of...Surfaces: Such maps are generalizations of the convex polyhedra so common in chemical applications. During the last twenty years, Tutte and others have

  2. Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials

    Science.gov (United States)

    2016-06-01

    of Additives and Impurities from Polymeric Materials; EPA 560/5-85-015; U.S. Environmental Protection Agency, Office of Pesticides and Toxic...performance, a penetrating decontaminant may cause damage to the material, such as the swelling of polymers caused by solvents or any active...Chemical Warfare Agent Degradation Products. Environ . Health Perspect. 1999, 107 (12), 933–974. 5. Kim, K.; Tsay, O.G.; Atwood, D.A.; Churchill, D.G

  3. Residence time and conversion in the extrusion of chemically reactive materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, W.; Jaluria, Y.

    1999-07-01

    Extrusion is one of the most versatile and energy-efficient processes for the manufacture of polymer products, including food, pharmaceuticals and plastics. Many functions including mixing, cooking and chemical reaction can be performed in an extruder. Here, twin-screw extruders offer improved control of the residence time distribution (RTD) and mixing in materials such as plastics, rubber and food. Based on the flow and the heat transfer characteristics obtained for a self-wiping, co-rotating twin-screw extruder, the residence time and chemical reaction are studied by tracking the particles. For normally starve-fed twin-screw extruders, the length of the completely filled section is calculated as function of the process variables using the coupling of the flow with the die. With a model of the solid conveying section, the RTD for the whole extruder is calculated for corn meal at different screw speeds and flow rates. The calculated variation of RTD with the screw speed and the flow rate yields good agreement with observations from many experiments. The variation of the fully filled section length, chemical conversion and mixing effectiveness are also obtained under different operation conditions. Most of the results are in qualitative agreement with experimental results and may be used as guidelines for extruder design and determination of optimal operating condition.

  4. Fluctuations in reactive networks subject to extrinsic noise studied in the framework of the chemical Langevin equation

    Science.gov (United States)

    Berthoumieux, H.

    2016-07-01

    Theoretical and experimental studies have shown that the fluctuations of in vivo systems break the fluctuation-dissipation theorem. One can thus ask what information is contained in the correlation functions of protein concentrations and how they relate to the response of the reactive network to a perturbation. Answers to these questions are of prime importance to extract meaningful parameters from the in vivo fluorescence correlation spectroscopy data. In this paper we study the fluctuations of the concentration of a reactive species involved in a cyclic network that is in a nonequilibrium steady state perturbed by a noisy force, taking into account both the breaking of detailed balance and extrinsic noises. Using a generic model for the network and the extrinsic noise, we derive a chemical Langevin equation that describes the dynamics of the system, we determine the expressions of the correlation functions of the concentrations, and we estimate the deviation of the fluctuation-dissipation theorem and the range of parameters in which an effective temperature can be defined.

  5. Reactivity of iron oxide with methane in a laboratory fluidized bed : application of chemical-looping combustion

    Energy Technology Data Exchange (ETDEWEB)

    Cho, P. [Chalmers Univ. of Technology, Goteborg (Sweden). Dept. of Inorganic and Environmental Chemistry; Mattisson, T.; Lyngfelt, A. [Chalmers Univ. of Technology, Goteborg (Sweden). Dept. of Energy Conversion

    2002-07-01

    Chemical looping combustion (CLC) is a promising method for separating carbon dioxide from flue gases during combustion. A study was conducted in which cyclic reduction-oxidation experiments were conducted with synthetic oxygen carrier particles under fluidized conditions. Two interconnected fluidized beds were used as reactors in which a metal oxide was used as an oxygen carrier providing oxygen from the combustion air to the fuel. In particular, this study examined the feasibility of using iron oxide as an oxygen carrier in repeated cycles of methane and air at 950 degrees C. The advantage of CLC compared to normal combustion is that carbon dioxide can be separated from the other components of the flue gas, nitrogen and unreacted oxygen. This avoids efficiency losses and the need for costly equipment for carbon dioxide separation. The reduction rates measured in this experiment were lower than in previous tests with fixed beds due to less efficient contact between gas and particles under fluidized bed conditions. High reactivities were still observed, suggesting that the particles should have sufficient reactivity for use in the proposed CLC system. 10 refs., 1 tab., 5 figs.

  6. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    Science.gov (United States)

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation.

  7. Fluctuations in reactive networks subject to extrinsic noise studied in the framework of the chemical Langevin equation.

    Science.gov (United States)

    Berthoumieux, H

    2016-07-01

    Theoretical and experimental studies have shown that the fluctuations of in vivo systems break the fluctuation-dissipation theorem. One can thus ask what information is contained in the correlation functions of protein concentrations and how they relate to the response of the reactive network to a perturbation. Answers to these questions are of prime importance to extract meaningful parameters from the in vivo fluorescence correlation spectroscopy data. In this paper we study the fluctuations of the concentration of a reactive species involved in a cyclic network that is in a nonequilibrium steady state perturbed by a noisy force, taking into account both the breaking of detailed balance and extrinsic noises. Using a generic model for the network and the extrinsic noise, we derive a chemical Langevin equation that describes the dynamics of the system, we determine the expressions of the correlation functions of the concentrations, and we estimate the deviation of the fluctuation-dissipation theorem and the range of parameters in which an effective temperature can be defined.

  8. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure.

    Science.gov (United States)

    Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Gonçalves, Théo P; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2016-04-01

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

  9. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan

    2016-03-11

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  10. A comprehensive characterisation of Asian dust storm particles: chemical composition, reactivity to SO2, and hygroscopic property

    Directory of Open Access Journals (Sweden)

    H. He

    2010-04-01

    Full Text Available Mineral dust comprises of a significant fraction of the globe's aerosol loading. Yet it remains the largest uncertainty in future climate predictions due to the complexity in its components and physico-chemical properties. Multi-analysis methods, including SEM-EDX, FTIR, BET, TPD/mass, and Knudsen cell/mass, were used in the present study to characterise Asian dust storm particles. The morphology, element fraction, source distribution, true uptake coefficient of SO2 and hygroscopic behaviour were studied. The major components of Asian dust storm particles were found to consist of aluminosilicate, SiO2, and CaCO3, which were coated with organic compounds and inorganic nitrate. The dust storm particles have a low reactivity to SO2 (true uptake coefficient of 5.767×10−6 which limits the conversion of SO2 to sulfate during a dust storm period. The low reactivity also demonstrated that the heterogeneous reaction of SO2, in both dry and humid air conditions, had little effect on the hygroscopic behaviour of the dust particles. These results indicate that the impact of dust storms on atmospheric SO2 removal should not be overestimated.

  11. On the chemical state and distribution of Zr- and V-based additives in reactive hydride composites

    Science.gov (United States)

    Bösenberg, U.; Vainio, U.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Goerigk, G.; Welter, E.; Dornheim, M.; Schreyer, A.; Bormann, R.

    2009-05-01

    Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.

  12. An alternative to fully coupled reactive transport simulations for long-term prediction of chemical reactions in complex geological systems

    Science.gov (United States)

    De Lucia, Marco; Kempka, Thomas; Kühn, Michael

    2014-05-01

    Fully-coupled reactive transport simulations involving multiphase hydrodynamics and chemical reactions in heterogeneous settings are extremely challenging from a computational point of view. This often leads to oversimplification of the investigated system: coarse spatial discretization, to keep the number of elements in the order of few thousands; simplified chemistry, disregarding many potentially important reactions. A novel approach for coupling non-reactive hydrodynamic simulations with the outcome of single batch geochemical simulations was therefore introduced to assess the potential long-term mineral trapping at the Ketzin pilot site for underground CO2 storage in Germany [1],[2]. The advantage of the coupling is the ability to use multi-million grid non-reactive hydrodynamics simulations on one side and few batch 0D geochemical simulations on the other, so that the complexity of both systems does not need to be reduced. This contribution shows the approach which was taken to validate this simplified coupling scheme. The procedure involved batch simulations of the reference geochemical model, then performing both non-reactive and fully coupled 1D and 3D reactive transport simulations and finally applying the simplified coupling scheme based on the non-reactive and geochemical batch model. The TOUGHREACT/ECO2N [3] simulator was adopted for the validation. The degree of refinement of the spatial grid and the complexity and velocity of the mineral reactions, along with a cut-off value for the minimum concentration of dissolved CO2 allowed to originate precipitates in the simplified approach were found out to be the governing parameters for the convergence of the two schemes. Systematic discrepancies between the approaches are not reducible, simply because there is no feedback between chemistry and hydrodynamics, and can reach 20 % - 30 % in unfavourable cases. However, even such discrepancy is completely acceptable, in our opinion, given the amount of

  13. Investigating the influence of subsurface heterogeneity on chemical weathering in the critical zone using high resolution reactive transport models

    Science.gov (United States)

    Pandey, S.; Rajaram, H.

    2014-12-01

    The critical zone (CZ) represents a major life-sustaining realm of the terrestrial surface. The processes controlling the development and transformation of the CZ are important to continued health of the planet as human influence continues to grow. The CZ encompasses the shallow subsurface, a region of reaction, unsaturated flow, and transport. Chemical weathering in the subsurface is one of the important processes involved in the formation and functioning of the CZ. We present two case studies of reactive transport modeling to investigate the influence of subsurface heterogeneity and unsaturated flow on chemical weathering processes in the CZ. The model is implemented using the reactive transport code PFLOTRAN. Heterogeneity in subsurface flow is represented using multiple realizations of conductive fracture networks in a hillslope cross-section. The first case study is motivated by observations at the Boulder Creek Critical Zone Observatory (BCCZO) including extensive hydrologic and geochemical datasets. The simulations show that fractures greatly enhance weathering as compared to a homogeneous porous medium. Simulations of north-facing slope hydrology with prolonged snowmelt pulses also increases weathering rates, showing the importance of slope aspect on weathering intensity. Recent work elucidates deteriorating water quality caused by climate change in the CZ of watersheds where acid rock drainage (ARD) occurs. The more complex reactions of ARD require a customized kinetic reaction module with PFLOTRAN. The second case study explores the mechanisms by which changes in hydrologic forcing, air and ground temperatures, and water table elevations influence ARD. For instance, unreacted pyrite exposed by a water table drop was shown to produce a 125% increase in annual pyrite oxidization rate, which provides one explanation for increased ARD.

  14. Chemical Analysis of Organic Aerosols Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2013-12-01

    Nanospray Desorption Electrospray Ionization (nano-DESI) technique integrated with high resolution mass spectrometry (HR-MS) enables molecular level analysis of organic aerosol (OA) samples. In nano-DESI, analyte is desorbed into a small volume solvent bridge formed between two capillaries positioned in contact with analyte and enables fast and efficient characterization of OA collected on substrates without sample preparation. We report applications of the nano-DESI/HR-MS approach in a number of our recent studies focused on molecular identification of organic compounds in laboratory and in field collected OA samples. Reactive nano-DESI approach where selected reagent is added to the solvent is used for examining the presence of individual species containing specific functional groups and for their quantification within complex mixtures of OA. Specifically, we use the Girard's reagent T (GT) to probe and quantify carbonyl compounds in the SOA mixtures. We estimate for the first time the amounts of dimers and trimers in the SOA mixtures. We found that the most abundant dimer in limonene/O3 SOA was detected at the ˜0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ˜11 pg. Understanding of the OA composition at the molecular level allowed us to identify key aging reactions, including the transformation of carbonyls to imines and carbonyl-imine oligomerization, that may contribute to the formation of brown carbon in the atmosphere.

  15. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  16. Diffusion of chemically reactive species in Casson fluid flow over an unsteady permeable stretching surface

    Institute of Scientific and Technical Information of China (English)

    MUKHOPADHYAY Swati; VAJRAVELU Kuppalapalle

    2013-01-01

    In this paper we investigate the two-dimensional flow of a non-Newtonian fluid over an unsteady stretching permeable surface.The Casson fluid model is used to characterize the non-Newtonian fluid behavior.First-order constructive/destructive chemical reaction is considered.With the help of a shooting method,numerical solutions for a class of nonlinear coupled differential equations subject to appropriate boundary conditions are obtained.For the steady flow,the exact solution is obtained.The flow features and the mass transfer characteristics for different values of the governing parameters are analyzed and discussed in detail.

  17. Coupling Chemical Kinetics and Flashes in Reactive, Thermal and Compositional Reservoir Simulation

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove;

    2007-01-01

    of convergence and error test failures by more than 50% compared to direct integration without the new algorithm. To facilitate the algorithmic development we construct a virtual kinetic cell model. We use implicit one-step ESDIRK (Explicit Singly Diagonal Implicit Runge-Kutta) methods for integration...... of the kinetics. The kinetic cell model serves both as a tool for the development and testing of tailored solvers as well as a testbed for studying the interactions between chemical kinetics and phase behavior. A comparison between a Kvalue correlation based approach and a more rigorous equation of state based...

  18. Modeling the Influence of Transport on Chemical Reactivity in Microbial Membranes: Mineral Precipitation/Dissolution Reactions.

    Science.gov (United States)

    Felmy, A. R.; Liu, C.; Clark, S.; Straatsma, T.; Rustad, J.

    2003-12-01

    It has long been known that microorganisms can alter the chemical composition of their immediate surroundings and influence such processes as ion uptake or adsorption and mineral precipitation dissolution. However, only recently have molecular imaging and molecular modeling capabilities been developed that begin to shed light on the nature of these processes at the nm to um scale at the surface of bacterial membranes. In this presentation we will show the results of recent molecular simulations of microbial surface reactions and describe our efforts to develop accurate non-equilibrium thermodynamic models for the microbial surface that can describe ion uptake and surface induced mineral precipitation. The thermodynamic models include the influence of the bacterial electrical double layer on the uptake of ions from solution and the removal, or exclusion, of ions from the surface of the cell, non-equilibrium diffusion and chemical reaction within the membrane, as well as a new thermodynamic approach to representing ion activities within the microbial membrane. In the latter case, the variability in the water content within the microbial membrane has a significant influence on the calculated mineral saturation indices. In such cases, we will propose the use of recently developed mixed solvent-electrolyte formalisms. Recent experimental data for mixed-solvent electrolyte systems will also be presented to demonstrate the potential impact of the variable water content on calculated ion activities within the membrane.

  19. Computational chemistry of natural products: a comparison of the chemical reactivity of isonaringin calculated with the M06 family of density functionals.

    Science.gov (United States)

    Glossman-Mitnik, Daniel

    2014-07-01

    The M06 family of density functionals has been assessed for the calculation of the molecular structure and properties of the Isonaringin flavonoid that can be an interesting material for dye-sensitized solar cells (DSSC). The chemical reactivity descriptors have been calculated through chemical reactivity theory within DFT (CR-DFT). The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices and the dual descriptor f ((2))(r). A comparison between the descriptors calculated through vertical energy values and those arising from the Janak's theorem approximation have been performed in order to check for the validity of the last procedure.

  20. Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

    Science.gov (United States)

    Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

    2017-06-01

    Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

  1. Transient analysis of diffusive chemical reactive species for couple stress fluid flow over vertical cylinder

    Institute of Scientific and Technical Information of China (English)

    H. P. RANI; G. J. REDDY; C. N. KIM

    2013-01-01

    The unsteady natural convective couple stress fluid flow over a semi-infinite vertical cylinder is analyzed for the homogeneous first-order chemical reaction effect. The couple stress fluid flow model introduces the length dependent effect based on the material constant and dynamic viscosity. Also, it introduces the biharmonic operator in the Navier-Stokes equations, which is absent in the case of Newtonian fluids. The solution to the time-dependent non-linear and coupled governing equations is carried out with an unconditionally stable Crank-Nicolson type of numerical schemes. Numerical results for the transient flow variables, the average wall shear stress, the Nusselt number, and the Sherwood number are shown graphically for both generative and destructive reactions. The time to reach the temporal maximum increases as the reaction constant K increases. The average values of the wall shear stress and the heat transfer rate decrease as K increases, while increase with the increase in the Sherwood number.

  2. Similarity transformation approach for ferromagnetic mixed convection flow in the presence of chemically reactive magnetic dipole

    Science.gov (United States)

    Hayat, Tasawar; Ijaz Khan, Muhammad; Imtiaz, Maria; Alsaedi, Ahmed; Waqas, Muhammad

    2016-10-01

    A simple model of chemical reactions for two dimensional ferrofluid flows is constructed. The impact of magnetic dipole and mixed convection is further analyzed. Flow is caused by linear stretching of the sheet. Similarity transformation is adopted to convert the partial differential equations into ordinary differential equations and then solved by Euler's explicit method. The characteristics of sundry parameters on the velocity, temperature, and concentration fields are graphically elaborated. It is noted that the impact of magneto-thermomechanical interaction is to slow down the fluid motion. The skin friction coefficient enhances and affects the rate of heat transfer. For higher values of ferrohydrodynamics, the interaction velocity shows decreasing behavior. Further the Prandtl number on temperature has opposite behavior when compared with thermal radiation and ferrohydrodynamics interaction.

  3. Genetic hemoglobin disorders rather than iron deficiency are a major predictor of hemoglobin concentration in women of reproductive age in rural prey Veng, Cambodia.

    Science.gov (United States)

    Karakochuk, Crystal D; Whitfield, Kyly C; Barr, Susan I; Lamers, Yvonne; Devlin, Angela M; Vercauteren, Suzanne M; Kroeun, Hou; Talukder, Aminuzzaman; McLean, Judy; Green, Timothy J

    2015-01-01

    Anemia is common in Cambodian women. Potential causes include micronutrient deficiencies, genetic hemoglobin disorders, inflammation, and disease. We aimed to investigate factors associated with anemia (low hemoglobin concentration) in rural Cambodian women (18-45 y) and to investigate the relations between hemoglobin disorders and other iron biomarkers. Blood samples were obtained from 450 women. A complete blood count was conducted, and serum and plasma were analyzed for ferritin, soluble transferrin receptor (sTfR), folate, vitamin B-12, retinol binding protein (RBP), C-reactive protein (CRP), and α1 acid glycoprotein (AGP). Hemoglobin electrophoresis and multiplex polymerase chain reaction were used to determine the prevalence and type of genetic hemoglobin disorders. Overall, 54% of women had a genetic hemoglobin disorder, which included 25 different genotypes (most commonly, hemoglobin E variants and α(3.7)-thalassemia). Of the 420 nonpregnant women, 29.5% had anemia (hemoglobin iron stores (ferritin iron deficiency (sTfR >8.3 mg/L), iron deficiency anemia (IDA) were 14.2% and 1.5% in those with and without hemoglobin disorders, respectively. There was no biochemical evidence of vitamin A deficiency (RBP 5 mg/L) and 26% (AGP >1 g/L) of nonpregnant women, respectively. By using an adjusted linear regression model, the strongest predictors of hemoglobin concentration were hemoglobin E homozygous disorder and pregnancy status. Other predictors were 2 other heterozygous traits (hemoglobin E and Constant Spring), parity, RBP, log ferritin, and vitamin B-12. Multiple biomarkers for anemia and iron deficiency were significantly influenced by the presence of hemoglobin disorders, hence reducing their diagnostic sensitivity. Further investigation of the unexpectedly low prevalence of IDA in Cambodian women is warranted. © 2015 American Society for Nutrition.

  4. Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

    Energy Technology Data Exchange (ETDEWEB)

    Bergren, Adam Johan [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    Electroanalytical chemistry is often utilized in chemical analysis and Fundamental studies. Important advances have been made in these areas since the advent of chemically modified electrodes: the coating of an electrode with a chemical film in order to impart desirable, and ideally, predictable properties. These procedures enable the exploitation of unique reactivity patterns. This dissertation presents studies that investigate novel reaction mechanisms at self-assembled monolayers on gold. In particular, a unique electrochemical current amplification scheme is detailed that relies on a selective electrode to enable a reactivity pattern that results in regeneration of the analyte (redox recycling). This regenerating reaction can occur up to 250 times for each analyte molecule, leading to a notable enhancement in the observed current. The requirements of electrode selectivity and the resulting amplification and detection limit improvements are described with respect to the heterogeneous and homogeneous electron transfer rates that characterize the system. These studies revealed that the heterogeneous electrolysis of the analyte should ideally be electrochemically reversible, while that for the regenerating agent should be held to a low level. Moreover, the homogeneous reaction that recycles the analyte should occur at a rapid rate. The physical selectivity mechanism is also detailed with respect to the properties of the electrode and redox probes utilized. It is shown that partitioning of the analyte into/onto the adlayer leads to the extraordinary selectivity of the alkanethiolate monolayer modified electrode. Collectively, these studies enable a thorough understanding of the complex electrode mechanism required for successful redox recycling amplification systems, Finally, in a separate (but related) study, the effect of the akyl chain length on the heterogeneous electron transfer behavior of solution-based redox probes is reported, where an odd-even oscillation

  5. Physico-chemical changes of the ground waters related to the 2011 El Hierro magmatic reactivation

    Science.gov (United States)

    Dionis, S.; Melián, G.; Padrón, E.; Padilla, G.; Nolasco, D.; Rodríguez, F.; Hernández, I.; Peraza, D.; Barrancos, J.; Hernández, P.; Calvo, D.; Pérez, N.

    2012-04-01

    The island of El Hierro (278 Km2), is the smallest, the southwesternmost and the youngest island (˜1.12 My) of the Canarian archipelago. The main geological characteristics of El Hierro consist on the presence of three convergent ridges of volcanic cones on a truncated trihedron shape and giant landslides between the three rift zones, being the most recent El Golfo on the northwest flank of the island. On July 2011 an anomalous seismic activity at Hierro Island started and suggested the initial stage of a volcanic unrest in the volcanic system. On October 10, after the occurrence of more than 10,000 earthquakes, a submarine eruption started. Evidences of this submarine volcanic eruption were visible on the sea surface to the south of La Restinga village, at the south of the island, in the form of large light-green coloured area, turbulent gas emission and the appearance of steamy volcanic fragments three days later. As part of its volcanic surveillance activities, the Instituto Volcanologico de Canarias (INVOLCAN) started a hydrogeochemical monitoring program on August 2011 in order to evaluate the temporal evolution of several physico-chemical parameters of the ground water system of El Hierro. Four observation sites were selected: three wells on the north of the island, where the seismic activity was located at the beginning of the volcano-seismic unrest (SIMO, FRON and PADO) and one horizontal well (gallery) in the south (TACO). Ground water sampling is being regularly collected, three times per week, at each observation site, and in-situ measurements of pH, conductivity and temperature measurements are performed. After 6 month of monitoring, no significant changes have been observed on pH and temperature measurements from all the observation sites. However, clear sharp decrease of conductivity was observed at SIMO on October 10 when the seismic tremor started. In addition, the strongest conductivity decrease pattern was observed later on at SIMO and PADO on

  6. Chemical reactivity of {alpha}-isosaccharinic acid in heterogeneous alkaline systems

    Energy Technology Data Exchange (ETDEWEB)

    Glaus, M. A.; Loon, L. R. Van

    2009-05-15

    Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, {alpha}- isosaccharinic acid ({alpha}-ISA) is the strongest complexant. The prediction of the equilibrium concentration of {alpha}-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of {alpha}-ISA in heterogeneous alkaline model systems containing either Ca(OH){sub 2} or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of {alpha}-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 {sup o}C or 90 {sup o}C, and under anaerobic atmospheres obtained by various methods. It was found that {alpha}-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than {alpha}-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was {approx} 50 % of the amount of {alpha}-ISA reacted. Sorption of {alpha}-ISA to Ca(OH){sub 2} contributed only to a minor extent to the loss of {alpha}-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of {alpha}-ISA. Under aerobic conditions {alpha}-ISA was

  7. Chemical exposure-response relationship between air pollutants and reactive oxygen species in the human respiratory tract

    Science.gov (United States)

    Lakey, P. S. J.; Berkemeier, T.; Tong, H.; Arangio, A. M.; Lucas, K.; Poeschl, U.; Shiraiwa, M.

    2016-12-01

    The inhalation of air pollutants such as O3 and particulate matter can lead to the formation of reactive oxygen species (ROS) which can cause damage to biosurfaces such as the lung epithelium unless they are effectively scavenged. Although the chemical processes that lead to ROS formation within the ELF upon inhalation of pollutants are well understood qualitatively, ROS concentrations within the ELF have hardly been quantified so far. The kinetic multi-layer model of surface and bulk chemistry in the epithelial lining fluid (KM-SUB-ELF) has been developed to describe chemical reactions and mass transport and to quantify ROS production rates and concentrations within the epithelial lining fluid. KM-SUB-ELF simulations suggest that O3 will rapidly saturate the ELF whereas antioxidants and surfactant species are effective scavengers of OH. High ambient concentrations of O3 can lead to the depletion of surfactants and antioxidants within the ELF, potentially leading to oxidative stress. KM-SUB-ELF reproduced measurements for the formation of H2O2 and OH due to the presence of iron, copper and quinones in surrogate lung lining fluid. This enabled ROS production rates and concentrations in the ELF to be quantified. We found that in polluted megacities the ROS concentration in the ELF due to inhalation of pollutants was at least as high as the concentrations in the ELF of patients suffering from respiratory diseases. Cu and Fe are found to be the most important redox-active aerosol components for ROS production upon inhalation of PM2.5 in polluted regions. Therefore, a reduction in the emission of Cu and Fe should be major targets of air pollution control. Chemical exposure-response relations provide a quantitative basis for assessing the relative importance of specific air pollutants in different regions of the world, showing that aerosol-induced epithelial ROS levels in polluted megacity air can be several orders of magnitude higher than in pristine rainforest air.

  8. Applications of the Information Theory to Problems of Molecular Electronic Structure and Chemical Reactivity

    Directory of Open Access Journals (Sweden)

    Roman F. Nalewajski

    2002-04-01

    Full Text Available Abstract: Recent studies on applications of the information theoretic concepts to molecular systems are reviewed. This survey covers the information theory basis of the Hirshfeld partitioning of molecular electron densities, its generalization to many electron probabilities, the local information distance analysis of molecular charge distributions, the charge transfer descriptors of the donor-acceptor reactive systems, the elements of a “thermodynamic” description of molecular charge displacements, both “vertical” (between molecular fragments for the fixed overall density and “horizontal” (involving different molecular densities, with the entropic representation description provided by the information theory. The average uncertainty measures of bond multiplicities in molecular “communication” systems are also briefly summarized. After an overview of alternative indicators of the information distance (entropy deficiency, missing information between probability distributions the properties of the “stockholder” densities, which minimize the entropy deficiency relative to the promolecule reference, are summarized. In particular, the surprisal analysis of molecular densities is advocated as an attractive information-theoretic tool in the electronic structure theory, supplementary to the familiar density difference diagrams. The subsystem information density equalization rules satisfied by the Hirshfeld molecular fragments are emphasized: the local values of alternative information distance densities of subsystems are equal to the corresponding global value, characterizing the molecule as a whole. These local measures of the information content are semi-quantitatively related to the molecular density difference function. In the density functional theory the effective external potentials of molecular fragments are defined, for which

  9. Exact Solutions of Chemically Reactive Solute Distribution in MHD Boundary Layer Flow over a Shrinking Surface

    Institute of Scientific and Technical Information of China (English)

    Chandaneswar Midya

    2012-01-01

    An analytical study of the distribution of a reactant solute undergoing a first-order chemical reaction in the boundary layer flow of an electrically conducting incompressible Buid over a linearly shrinking surface is presented. The Row is permeated by an externally applied magnetic Geld normal to the plane of the flow. The equations governing the Row and concentration Reid are reduced into a set of nonlinear ordinary differential equations using similarity variables. Closed form exact solutions of the reduced concentration equation are obtained for both prescribed power-law surface concentration (PSC) and power-law wall mass flux (PMF) as boundary conditions. The study reveals that the concentration over a shrinking sheet is signiRcantly different from that of a stretching surface. It s found that te solute boundary layer thickness is enhanced with the increasing values of the Schmidt number and the power-law index parameter, but decreases with enhanced vaJues of magnetic and reaction rate parameters for the PSC case. For the PMF case, the solute boundary layer thickness decreases with the increase of the Schmidt number, magnetic and reaction rate parameter for power-law index parameter n = 0. Negative solute boundary layer thickness is observed for the PMF case when n = 1 and 2, and these facts may not be realized in real-world applications.%An analytical study of the distribution of a reactant solute undergoing a first-order chemical reaction in the boundary layer flow of an electrically conducting incompressible fluid over a linearly shrinking surface is presented.The flow is permeated by an externally applied magnetic field normal to the plane of the flow.The equations governing the flow and concentration field are reduced into a set of nonlinear ordinary differential equations using similarity variables.Closed form exact solutions of the reduced concentration equation are obtained for both prescribed power-law surface concentration (PSC) and power-law wall

  10. Structure, surface reactivity and physico-chemical degradation of fluoride containing phospho-silicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kansal, Ishu; Goel, Ashutosh; Tulyaganov, Dilshat U.; Santos, Luis F.; Ferreira, Jose M.

    2011-03-28

    We report on the structure, apatite-forming ability and physicochemical degradation of glasses along fluorapatite [FA; Ca5(PO4)3F] - diopside (Di; CaMgSi2O6) join. A series of glasses with varying FA/Di ratio have been synthesised by melt-quenching technique. The amorphous glasses could be obtained only for compositions up to 40 wt.% of FA. The detailed structural analysis of glasses has been made by infra-red spectroscopy (FTIR), Raman spectroscopy and magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR). Silicon was predominantly present as Q2 (Si) species while phosphorus was found in orthophosphate type environment in all the investigated glasses. The apatite forming ability of glasses was investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h – 28 days. An extensive precipitation of calcite (CaCO3) after immersion in SBF was found in all the glasses which considerably masked the formation of hydroxyapatite [HA; Ca5(PO4)3OH] as depicted by X-ray diffraction (XRD) and FTIR. The possible mechanism favouring formation of calcite instead of HA has been explained on the basis of experimental results obtained for structure of glasses, leaching profile of glass powders in SBF solution and pH variation in SBF solution. Further, physico-chemical degradation of glasses has been studied in accordance with ISO 10993-14 “Biological evaluation of medical devices – Part 14: Identification and quantification of degradation products from ceramics” in Tris HCl and citric acid buffer. All the FA containing glasses exhibited a weight gain (instead of weight loss) after immersion in citric acid buffer due to the formation of different crystalline products.

  11. Influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with carcinogenic and anticoagulant effect of 17β-aminoestrogens

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: socc@puma2.zaragoza.unam.mx [Química Computacional, FES-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, Mexico City (Mexico); Raya, Angélica [Unidad Profesional Interdisciplinaria de Ingeniería Campus Guanajuato, Instituto Politécnico Nacional (IPN), Silao de la Victoria, Guanajuato (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz - Boca del Río, Universidad Veracruzana, Veracruz (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), Mexico City (Mexico)

    2014-06-25

    Highlights: • The aromatic A-ring of 17β-aminoestrogens contribute to its anticoagulant effect. • The electron-donor substituent groups favored the basicity of 17β-aminoestrogens. • The physicochemical properties are important in the carcinogenic effect of anticoagulant molecules. - Abstract: Activity of steroid hormones is dependent upon a number of factors, as solubility, transport and metabolism. The functional differences caused by structural modifications could exert an influence on the chemical reactivity and biological effect. The goal of this work is to study the influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with the carcinogenic risk that can associate with the anticoagulant effect of 17β-aminoestrogens using quantum-chemical descriptors at the DFT-B3LYP, BH and HLYP and M06-2X levels. The relative acidity of (H1) of the hydroxyl group increases with electron-withdrawing groups. Electron-donor groups favor the basicity. The steric hindrance of the substituents decreases the aromatic character and consequently diminution the carcinogenic effect. Density descriptors: hardness, electrophilic index, atomic charges, molecular orbitals, electrostatic potential and their geometric parameters permit analyses of the chemical reactivity and physicochemical features and to identify some reactive sites of 17β-aminoestrogens.

  12. 妊娠期糖代谢异常与尿酸、C肽、超敏C反应蛋白、糖化血红蛋白相关性%Correlation of gestational abnormal glucose metabolism and uric acid,C peptide,high sensitivity C reactive protein,glycated hemoglobin

    Institute of Scientific and Technical Information of China (English)

    周静姝; 金海甲; 刘飞; 郝凤燕

    2015-01-01

    目的:探讨C肽、超敏C反应蛋白、糖化血红蛋白、尿酸及血脂等多因素与妊娠期糖代谢异常的相关性。方法:2010年1月-2011年8月收集分娩孕妇,统计其在孕24~28周前后检测的血糖与尿酸、CRP、血脂、超敏CRP、C肽、糖化血红蛋白、体重、血压及文化背景等,其中异常23例;随机抽取40例正常者为对照。C肽采用电化学发光方法,超敏C反应蛋白采用芬兰试剂,糖化血红蛋白用TDM100糖化血红蛋白分析仪测定。采用多因素分析评价其相关性。结果:多因素联合分析比单个独立因素评价糖代谢异常相关性高。结论:多项联合检测能提前预测糖代谢异常的发生,提前采取治疗措施,预防疾病发生,得到很好的预后效果。%Objective:To explore the correlation of gestational abnormal glucose metabolism and C peptide,high sensitivity C reactive protein,glycated hemoglobin,uric acid,blood lipid and other factors.Methods:Childbirth pregnant womens were selected from January 2010 to August 2011.The blood glucose and uric acid,CRP,blood lipid,high sensitivity CRP,C peptide,glycated hemoglobin that were detected before and after pregnancy 24 to 28 weeks.Weight,blood pressure and cultural background were statistically analyzed,in which 23 cases were abnormal.A random sample of 40 normal persons was as the control.C peptide used electrochemiluminescence method,the high sensitive C reactive protein used finland reagent,the glycated hemoglobin was detected by TDM100 glycated hemoglobin analyzer instrument.The correlation was analyzed and evaluated by multi factors. Results:The multi factor combined analysis in the evaluation of abnormal glucose metabolism correlation was higher than a single independent factor.Conclusion:The multiple combined detection can predict abnormal glucose metabolism in advance.It can advance to take treatment,prevent disease,and obtain very good prognosis effect.

  13. Structure and chemical reactivity of the polar three-fold surfaces of GaPd: a density-functional study.

    Science.gov (United States)

    Krajčí, M; Hafner, J

    2013-03-28

    The polar threefold surfaces of the GaPd compound crystallizing in the B20 (FeSi-type) structure (space group P2(1)3) have been investigated using density-functional methods. Because of the lack of inversion symmetry the B20 structure exists in two enantiomorphic forms denoted as A and B. The threefold {111} surfaces have polar character. In both nonequivalent (111) and (111) directions several surface terminations differing in structure and chemical composition are possible. The formation of the threefold surfaces has been studied by simulated cleavage experiments and by calculations of the surface energies. Because of the polar character of the threefold surfaces calculations for stoichiometric slabs permit only the determination of the average energy of the surfaces exposed on both sides of the slab. Calculations for nonstoichiometric slabs performed in the grand canonical ensemble yield differences of the surface energies for the possible terminations as a function of the chemical potential in the reactive atmosphere above the surface and predict a transition between Ga- and Pd-terminated surfaces as a function of the chemical potential. The {100} surfaces are stoichiometric and uniquely defined. The calculated surface energies are identical to the average energies of the {100} surfaces of the pure metals. The {210} surfaces are also stoichiometric, with an energy very close to that of the {100} surfaces. Assuming that for the {111} surfaces the energies of different possible terminations are in a proportion equal to that of the concentration-weighted energies of the {111} surfaces of the pure metals, surface energies for all possible {111} terminations may be calculated. The preferable termination perpendicular to the A direction consists of a bilayer with three Ga atoms in the upper and three Pd atoms in the lower part. The surface energy of this termination further decreases if the Pd triplet is covered by additional Ga atom. Perpendicular to the A direction

  14. Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

    Energy Technology Data Exchange (ETDEWEB)

    Jacques, S., E-mail: jacques@lcts.u-bordeaux1.fr [LCTS, University of Bordeaux 1, CNRS, Herakles-Safran, CEA, 3 allee de la Boetie, F-33600 Pessac (France); Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P. [LCTS, University of Bordeaux 1, CNRS, Herakles-Safran, CEA, 3 allee de la Boetie, F-33600 Pessac (France)

    2013-06-15

    In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called “interphase” between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC–TiC){sub n} interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC–TiC){sub n} films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

  15. Non-invasive hemoglobin monitoring.

    Science.gov (United States)

    Joseph, Bellal; Haider, Ansab; Rhee, Peter

    2016-09-01

    Technology has transformed the practice of medicine and surgery in particular over the last several decades. This change in practice has allowed diagnostic and therapeutic tests to be performed less invasively. Hemoglobin monitoring remains one of the most commonly performed diagnostic tests in the United States. Recently, non-invasive hemoglobin monitoring technology has gained popularity. The aim of this article is to review the principles of how this technology works, pros and cons, and the implications of non-invasive hemoglobin technology particularly in trauma surgery.

  16. Optical and chemical properties of mixed-valent rhenium oxide films synthesized by reactive DC magnetron sputtering

    Science.gov (United States)

    Murphy, Neil R.; Gallagher, Regina C.; Sun, Lirong; Jones, John G.; Grant, John T.

    2015-07-01

    Mixed-valent rhenium oxide thin films were deposited using reactive magnetron sputtering employing a metallic rhenium target within an oxygen-argon environment. The oxygen and argon flow rates were systematically varied, while the extinction coefficient, k, of the deposited layers was monitored using in situ spectroscopic ellipsometry. In situ monitoring was used to identify absorption features specific to ReO3, namely, the minimization of k brought on by the gap between interband absorption features in the UV at 310 nm and the onset of free electron absorption at wavelengths above 540 nm. Based on these results, oxygen flow ratios of 50% and 60% were shown to produce films having optical properties characteristic of ReO3, and thus, were selected for detailed ex situ characterization. Chemical analysis via X-ray photoelectron spectroscopy confirmed that all films consisted largely of ReO3, but had some contributions from Re2O3, ReO2 and Re2O7. Additional monitoring of the chemistry, as a function of environmental exposure time, indicated a correlation between structural instability and the presence of Re2O3 and Re2O7 in the films.

  17. A Sliding-Mode Triboelectric Nanogenerator with Chemical Group Grated Structure by Shadow Mask Reactive Ion Etching.

    Science.gov (United States)

    Shang, Wanyu; Gu, Guang Qin; Yang, Feng; Zhao, Lei; Cheng, Gang; Du, Zu-Liang; Wang, Zhong Lin

    2017-08-25

    The sliding-mode triboelectric nanogenerator (S-TENG) with grated structure has important applications in energy harvest and active sensors; however its concavo-convex structure leads to large frictional resistance and abrasion. Here, we developed a S-TENG with a chemical group grated structure (S-TENG-CGG), in which the triboelectric layer's triboelectric potential has a positive-negative alternating charged structure. The triboelectric layer of the S-TENG-CGG was fabricated through a reactive ion etching process with a metal shadow mask with grated structure. In the etched region, the nylon film, originally positively charged as in friction with stainless steel, gained opposite triboelectric potential and became negatively charged because of the change of surface functional groups. The output signals of the S-TENG-CGG are alternating and the frequency is determined by both the segment numbers and the moving speed. The applications of the S-TENG-CGG in the charging capacitor and driving calculator are demonstrated. In the S-TENG-CGG, since there is no concavo-convex structure, the frictional resistance and abrasion are largely reduced, which enhances its performances in better stability and longer working time.

  18. Molecular structure, IR spectra, and chemical reactivity of cisplatin and transplatin: DFT studies, basis set effect and solvent effect.

    Science.gov (United States)

    Wang, Yang; Liu, Qingzhu; Qiu, Ling; Wang, Tengfei; Yuan, Haoliang; Lin, Jianguo; Luo, Shineng

    2015-01-01

    Three different density functional theory (DFT) methods were employed to study the molecular structures of cis-diamminedichloroplatinum(II) (CDDP) and trans-diamminedichloroplatinum(II) (TDDP). The basis set effect on the structure was also investigated. By comparing the optimized structures with the experimental data, a relatively more accurate method was chosen for further study of the IR spectra and other properties as well as the solvent effect. Nineteen characteristic vibrational bands of the title compounds were assigned and compared with available experimental data. The number of characteristic peaks for the asymmetric stretching and deformation vibrations of N-H can serve as a judgment for the isomer between CDDP and TDDP. Significant solvent effect was observed on the molecular structures and IR spectra. The reduced density gradient analysis was performed to study the intramolecular interactions of CDDP and TDDP, and the nature of changes in the structures caused by the solvent was illustrated. Several descriptors determined from the energies of frontier molecular orbitals (HOMO and LUMO) were applied to describe the chemical reactivity of the title compounds. The molecular electrostatic potential (MESP) surfaces showed that the amino groups were the most favorable sites that nucleophilic reagents tend to attack, and CDDP was easier to be attacked by nucleophilic reagents than TDDP.

  19. Chemical Reactivity Dynamics and Quantum Chaos in Highly Excited Hydrogen Atoms in an External Field: A Quantum Potential Approach

    Directory of Open Access Journals (Sweden)

    B. Maiti

    2002-04-01

    Full Text Available Abstract: Dynamical behavior of chemical reactivity indices like electronegativity, hardness, polarizability, electrophilicity and nucleophilicity indices is studied within a quantum fluid density functional framework for the interactions of a hydrogen atom in its ground electronic state (n = 1 and an excited electronic state (n = 20 with monochromatic and bichromatic laser pulses. Time dependent analogues of various electronic structure principles like the principles of electronegativity equalization, maximum hardness, minimum polarizability and maximum entropy have been found to be operative. Insights into the variation of intensities of the generated higher order harmonics on the color of the external laser field are obtained. The quantum signature of chaos in hydrogen atom has been studied using a quantum theory of motion and quantum fluid dynamics. A hydrogen atom in the electronic ground state (n = 1 and in an excited electronic state ( n = 20 behaves differently when placed in external oscillating monochromatic and bichromatic electric fields. Temporal evolutions of Shannon entropy, quantum Lyapunov exponent and Kolmogorov – Sinai entropy defined in terms of the distance between two initially close Bohmian trajectories for these two cases show marked differences. It appears that a larger uncertainty product and a smaller hardness value signal a chaotic behavior.

  20. Evaluation of molecular assembly, spectroscopic interpretation, intra-/inter molecular hydrogen bonding and chemical reactivity of two pyrrole precursors

    Science.gov (United States)

    Rawat, Poonam; Singh, R. N.

    2014-10-01

    This paper describes the evaluation of conformational, spectroscopic, hydrogen bonding and chemical reactivity of pyrrole precursor: ethyl 3,5 dimethyl-1H-pyrrole-2-carboxylate (EDPC) and ethyl 3,4-dimethyl-4-acetyl-1H-pyrrole-2-carboxylate (EDAPC) for the convenient characterization, synthetic usefulness and comparative evaluations. All experimental spectral values of 1H NMR, UV-Vis and FT-IR spectra coincide well with calculated values by DFT. The orbital interactions in EDPC and EDAPC are found to lengthen their Nsbnd H and Cdbnd O bonds and lowers their vibrational frequencies (red shift) resulting to dimer formation. The QTAIM and NBO analyses provide the strength of interactions and charge transfer in the hydrogen bonding unit and stability of dimers. The binding energy of EDPC and EDPAC dimer are found to be 9.92, 10.22 kcal/mol, respectively. In EDPAC and EDPC dimer, hyperconjugative interactions between monomer units is due to n1(O) → σ*(Nsbnd H) that stabilize the molecule up to 9.7 and 9.3 kcal/mol, respectively. On evaluation of molecular electrostatic potential (MEP) and electronic descriptors for EDPC it has been found that it is a good precursor for synthesis of formyl and acetyl derivatives whereas EDAPC has been found to be a good precursor for synthesis of schiff base, hydrazones, hydrazide-hydrazones and chalcones.

  1. Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants.

    Science.gov (United States)

    Gu, Qing; Bravo-Díaz, Carlos; Romsted, Laurence S

    2013-06-15

    Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

  2. Characterization of glycidol-hemoglobin adducts as biomarkers of exposure and in vivo dose.

    Science.gov (United States)

    Honda, Hiroshi; Törnqvist, Margareta; Nishiyama, Naohiro; Kasamatsu, Toshio

    2014-03-15

    Hemoglobin adducts have been used as biomarkers of exposure to reactive chemicals. Glycidol, an animal carcinogen, has been reported to form N-(2,3-dihydroxy-propyl)valine adducts to hemoglobin (diHOPrVal). To support the use of these adducts as markers of glycidol exposure, we investigated the kinetics of diHOPrVal formation and its elimination in vitro and in vivo. Five groups of rats were orally administered a single dose of glycidol ranging from 0 to 75mg/kg bw, and diHOPrVal levels were measured 24h after administration. A dose-dependent increase in diHOPrVal levels was observed with high linearity (R(2)=0.943). Blood sampling at different time points (1, 10, 20, or 40days) from four groups administered glycidol at 12mg/kg bw suggested a linear decrease in diHOPrVal levels compatible with the normal turnover of rat erythrocytes (life span, 61days), with the calculated first-order elimination rate constant (kel) indicating that the diHOPrVal adduct was chemically stable. Then, we measured the second-order rate constant (kval) for the reaction of glycidol with N-terminal valine in rat and human hemoglobin in in vitro experiments with whole blood. The kval was 6.7±1.1 and 5.6±1.3 (pmol/g globin per μMh) in rat and human blood, respectively, indicating no species differences. In vivo doses estimated from kval and diHOPrVal levels were in agreement with the area under the (concentration-time) curve values determined in our earlier toxicokinetic study in rats. Our results indicate that diHOPrVal is a useful biomarker for quantification of glycidol exposure and for risk assessment.

  3. Assembly processes in oligomers containing structurally distinct subunits. [Hemoglobin, Hemocyanin

    Energy Technology Data Exchange (ETDEWEB)

    Bonaventura, C. (Duke Univ. Marine Laboratory, Beaufort, NC); Bonaventura, J.; Brouwer, M.

    1980-10-01

    There are two major classes of oxygen carrying proteins: the hemoglobins and the hemocyanins. Thetrameric hemoglobin is an oxygen carrier that has long served as a model in the analysis of allostery in proteins. In assembly processes as well, the oxygen carrying proteins appear to be good model systems which illustrate the distinct roles played by structurally diverse subunits. Thetrameric human hemoglobin shows definite differences in assembly and tetrameric stability depending on alpha-beta, alpha-alpha, beta-beta, alpha-gamma, etc., interactions. The blue-colored hemocyanins are found in the hemolymph of many molluscs and arthropods. In these molecules, oxygen binds at dimeric copper centers. Te reactivity toward oxygen is typically modulated by external factors such as pH and sodium chloride. Because of their extremely large size and subunit diversity, the hemocyanins may be particularly useful as assembly models.

  4. More Refined Experiments with Hemoglobin.

    Science.gov (United States)

    Morin, Phillippe

    1985-01-01

    Discusses materials needed, procedures used, and typical results obtained for experiments designed to make a numerical stepwise study of the oxygenation of hemoglobin, myoglobin, and other oxygen carriers. (JN)

  5. Nonlinear photoacoustic spectroscopy of hemoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Danielli, Amos; Maslov, Konstantin; Favazza, Christopher P.; Xia, Jun; Wang, Lihong V., E-mail: LHWANG@WUSTL.EDU [Optical Imaging Laboratory, Department of Biomedical Engineering, Washington University in St. Louis, One Brookings Drive, St. Louis, Missouri 63130 (United States)

    2015-05-18

    As light intensity increases in photoacoustic imaging, the saturation of optical absorption and the temperature dependence of the thermal expansion coefficient result in a measurable nonlinear dependence of the photoacoustic (PA) signal on the excitation pulse fluence. Here, under controlled conditions, we investigate the intensity-dependent photoacoustic signals from oxygenated and deoxygenated hemoglobin at varied optical wavelengths and molecular concentrations. The wavelength and concentration dependencies of the nonlinear PA spectrum are found to be significantly greater in oxygenated hemoglobin than in deoxygenated hemoglobin. These effects are further influenced by the hemoglobin concentration. These nonlinear phenomena provide insights into applications of photoacoustics, such as measurements of average inter-molecular distances on a nm scale or with a tuned selection of wavelengths, a more accurate quantitative PA tomography.

  6. Localised IR spectroscopy of hemoglobin

    CERN Document Server

    Yarrow, Fiona

    2010-01-01

    IR absorption spectroscopy of hemoglobin was performed using an IR optical parametric oscillator laser and a commercial atomic force microscope in a novel experimental arrangement based on the use of a bottom-up excitation alignment. This experimental approach enables detection of protein samples with a resolution that is much higher than that of standard IR spectroscopy. Presented here are AFM based IR absorption spectra of micron sized hemoglobin features

  7. Characterization of glycidol-hemoglobin adducts as biomarkers of exposure and in vivo dose

    Energy Technology Data Exchange (ETDEWEB)

    Honda, Hiroshi, E-mail: honda.hiroshi@kao.co.jp [R and D Safety Science Research, Kao Corporation, 2606 Akabane, Ichikai-Machi, Haga-Gun, Tochigi 321-3497 (Japan); Törnqvist, Margareta [Department of Materials and Environmental Chemistry, Environmental Chemistry Unit, Stockholm University, SE-106 91 Stockholm (Sweden); Nishiyama, Naohiro [R and D Safety Science Research, Kao Corporation, 2606 Akabane, Ichikai-Machi, Haga-Gun, Tochigi 321-3497 (Japan); Kasamatsu, Toshio, E-mail: kasamatsu.toshio@kao.co.jp [R and D Safety Science Research, Kao Corporation, 2606 Akabane, Ichikai-Machi, Haga-Gun, Tochigi 321-3497 (Japan)

    2014-03-15

    Hemoglobin adducts have been used as biomarkers of exposure to reactive chemicals. Glycidol, an animal carcinogen, has been reported to form N-(2,3-dihydroxy-propyl)valine adducts to hemoglobin (diHOPrVal). To support the use of these adducts as markers of glycidol exposure, we investigated the kinetics of diHOPrVal formation and its elimination in vitro and in vivo. Five groups of rats were orally administered a single dose of glycidol ranging from 0 to 75 mg/kg bw, and diHOPrVal levels were measured 24 h after administration. A dose-dependent increase in diHOPrVal levels was observed with high linearity (R{sup 2} = 0.943). Blood sampling at different time points (1, 10, 20, or 40 days) from four groups administered glycidol at 12 mg/kg bw suggested a linear decrease in diHOPrVal levels compatible with the normal turnover of rat erythrocytes (life span, 61 days), with the calculated first-order elimination rate constant (k{sub el}) indicating that the diHOPrVal adduct was chemically stable. Then, we measured the second-order rate constant (k{sub val}) for the reaction of glycidol with N-terminal valine in rat and human hemoglobin in in vitro experiments with whole blood. The k{sub val} was 6.7 ± 1.1 and 5.6 ± 1.3 (pmol/g globin per μMh) in rat and human blood, respectively, indicating no species differences. In vivo doses estimated from k{sub val} and diHOPrVal levels were in agreement with the area under the (concentration–time) curve values determined in our earlier toxicokinetic study in rats. Our results indicate that diHOPrVal is a useful biomarker for quantification of glycidol exposure and for risk assessment. - Highlight: • Glycidol-hemoglobin adduct (diHOPrVal) was characterized for exposure evaluation. • We studied the kinetics of diHOPrVal formation and elimination in vitro and in vivo. • Dose dependent formation and chemical stability were confirmed in the rat study. • In vivo dose (AUC) of glycidol could be estimated from diHOPrVal levels

  8. Chemical reactivity of C-F bonds attached to graphene with diamines depending on their nature and location.

    Science.gov (United States)

    Li, Baoyin; He, Taijun; Wang, Zaoming; Cheng, Zheng; Liu, Yang; Chen, Teng; Lai, Wenchuan; Wang, Xu; Liu, Xiangyang

    2016-06-29

    The attachment of fluorine to graphene is a facile means to activate the carbon bonds for subsequent covalent bonding to other molecules for the preparation of desired graphene derivatives. Therefore, an insight into the chemical reactivity of fluorinated graphene (FG) is very essential to enable precise control of the composition and structure of the final products. In this study, FG has been treated with various mass amounts of poly(oxypropylene)diamine (PEA) ranging from starvation to saturation to explore the dependence of a substitution reaction of diamines on the nature and location (attached onto the basal planes or along defects or edges) of C-F bonds. X-ray photoelectron spectroscopy directly tracked the atomic percentage of fluorine present and the carbon 1s bonding state, showing that the grafting ratio of diamines gradually increases with increased diamine mass ratio. The varying of the types and orientation of C-F bonds characterized by polarized attenuated total reflectance Fourier transform infrared spectroscopy indicates that "covalent" C-F bonds are more sensitive to the substitution reaction of diamines than ''semi-ionic'' C-F bonds, and the C-F bonds attached onto basal planes more preferably participate in the functionalization reaction of diamines than that of C-F bonded on non-coplanar regions (edges or defects). The one-dimensional expansion along the graphene c-axis shown by wide angle X-ray diffraction provides further evidence on the preferred functionalization reaction of C-F attached on the basal planes, resulting in a change of the average intersheet distance by various magnitudes.

  9. Impact of Lewis base on chemical reactivity and separation efficiency for hydrated fourth-row transition metal (II) complexes: an ONIOM DFT/MM study.

    Science.gov (United States)

    He, Dingsheng; Ma, Ming

    2014-04-24

    In this paper, two-layer ONIOM combinations of high-level quantum mechanics (QM) and inexpensive molecular mechanics (MM) are successfully used to investigate the structural characters of metal (M, all the transition metals in the fourth period)-H2O-Lewis base (A(-)) complexes. Global and local descriptors of chemical reactivity and selectivity from conceptual density functional theory are employed to show the properties of the active complexes of M(H2O)2A2 and to study the effect of the Lewis base for the separation of transition metal ions. It is shown that chemical potential, hardness, electrophilicity, as well as the dual and multiphilic descriptors are adequate for characterizing the global and local reactivity trends of the M(H2O)2A2 complex. It is found that the reactivity is well localized at the metallic center in M(H2O)2A2 and the dual descriptor (ΔfM(r)) can also be used to characterize the directional attack of the electrophile and nucleophile except for the selectivity of the reaction. On the basis of the values of ωM and Δsk, and the sign of ΔfM(r), the selectivity of the nucleophilic reagent (R(-)) for M(II) in M(H2O)2A2 (from high to low) follows this order: Cu(II) > Ni(II) > Co(II) > Fe(II) ≫ Mn(II) > Zn(II) > Cr(II). The Lewis base (A(-)) improves chemical reactivity and selectivity because of changing the reaction path and forming an intermediate, which possesses the higher antibonding character and the larger HOMO/LUMO gap. NBO or AIMALL analysis and Frontier orbital theory results presented here provided more theoretical support for the above reactivity and selectivity studies.

  10. Induction of Fetal Hemoglobin In Vivo Mediated by a Synthetic γ-Globin Zinc Finger Activator

    Directory of Open Access Journals (Sweden)

    Flávia C. Costa

    2012-01-01

    Full Text Available Sickle cell disease (SCD and β-thalassemia patients are phenotypically normal if they carry compensatory hereditary persistence of fetal hemoglobin (HPFH mutations that result in increased levels of fetal hemoglobin (HbF, γ-globin chains in adulthood. Thus, research has focused on manipulating the reactivation of γ-globin gene expression during adult definitive erythropoiesis as the most promising therapy to treat these hemoglobinopathies. Artificial transcription factors (ATFs are synthetic proteins designed to bind at a specific DNA sequence and modulate gene expression. The artificial zinc finger gg1-VP64 was designed to target the −117 region of the Aγ-globin gene proximal promoter and activate expression of this gene. Previous studies demonstrated that HbF levels were increased in murine chemical inducer of dimerization (CID-dependent bone marrow cells carrying a human β-globin locus yeast artificial chromosome (β-YAC transgene and in CD34+ erythroid progenitor cells from normal donors and β-thalassemia patients. Herein, we report that gg1-VP64 increased γ-globin gene expression in vivo, in peripheral blood samples from gg1-VP64 β-YAC double-transgenic (bigenic mice. Our results demonstrate that ATFs function in an animal model to increase gene expression. Thus, this class of reagent may be an effective gene therapy for treatment of some inherited diseases.

  11. Reactions of arsine with hemoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Hatlelid, K.M.; Brailsford, C.; Carter, D.E. [Univ. of Arizona, Tucson, AZ (United States)

    1996-02-09

    The mechanism of arsine (AsH{sub 3}) induced hemolysis was studied in vitro using isolated red blood cells (RBCs) from the rat or dog. AsH{sub 3}-induced hemolysis of dog red blood cells was completely blocked by carbon monoxide (CO) preincubation and was reduced by pure oxygen (O{sub 2}) compared to incubations in air. Since CO and O{sub 2} bind to heme and also reduced hemolysis, these results suggested a reaction between AsH{sub 3} and hemoglobin in the hemeligand binding pocket or with the heme iron. Further, sodium nitrite induction of methemoglobin (metHb) to 85% and 34% of total Hb in otherwise intact RBCs resulted in 56% and 16% decreases in hemolysis, respectively, after incubation for 4 h. This provided additional evidence for the involvement of hemoglobin in the AsH{sub 3}-induced hemolysis mechanism. Reactions between AsH{sub 3} and hemoglobin were studied in solutions of purified dog hemoglobin. Spectrophotometric studies of the reaction of AsH{sub 3} with various purified hemoglobin species revealed that AsH{sub 3} reacted with HbO{sub 2} to produce metHb and, eventually, degraded Hb characterized by gross precipitation of the protein. AsH{sub 3} did not alter the spectrum of deoxyHb and did not cause degradation of metHb in oxygen, but bound to and reduced metHb in the absence of oxygen. These data indicate that a reaction of AsH{sub 3} with oxygenated hemoglobin, HbO{sub 2}, may lead to hemolysis, but there are reactions between AsH{sub 3} and metHb that may not be directly involved in the hemolytic process. 17 refs., 6 figs.

  12. Reactivity Boundaries to Separate the Fate of a Chemical Reaction Associated with an Index-two saddle

    CERN Document Server

    Nagahata, Yutaka; Li, Chun-Biu; Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2013-01-01

    Reactivity boundaries that divide the destination and the origin of trajectories are of crucial importance to reveal the mechanism of reactions. We investigate whether such reactivity boundaries can be extracted for higher index saddles in terms of a nonlinear canonical transformation successful for index-one saddles by using a model system with an index-two saddle. It is found that the true reactivity boundaries do not coincide with those extracted by the transformation taking into account a nonlinearity in the region of the saddle even for small perturbations, and the discrepancy is more pronounced for the less repulsive direction of the index-two saddle system. The present result indicates an importance of the global properties of the phase space to identify the reactivity boundaries, relevant to the question of what reactant and product are in phase space, for saddles with index more than one.

  13. Reactivity boundaries to separate the fate of a chemical reaction associated with an index-two saddle.

    Science.gov (United States)

    Nagahata, Yutaka; Teramoto, Hiroshi; Li, Chun-Biu; Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2013-06-01

    Reactivity boundaries that divide the destination and the origin of trajectories are of crucial importance to reveal the mechanism of reactions. We investigate whether such reactivity boundaries can be extracted for higher index saddles in terms of a nonlinear canonical transformation successful for index-one saddles by using a model system with an index-two saddle. It is found that the true reactivity boundaries do not coincide with those extracted by the transformation taking into account a nonlinearity in the region of the saddle even for small perturbations, and the discrepancy is more pronounced for the less repulsive direction of the index-two saddle system. The present result indicates an importance of the global properties of the phase space to identify the reactivity boundaries, relevant to the question of what reactant and product are in phase space, for saddles with index more than one.

  14. [A new case of hemoglobin J Capetown alpha 92 (FG 4) Arg replaced by gln].

    Science.gov (United States)

    Gacon, G; Amegnizin, K E; Belkhodja, O; Denis, P; Krishnamoorthy, R; Labie, D; Lefrancois, R; Michel, Y; Pasquis, P; Wajcman, H

    1977-01-01

    Hemoglobin J Capetown was found incidentally in a patient of french origin suffering from urticaria with delayed pressure oedema. Using a preparative finger-print technique, the structural determination was easy. A functional study of the purified component confirmed the high oxygen affinity of hemoglobin J Capetown and demonstrated a low reactivity for organic phosphates. These results may explain the perturbations observed in the whole blood.

  15. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH2-CH=CH-CH2-) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than 1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  16. 不同年龄重症冠心病患者高敏C反应蛋白、应激性血糖及糖化血红蛋白的比较%Comparison in changes of high-sensitivity C-reactive protein, stress blood glucose and glycated hemoglobin in patients with severe coronary heart disease in different ages

    Institute of Scientific and Technical Information of China (English)

    鲁琳; 任平香; 于大勇; 卢新; 赵建玲

    2014-01-01

    目的:探讨不同年龄重症冠状动脉粥样硬化性心脏病(冠心病)患者高敏C反应蛋白(hs-CRP)、应激性血糖和糖化血红蛋白的变化。方法入选2012年1月到2013年1月在唐山市工人医院ICU及CCU住院的重症冠心病患者514例,其中男性284例,女性230例,年龄24~91岁,平均年龄(67.65±12.68)岁。根据患者年龄分为4组:A组(<60岁,n=134);B组(60~69岁,n=132);C组(70~80岁,n=154);D组(≥80岁,n=94)。检测各组患者血清hs-CRP、全血血糖和全血糖化血红蛋白水平。结果与A组[(7.10±22.67)mg/L]比较,B组[(15.56±35.23)mg/L]、C组[(19.57±37.97)mg/L]、D组[(29.29±44.43)mg/L]hs-CRP呈逐渐增高趋势,差异具有统计学意义(P<0.05)。与A组[(8.67±4.13)mmol/L]比较,B组[(9.26±5.93)mmol/L]、C组[(10.84±6.05)mmol/L]血糖呈逐渐增高趋势,差异具有统计学意义(P<0.05)。C组与D组血糖比较无统计学差异(P>0.05)。各组间糖化血红蛋白比较均无统计学差异(P>0.05)。结论不同年龄重症冠心病患者入院时hs-CRP和应激性血糖随着年龄的增长而增加,而糖化血红蛋白无明显变化。%Objective To investigate the changes of high-sensitivity C-reactive protein (hs-CRP), stress blood glucose and glycated hemoglobin in patients with severe coronary heart disease (CHD) in different ages. Methods The patients (n=514) were chosen (male 284 and female 230) aged from 24 to 91 (average age=67.65 ±12.68) from Jan. 2012 to Jan. 2013. All patients were divided, according to their age, into group A (age0.05), and comparison in glycated hemoglobin among all groups had no statistical difference (P>0.05). Conclusion The levels of hs-CRP and stress blood glucose increase as aging and level of glycated hemoglobin has no significant change in patients with severe CHD in different ages.

  17. From solution to in-cell study of the chemical reactivity of acid sensitive functional groups: a rational approach towards improved cleavable linkers for biospecific endosomal release.

    Science.gov (United States)

    Jacques, Sylvain A; Leriche, Geoffray; Mosser, Michel; Nothisen, Marc; Muller, Christian D; Remy, Jean-Serge; Wagner, Alain

    2016-06-07

    pH-Sensitive linkers designed to undergo selective hydrolysis at acidic pH compared to physiological pH can be used for the selective release of therapeutics at their site of action. In this paper, the hydrolytic cleavage of a wide variety of molecular structures that have been reported for their use in pH-sensitive delivery systems was examined. A wide variety of hydrolytic stability profiles were found among the panel of tested chemical functionalities. Even within a structural family, a slight modification of the substitution pattern has an unsuspected outcome on the hydrolysis stability. This work led us to establish a first classification of these groups based on their reactivities at pH 5.5 and their relative hydrolysis at pH 5.5 vs. pH 7.4. From this classification, four representative chemical functions were selected and studied in-vitro. The results revealed that only the most reactive functions underwent significant lysosomal cleavage, according to flow cytometry measurements. These last results question the acid-based mechanism of action of known drug release systems and advocate for the importance of an in-depth structure-reactivity study, using a tailored methodology, for the rational design and development of bio-responsive linkers.

  18. The coordination chemistry of boron porphyrin complexes B2OX2 (TYPP) (X = OH, F; Y = Cl, CH3) and their chemical reactivities

    Indian Academy of Sciences (India)

    G I Cárdenas-Jirón; F Espinoza-Leyton; T L Sordo

    2005-09-01

    The structure and coordination chemistry of boron porphyrin complexes B2OX2 (TYPP) (X = OH, F; Y = Cl, CH3) in connection with its chemical reactivity are analyzed at ab initio density functional theory B3LYP/6-31G∗ and restricted Hartree-Fock RHF/6-31G∗ levels of theory. Global reactivity and local selectivity descriptors are used as adequate tools to analyze the isomerism effect ( or isomer) and the substitution effect (X: in axial ligand; or Y: in porphyrin ligand). In all the cases, we find that the conformation is the most stable one, in agreement with X-ray results, and that a principle of maximum hardness in the isomerism analysis is fullfilled. In the substitution analysis, we find that the three global reactivity indexes (, , ) and the two local reactivity indexes (, electrostatic potential) used in this paper predict the same trend when an electron-withdrawing substituent is replaced by an electron donor. Finally, we show that substitution in the porphyrin ligand is slightly more significant than that in the axial ligand.

  19. Role of alpha-hemoglobin-stabilizing protein in normal erythropoiesis and beta-thalassemia.

    Science.gov (United States)

    Weiss, Mitchell J; Zhou, Suiping; Feng, Liang; Gell, David A; Mackay, Joel P; Shi, Yigong; Gow, Andrew J

    2005-01-01

    Hemoglobin (Hb) synthesis is coordinated by homeostatic mechanisms to limit the accumulation of free alpha or beta subunits, which are cytotoxic. Alpha hemoglobin-stabilizing protein (AHSP) is an abundant erythroid protein that specifically binds free alphaHb, stabilizes its structure, and limits its ability to participate in chemical reactions that generate reactive oxygen species. Gene ablation studies in mice demonstrate that AHSP is required for normal erythropoiesis. AHSP-null erythrocytes are short-lived, contain Hb precipitates, and exhibit signs of oxidative damage. Loss of AHSP exacerbates beta-thalassemia in mice, indicating that altered AHSP expression or function could modify thalassemia phenotypes in humans, a topic that is beginning to be explored in clinical studies. We used biochemical, spectroscopic, and crystallographic methods to examine how AHSP stabilizes alphaHb. AHSP binds the G and H helices of alphaHb on a surface that largely overlaps with the alpha1-beta1 interface of HbA. This result explains previous findings that betaHb can competitively displace AHSP from alphaHb to form HbA tetramer. Remarkably, binding of AHSP to oxygenated alphaHb induces dramatic conformational changes and converts the heme-bound iron to an oxidized hemichrome state in which all six coordinate positions are occupied. This structure limits the reactivity of heme iron, providing a mechanism by which AHSP stabilizes alphaHb. These findings suggest a biochemical pathway through which AHSP might participate in normal Hb synthesis and modulate the severity of thalassemias. Moreover, understanding how AHSP stabilizes alphaHb provides a theoretical basis for new strategies to inhibit the damaging effects of free alphaHb that accumulates in beta-thalassemia.

  20. Reactive scalar field near the turbulent/non-turbulent interface in a planar jet with a second-order chemical reaction

    Science.gov (United States)

    Watanabe, T.; Sakai, Y.; Nagata, K.; Ito, Y.; Hayase, T.

    2014-10-01

    The reactive scalar field near the turbulent/non-turbulent (T/NT) interface is analyzed using a direct numerical simulation (DNS) of a planar jet with an isothermal second-order chemical reaction A + B → P. Reactants A and B are supplied from the jet and ambient flows, respectively. The DNS of the reactive jet is performed for Damköhler numbers Da = 0.1, 1, and 10. A visualization of the T/NT interface shows that most of the product P is contained in the turbulent region. The conditional mean concentrations of the reactive species change sharply near the T/NT interface. The width of the jump in the conditional mean concentration is almost independent of the chemical species and the Damköhler number. For the slow reaction (Da = 0.1), the conditional average of the chemical production rate gradually increases from the non-turbulent region toward the turbulent region. In contrast, the conditional average of the production rate for Da = 1 and 10 has a large peak value slightly inside the T/NT interface. The chemical reaction near the T/NT interface strongly depends on the interface orientation. The reactant A is deficient near the T/NT interface. The production rate is large near the interface toward which the deficient reactant A is frequently transported by the velocity fields. The transport due to the velocity relative to the interface movement strongly depends on the relationship between the interface geometry and the mean flow field. The dependence of the chemical reaction on the interface orientation becomes strong as Da increases. When the interface propagates toward the non-turbulent region, the reactant A and product P are contained in the turbulent region although the molecular diffusion and reaction contribute to the increase in the concentrations of A (non-reactive case) and P in the non-turbulent region. In contrast, the interface propagation toward the turbulent region leaves the fluids containing A and P in the non-turbulent region.

  1. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111).

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-21

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  2. Charting the Chemical Reactivity Space of 2,3-Substituted Furo[2,3-b]pyridines Synthesized via the Heterocyclization of Pyridine-N-oxide Derivatives.

    Science.gov (United States)

    Fumagalli, Fernando; da Silva Emery, Flavio

    2016-11-04

    A concise strategy for the synthesis of 2,3-substituted furo[2,3-b]pyridines is described. Mild, metal-free conditions were successfully applied to produce a range of 2-(alkyl or aryl)-3-ethylcarboxylate-furo[2,3-b]pyridines in yields of 50-91%. Then, the chemical reactivity of this heterocyclic framework was explored to develop straightforward methods for its functionalization. The pyridine moiety reactivity was successfully explored by C-H amination and borylation reactions, although C-H fluorination and radical C-H arylation processes were not as efficient. In addition, while the furopyridine core proved stable under basic conditions, the ring-opening reaction of the furan moiety with hydrazine generated a valuable new pyridine-dihydropyrazolone scaffold.

  3. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  4. Blood Test: Hemoglobin A1C

    Science.gov (United States)

    ... 2014 previous 1 • 2 • 3 For Teens For Kids For Parents MORE ON THIS TOPIC Diabetes Control: Why It's Important Monitoring Blood Sugar Helping Kids Deal With Injections and Blood Tests Blood Test: Hemoglobin ... Center Word! Glycosylated Hemoglobin Test (Hemoglobin A1c) Medical ...

  5. Distillation and isolation of commodity chemicals from Bio-oil made by tail-gas reactive prolysis

    Science.gov (United States)

    Owing to instabilities, very little has been accomplished with regards to simple cost-effective separations of fast-pyrolysis bio-oil. However, recent developments in the use of tail-gas reactive pyrolysis (TGRP) (Mullen and Boateng 2013) provide higher quality bio-oils that are thermally stable. We...

  6. Assessment of conformational, spectral, antimicrobial activity, chemical reactivity and NLO application of Pyrrole-2,5-dicarboxaldehyde bis(oxaloyldihydrazone)

    Science.gov (United States)

    Rawat, Poonam; Singh, R. N.

    2015-04-01

    An orange colored pyrrole dihydrazone: Pyrrole-2,5-dicarboxaldehyde bis(oxaloyldihydrazone) (PDBO) has been synthesized by reaction of oxalic acid dihydrazide with 2,5 diformyl-1H-pyrrole and has been characterized by spectroscopic analysis (1H, 13C NMR, UV-visible, FT-IR and DART Mass). The properties of the compound has been evaluated using B3LYP functional and 6-31G(d,p)/6-311+G(d,p) basis set. The symmetric (3319, 3320 cm-1) and asymmetric (3389, 3382 cm-1) stretching wave number confirm free NH2 groups in PDBO. NBO analysis shows, inter/intra molecular interactions within the molecule. Topological parameters have been analyzed by QTAIM theory and provide the existence of intramolecular hydrogen bonding (N-H⋯O). The local reactivity descriptors analyses determine the reactive sites within molecule. The calculated first hyperpolarizability value (β0 = 23.83 × 10-30 esu) of pyrrole dihydrazone shows its suitability for non-linear optical (NLO) response. The preliminary bioassay suggested that the PDBO exhibits relatively good antibacterial and fungicidal activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Streptococcus pyogenes, Candida albicans, Aspergillus niger. The local reactivity descriptors - Fukui functions (fk+, fk-), local softnesses (sk+, sk-) and electrophilicity indices (ωk+, ωk-) analyses have been used to determine the reactive sites within molecule.

  7. Assessment of conformational, spectral, antimicrobial activity, chemical reactivity and NLO application of Pyrrole-2,5-dicarboxaldehyde bis(oxaloyldihydrazone).

    Science.gov (United States)

    Rawat, Poonam; Singh, R N

    2015-04-05

    An orange colored pyrrole dihydrazone: Pyrrole-2,5-dicarboxaldehyde bis(oxaloyldihydrazone) (PDBO) has been synthesized by reaction of oxalic acid dihydrazide with 2,5 diformyl-1H-pyrrole and has been characterized by spectroscopic analysis (1H, 13C NMR, UV-visible, FT-IR and DART Mass). The properties of the compound has been evaluated using B3LYP functional and 6-31G(d,p)/6-311+G(d,p) basis set. The symmetric (3319, 3320 cm(-1)) and asymmetric (3389, 3382 cm(-1)) stretching wave number confirm free NH2 groups in PDBO. NBO analysis shows, inter/intra molecular interactions within the molecule. Topological parameters have been analyzed by QTAIM theory and provide the existence of intramolecular hydrogen bonding (N-H⋯O). The local reactivity descriptors analyses determine the reactive sites within molecule. The calculated first hyperpolarizability value (β0=23.83×10(-30) esu) of pyrrole dihydrazone shows its suitability for non-linear optical (NLO) response. The preliminary bioassay suggested that the PDBO exhibits relatively good antibacterial and fungicidal activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Streptococcus pyogenes, Candida albicans, Aspergillus niger. The local reactivity descriptors--Fukui functions (fk+, fk-), local softnesses (sk+, sk-) and electrophilicity indices (ωk+, ωk-) analyses have been used to determine the reactive sites within molecule. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. 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.

  9. Reaction of melatonin with hemoglobin-derived oxoferryl radicals and inhibition of the hydroperoxide-induced hemoglobin denaturation in red blood cells.

    Science.gov (United States)

    Tesoriere, L; Allegra, M; D'Arpa, D; Butera, D; Livrea, M A

    2001-09-01

    Melatonin has been shown to act as a radical scavenger in various chemical and biological model systems in vitro. Kinetic evidence is now provided showing that melatonin inhibits the irreversible degradation of hemoglobin (Hb), when incubated with red blood cells exposed to the oxidant activity of cumene hydroperoxide (cumOOH). A decrease of heme loss and accumulation of soluble methemoglobin (met-Hb) are explained in terms of the interaction of the indoleamine with perferryl Hb (Hb[Fe(IV)=O]), a highly reactive Hb-derived radical species responsible for the irreversible Hb degradation. A kinetic study, in pure chemical solution, showed that melatonin can effectively reduce the oxoferryl heme group of perferryl-Hb, thus forming met-Hb. The reducing activity of melatonin is of the same order as that of Trolox, the water-soluble vitamin E analog. This novel radical-scavenging activity of melatonin may contribute to the previously observed protective effects of melatonin in ischemia-reperfusion injury.

  10. Communication: Ro-vibrational control of chemical reactivity in H+CH₄→ H₂+CH₃: full-dimensional quantum dynamics calculations and a sudden model.

    Science.gov (United States)

    Welsch, Ralph; Manthe, Uwe

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  11. Formation of distinctive structures of GaN by inductively-coupled-plasma and reactive ion etching under optimized chemical etching conditions

    Directory of Open Access Journals (Sweden)

    N. Okada

    2017-06-01

    Full Text Available We focused on inductively coupled plasma and reactive ion etching (ICP–RIE for etching GaN and tried to fabricate distinctive GaN structures under optimized chemical etching conditions. To determine the optimum chemical etching conditions, the flow rates of Ar and Cl2, ICP power, and chamber pressure were varied in the etching of c-plane GaN layers with stripe patterns. It was determined that the combination of Ar and Cl2 flow rates of 100 sccm, chamber pressure of 7 Pa, and ICP power of 800 W resulted in the most enhanced reaction, yielding distinctive GaN structures such as pillars with inverted mesa structures for c-plane GaN and a semipolar GaN layer with asymmetric inclined sidewalls. The selectivity and etching rate were also investigated.

  12. Formation of distinctive structures of GaN by inductively-coupled-plasma and reactive ion etching under optimized chemical etching conditions

    Science.gov (United States)

    Okada, N.; Nojima, K.; Ishibashi, N.; Nagatoshi, K.; Itagaki, N.; Inomoto, R.; Motoyama, S.; Kobayashi, T.; Tadatomo, K.

    2017-06-01

    We focused on inductively coupled plasma and reactive ion etching (ICP-RIE) for etching GaN and tried to fabricate distinctive GaN structures under optimized chemical etching conditions. To determine the optimum chemical etching conditions, the flow rates of Ar and Cl2, ICP power, and chamber pressure were varied in the etching of c-plane GaN layers with stripe patterns. It was determined that the combination of Ar and Cl2 flow rates of 100 sccm, chamber pressure of 7 Pa, and ICP power of 800 W resulted in the most enhanced reaction, yielding distinctive GaN structures such as pillars with inverted mesa structures for c-plane GaN and a semipolar GaN layer with asymmetric inclined sidewalls. The selectivity and etching rate were also investigated.

  13. Reactive transport modeling of chemical and isotope data to identify degradation processes of chlorinated ethenes in a diffusion-dominated media

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Damgaard, Ida; Jeannottat, Simon

    . Degradation and transport processes of chlorinated ethenes are not well understood in such geological settings, therefore risk assessment and remediation at these sites are particularly challenging. In this work, a combined approach of chemical and isotope analysis on core samples, and reactive transport...... modeling has been used to identify the degradation processes occurring at the core scale. The field data was from a site located at Vadsby, Denmark, where chlorinated solvents were spilled during the 1960-70’s, resulting in contamination of the clay till and the underlying sandy layer (15 meters below...... is an important finding, that is further supported by microbial and chemical data. Improved understanding of degradation processes in clay tills is useful for improving the reliability of risk assessment and the design of remediation schemes for chlorinated solvents....

  14. Acid Denaturation Inducing Self-Assembly of Curcumin-Loaded Hemoglobin Nanoparticles

    Directory of Open Access Journals (Sweden)

    Kaikai Wang

    2015-12-01

    Full Text Available Hemoglobin is a promising drug carrier but lacks extensive investigation. The chemical conjugation of hemoglobin and drugs is costly and complex, so we have developed curcumin-loaded hemoglobin nanoparticles (CCM-Hb-NPs via self-assembly for the first time. Using the acid-denaturing method, we avoid introducing denaturants and organic solvents. The nanoparticles are stable with uniform size. We have conducted a series of experiments to examine the interaction of hemoglobin and CCM, including hydrophobic characterization, SDS-PAGE. These experiments substantiate that this self-assembly process is mainly driven by hydrophobic forces. Our nanoparticles achieve much higher cell uptake efficiency and cytotoxicity than free CCM solution in vitro. The uptake inhibition experiments also demonstrate that our nanoparticles were incorporated via the classic clathrin-mediated endocytosis pathway. These results indicate that hemoglobin nanoparticles formed by self-assembly are a promising drug delivery system for cancer therapy.

  15. Cross-reactivity virtual profiling of the human kinome by X-react(KIN): a chemical systems biology approach.

    Science.gov (United States)

    Brylinski, Michal; Skolnick, Jeffrey

    2010-12-06

    Many drug candidates fail in clinical development due to their insufficient selectivity that may cause undesired side effects. Therefore, modern drug discovery is routinely supported by computational techniques, which can identify alternate molecular targets with a significant potential for cross-reactivity. In particular, the development of highly selective kinase inhibitors is complicated by the strong conservation of the ATP-binding site across the kinase family. In this paper, we describe X-React(KIN), a new machine learning approach that extends the modeling and virtual screening of individual protein kinases to a system level in order to construct a cross-reactivity virtual profile for the human kinome. To maximize the coverage of the kinome, X-React(KIN) relies solely on the predicted target structures and employs state-of-the-art modeling techniques. Benchmark tests carried out against available selectivity data from high-throughput kinase profiling experiments demonstrate that, for almost 70% of the inhibitors, their alternate molecular targets can be effectively identified in the human kinome with a high (>0.5) sensitivity at the expense of a relatively low false positive rate (cross-reactivity profiles for the human kinome are freely available to the academic community at http://cssb.biology.gatech.edu/kinomelhm/ .

  16. Synthesis, chemical reactivity as Michael acceptors, and biological potency of monocyclic cyanoenones, novel and highly potent anti-inflammatory and cytoprotective agents.

    Science.gov (United States)

    Zheng, Suqing; Santosh Laxmi, Y R; David, Emilie; Dinkova-Kostova, Albena T; Shiavoni, Katherine H; Ren, Yanqing; Zheng, Ying; Trevino, Isaac; Bumeister, Ronald; Ojima, Iwao; Wigley, W Christian; Bliska, James B; Mierke, Dale F; Honda, Tadashi

    2012-05-24

    Novel monocyclic cyanoenones examined to date display unique features regarding chemical reactivity as Michael acceptors and biological potency. Remarkably, in some biological assays, the simple structure is more potent than pentacyclic triterpenoids (e.g., CDDO and bardoxolone methyl) and tricycles (e.g., TBE-31). Among monocyclic cyanoenones, 1 is a highly reactive Michael acceptor with thiol nucleophiles. Furthermore, an important feature of 1 is that its Michael addition is reversible. For the inhibition of NO production, 1 shows the highest potency. Notably, its potency is about three times higher than CDDO, whose methyl ester (bardoxolone methyl) is presently in phase III clinical trials. For the induction of NQO1, 1 also demonstrated the highest potency. These results suggest that the reactivity of these Michael acceptors is closely related to their biological potency. Interestingly, in LPS-stimulated macrophages, 1 causes apoptosis and inhibits secretion of TNF-α and IL-1β with potencies that are higher than those of bardoxolone methyl and TBE-31.

  17. Chemical Reactivity and Respiratory Toxicity of the α-Diketone Flavoring Agents: 2,3-Butanedione, 2,3-Pentanedione, and 2,3-Hexanedione.

    Science.gov (United States)

    Morgan, Daniel L; Jokinen, Micheal P; Johnson, Crystal L; Price, Herman C; Gwinn, William M; Bousquet, Ronald W; Flake, Gordon P

    2016-07-01

    Occupational exposure to 2,3-butanedione (BD) vapors has been associated with severe respiratory disease leading to the use of potentially toxic substitutes. We compared the reactivity and respiratory toxicity of BD with that of two structurally related substitutes, 2,3-pentanedione (PD) and 2,3-hexanedione (HD). Chemical reactivity of the diketones with an arginine substrate decreased with increasing chain length (BD > PD > HD). Animals were evaluated the morning after a 2-week exposure to 0, 100, 150, or 200 ppm BD, PD, or HD (postexposure) or 2 weeks later (recovery). Bronchial fibrosis was observed in 5/5 BD and 5/5 PD rats at 200 ppm and in 4/6 BD and 6/6 PD rats at 150 ppm in the postexposure groups. Following recovery, bronchial fibrosis was observed in all surviving rats exposed to 200 ppm BD (5/5) or PD (3/3) and in 2/10 BD and 7/9 PD rats exposed to 150 ppm. Bronchial fibrosis was observed only in 2/12 HD-exposed rats in the 200 ppm postexposure group. Patchy interstitial fibrosis affected lungs of recovery groups exposed to 200 ppm PD (3/3) or BD (1/5) and to 150 ppm PD (4/9) or BD (7/10) and correlated with pulmonary function deficits. BD and PD were more reactive and produced more bronchial fibrosis than HD. © The Author(s) 2016.

  18. Oral Administration of the Japanese Traditional Medicine Keishibukuryogan-ka-yokuinin Decreases Reactive Oxygen Metabolites in Rat Plasma: Identification of Chemical Constituents Contributing to Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Yosuke Matsubara

    2017-02-01

    Full Text Available Insufficient detoxification and/or overproduction of reactive oxygen species (ROS induce cellular and tissue damage, and generated reactive oxygen metabolites become exacerbating factors of dermatitis. Keishibukuryogan-ka-yokuinin (KBGY is a traditional Japanese medicine prescribed to treat dermatitis such as acne vulgaris. Our aim was to verify the antioxidant properties of KBGY, and identify its active constituents by blood pharmacokinetic techniques. Chemical constituents were quantified in extracts of KBGY, crude components, and the plasma of rats treated with a single oral administration of KBGY. Twenty-three KBGY compounds were detected in plasma, including gallic acid, prunasin, paeoniflorin, and azelaic acid, which have been reported to be effective for inflammation. KBGY decreased level of the diacron-reactive oxygen metabolites (d-ROMs in plasma. ROS-scavenging and lipid hydroperoxide (LPO generation assays revealed that gallic acid, 3-O-methylgallic acid, (+-catechin, and lariciresinol possess strong antioxidant activities. Gallic acid was active at a similar concentration to the maximum plasma concentration, therefore, our findings indicate that gallic acid is an important active constituent contributing to the antioxidant effects of KBGY. KBGY and its active constituents may improve redox imbalances induced by oxidative stress as an optional treatment for skin diseases.

  19. Dynamic behavior of chemical reactivity indices in density functional theory: A Bohn-Oppenheimer quantum molecular dynamics study

    Indian Academy of Sciences (India)

    Shubin Liu

    2005-09-01

    Dynamic behaviors of chemical concepts in density functional theory such as frontier orbitals (HOMO/LUMO), chemical potential, hardness, and electrophilicity index have been investigated in this work in the context of Bohn-Oppenheimer quantum molecular dynamics in association with molecular conformation changes. Exemplary molecular systems like CH$^{+}_{5}$ , Cl- (H2O)30 and Ca2+ (H2O)15 are studied at 300 K in the gas phase, demonstrating that HOMO is more dynamic than LUMO, chemical potential and hardness often fluctuate concurrently. It is argued that DFT concepts and indices may serve as a good framework to understand molecular conformation changes as well as other dynamic phenomena.

  20. In situ chemical behaviour of methylisothiazolinone (MI) and methylchloroisothiazolinone (MCI) in reconstructed human epidermis: a new approach to the cross-reactivity issue.

    Science.gov (United States)

    Debeuckelaere, Camille; Moussallieh, François-Marie; Elbayed, Karim; Namer, Izzie-Jacques; Berl, Valérie; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre

    2016-03-01

    Methylisothiazolinone (MI) [with methylchloroisothiazolinone (MCI) in a ratio of 1:3, a well-recognized allergenic preservative] was released as an individual preservative in the 2000s for industrial products and in 2005 for cosmetics. The high level of exposure to MI since then has provoked an epidemic of contact allergy to MI, and an increase in MI/MCI allergy. There are questions concerning the MI/MCI cross-reaction pattern. To bring a new perspective on the MI/MCI cross-reactivity issue by studying their in situ chemical behaviour in 3D reconstructed human epidermis (RHE). MI and MCI were synthesized with (13) C substitution at positions C-4/C-5 and C-5, respectively. Their in situ chemical behaviours in an RHE model were followed by use of the high-resolution magic angle spinning nuclear magnetic resonance technique. MI was found to react exclusively with cysteine thiol residues, whereas MCI reacted with histidines and lysines. The reaction mechanisms were found to be different for MI and MCI, and the adducts formed had different molecular structures. In RHE, different MI/MCI reactions towards different nucleophilic amino acids were observed, making it difficult to explain cross-reactivity between MI and MCI. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  1. Reactivity of chemical sensitizers toward amino acids in cellulo plays a role in the activation of the Nrf2-ARE pathway in human monocyte dendritic cells and the THP-1 cell line.

    Science.gov (United States)

    Migdal, Camille; Botton, Jérémie; El Ali, Zeina; Azoury, Marie-Eliane; Guldemann, Joan; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre; Kerdine-Römer, Saadia; Pallardy, Marc

    2013-06-01

    Allergic contact dermatitis resulting from skin sensitization is an inflammatory skin disease linked to the use of chemicals termed haptens. Chemical reactivity is necessary for a chemical to be a sensitizer, allowing both covalent binding to proteins and maturation of dendritic cells (DCs) by mimicking "danger signals." The aim of this study was to evaluate how the reactivity of chemical sensitizers toward amino acids translates into a biological response using the activation of the nuclear factor-erythroid 2-related factor 2 (Nrf2) pathway, which was assessed by the induction of three Nrf2 target genes (ho-1, nqo1, and il-8) and Nrf2 protein accumulation. Nrf2 activation is known to play a role in numerous detoxification mechanisms that could regulate danger signal outcomes in myeloid cells. Monocyte-derived DCs and THP-1 cells were exposed to (a) haptens with cysteine, lysine, or cysteine/lysine reactivity, (b) pro-/prehaptens, and (c) nonsensitizing molecules with reducing or oxidative properties (17 molecules in total). Chemicals were classified as "Nrf2 pathway activators" when at least two Nrf2 target genes associated with Nrf2 protein expression were induced. Results showed that most chemical sensitizers having cysteine and cysteine/lysine affinities were inducers of the Nrf2 pathway in both cell models, whereas lysine-reactive chemicals were less efficient. In THP-1 cells, the Nrf2 pathway was also activated by pro-/prehaptens. Regression analysis revealed that ho-1 and nqo1 expressions were found to be associated with chemical sensitizer reactivity to cysteine, providing evidence of the importance of chemical reactivity, as a part of danger signals, in DC biology.

  2. Hemoglobin

    Science.gov (United States)

    ... Failure of the right side of the heart ( cor pulmonale ) Severe chronic obstructive pulmonary disease (COPD) Scarring or ... chronic disease Aplastic anemia Bleeding CBC blood test Cor pulmonale Diabetes Drug-induced immune hemolytic anemia Erythropoietin test ...

  3. Hemoglobin

    Science.gov (United States)

    Advertisement Proceeds from website advertising help sustain Lab Tests Online. AACC is a not-for-profit organization and does not endorse non-AACC products and services. Advertising & Sponsorship: Policy | Opportunities ...

  4. Allylation of intraerythrocytic hemoglobin by raw garlic extracts.

    Science.gov (United States)

    Bonaventura, Joseph; Rodriguez, Eva N; Beyley, Veronica; Vega, Irving E

    2010-08-01

    Recent studies have shown that deoxygenated human red blood cells (RBCs) converted garlic-derived polysulfides into hydrogen sulfide, which in turn produced vasorelaxation in aortic ring preparations. The vasoactivity was proposed to occur via glucose- and thiol-dependent acellular reactions. In the present study, we investigated the interaction of garlic extracts with human deoxygenated RBCs and its effect on intracellular hemoglobin molecules. The results showed that garlic extract covalently modified intraerythrocytic deoxygenated hemoglobin. The modification identified consisted of an addition of 71 atomic mass units, suggesting allylation of the cysteine residues. Consistently, purified human deoxyhemoglobin reacted with chemically pure diallyl disulfide, showing the same modification as garlic extracts. Tandem mass spectrometry analysis demonstrated that garlic extract and diallyl disulfide modified hemoglobin's beta-chain at cysteine-93 (beta-93C) or cysteine-112 (beta-112C). These results indicate that garlic-derived organic disulfides as well as pure diallyl disulfide must permeate the RBC membrane and modified deoxyhemoglobin at beta-93C or beta-112C. Although the physiological role of the reported garlic extract-induced allyl modification on human hemoglobin warrants further study, the results indicate that constituents of natural products, such as those from garlic extract, modify intracellular proteins.

  5. Hemoglobin variant (hemoglobin Aalborg) mimicking interstitial pulmonary disease.

    Science.gov (United States)

    Panou, Vasiliki; Jensen, Peter-Diedrich Mathias; Pedersen, Jan Freddy; Thomsen, Lars Pilegaard; Weinreich, Ulla Møller

    2014-01-01

    Hemoglobin Aalborg is a moderately unstable hemoglobin variant with no affiliation to serious hematological abnormality or major clinical symptoms under normal circumstances. Our index person was a healthy woman of 58, not previously diagnosed with hemoglobinopathy Aalborg, who developed acute respiratory failure after a routine cholecystectomy. Initially she was suspected of idiopathic interstitial lung disease, yet a series of tests uncovered various abnormal physiological parameters and set the diagnosis of hemoglobinopathy Aalborg. This led us to examine a group of the index person's relatives known with hemoglobinopathy Aalborg in order to study whether the same physiological abnormalities would be reencountered. They were all subjected to spirometry and body plethysmography, six-minute walking test, pulse oximetry, and arterial blood gas samples before and after the walking test. The entire study population presented the same physiological anomalies: reduction in diffusion capacity, and abnormalities in P(a)O2 and p50 values; the latter could not be presented by the arterial blood gas analyzer; furthermore there was concordance between pulse oximetry and arterial blood gas samples regarding saturation. These data suggest that, based upon the above mentioned anomalies in physiological parameters, the diagnosis of hemoglobinopathy Aalborg should be considered.

  6. Hemoglobin Variant (Hemoglobin Aalborg Mimicking Interstitial Pulmonary Disease

    Directory of Open Access Journals (Sweden)

    Vasiliki Panou

    2014-01-01

    Full Text Available Hemoglobin Aalborg is a moderately unstable hemoglobin variant with no affiliation to serious hematological abnormality or major clinical symptoms under normal circumstances. Our index person was a healthy woman of 58, not previously diagnosed with hemoglobinopathy Aalborg, who developed acute respiratory failure after a routine cholecystectomy. Initially she was suspected of idiopathic interstitial lung disease, yet a series of tests uncovered various abnormal physiological parameters and set the diagnosis of hemoglobinopathy Aalborg. This led us to examine a group of the index person’s relatives known with hemoglobinopathy Aalborg in order to study whether the same physiological abnormalities would be reencountered. They were all subjected to spirometry and body plethysmography, six-minute walking test, pulse oximetry, and arterial blood gas samples before and after the walking test. The entire study population presented the same physiological anomalies: reduction in diffusion capacity, and abnormalities in PaO2 and p50 values; the latter could not be presented by the arterial blood gas analyzer; furthermore there was concordance between pulse oximetry and arterial blood gas samples regarding saturation. These data suggest that, based upon the above mentioned anomalies in physiological parameters, the diagnosis of hemoglobinopathy Aalborg should be considered.

  7. Using laboratory flow experiments and reactive chemical transport modeling for designing waterflooding of the Agua Fria Reservoir, Poza Rica-Altamira Field, Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Birkle, P.; Pruess, K.; Xu, T.; Figueroa, R.A. Hernandez; Lopez, M. Diaz; Lopez, E. Contreras

    2008-10-01

    Waterflooding for enhanced oil recovery requires that injected waters must be chemically compatible with connate reservoir waters, in order to avoid mineral dissolution-and-precipitation cycles that could seriously degrade formation permeability and injectivity. Formation plugging is a concern especially in reservoirs with a large content of carbonates, such as calcite and dolomite, as such minerals typically react rapidly with an aqueous phase, and have strongly temperature-dependent solubility. Clay swelling can also pose problems. During a preliminary waterflooding pilot project, the Poza Rica-Altamira oil field, bordering the Gulf coast in the eastern part of Mexico, experienced injectivity loss after five months of reinjection of formation waters into well AF-847 in 1999. Acidizing with HCl restored injectivity. We report on laboratory experiments and reactive chemistry modeling studies that were undertaken in preparation for long-term waterflooding at Agua Frma. Using analogous core plugs obtained from the same reservoir interval, laboratory coreflood experiments were conducted to examine sensitivity of mineral dissolution and precipitation effects to water composition. Native reservoir water, chemically altered waters, and distilled water were used, and temporal changes in core permeability, mineral abundances and aqueous concentrations of solutes were monitored. The experiments were simulated with the multi-phase, nonisothermal reactive transport code TOUGHREACT, and reasonable to good agreement was obtained for changes in solute concentrations. Clay swelling caused an additional impact on permeability behavior during coreflood experiments, whereas the modeled permeability depends exclusively on chemical processes. TOUGHREACT was then used for reservoir-scale simulation of injecting ambient-temperature water (30 C, 86 F) into a reservoir with initial temperature of 80 C (176 F). Untreated native reservoir water was found to cause serious porosity and

  8. Hemoglobin Labeled by Radioactive Lysine

    Science.gov (United States)

    Bale, W. F.; Yuile, C. L.; DeLaVergne, L.; Miller, L. L.; Whipple, G. H.

    1949-12-08

    This paper reports on the utilization of tagged epsilon carbon of DL-lysine by a dog both anemic and hypoproteinemic due to repeated bleeding plus a diet low in protein. The experiment extended over period of 234 days, a time sufficient to indicate an erythrocyte life span of at least 115 days based upon the rate of replacement of labeled red cell proteins. The proteins of broken down red cells seem not to be used with any great preference for the synthesis of new hemoglobin.

  9. Hemoglobin variants: biochemical properties and clinical correlates.

    Science.gov (United States)

    Thom, Christopher S; Dickson, Claire F; Gell, David A; Weiss, Mitchell J

    2013-03-01

    Diseases affecting hemoglobin synthesis and function are extremely common worldwide. More than 1000 naturally occurring human hemoglobin variants with single amino acid substitutions throughout the molecule have been discovered, mainly through their clinical and/or laboratory manifestations. These variants alter hemoglobin structure and biochemical properties with physiological effects ranging from insignificant to severe. Studies of these mutations in patients and in the laboratory have produced a wealth of information on hemoglobin biochemistry and biology with significant implications for hematology practice. More generally, landmark studies of hemoglobin performed over the past 60 years have established important paradigms for the disciplines of structural biology, genetics, biochemistry, and medicine. Here we review the major classes of hemoglobin variants, emphasizing general concepts and illustrative examples.

  10. Patch testing with a new fragrance mix - reactivity to the individual constituents and chemical detection in relevant cosmetic products

    DEFF Research Database (Denmark)

    Frosch, Peter J; Rastogi, Suresh C; Pirker, Claudia

    2005-01-01

    A new fragrance mix (FM II), with 6 frequently used chemicals not present in the currently used fragrance mix (FM I), was evaluated in 6 dermatological centres in Europe, as previously reported. In this publication, test results with the individual constituents and after repeated open application...

  11. Responses of Solid Tumor Cells in DMEM to Reactive Oxygen Species Generated by Non-Thermal Plasma and Chemically Induced ROS Systems

    Science.gov (United States)

    Kaushik, Neha; Uddin, Nizam; Sim, Geon Bo; Hong, Young June; Baik, Ku Youn; Kim, Chung Hyeok; Lee, Su Jae; Kaushik, Nagendra Kumar; Choi, Eun Ha

    2015-02-01

    In this study, we assessed the role of different reactive oxygen species (ROS) generated by soft jet plasma and chemical-induced ROS systems with regard to cell death in T98G, A549, HEK293 and MRC5 cell lines. For a comparison with plasma, we generated superoxide anion (O2-), hydroxyl radical (HO.), and hydrogen peroxide (H2O2) with chemicals inside an in vitro cell culture. Our data revealed that plasma decreased the viability and intracellular ATP values of cells and increased the apoptotic population via a caspase activation mechanism. Plasma altered the mitochondrial membrane potential and eventually up-regulated the mRNA expression levels of BAX, BAK1 and H2AX gene but simultaneously down-regulated the levels of Bcl-2 in solid tumor cells. Moreover, a western blot analysis confirmed that plasma also altered phosphorylated ERK1/2/MAPK protein levels. At the same time, using ROS scavengers with plasma, we observed that scavengers of HO. (mannitol) and H2O2 (catalase and sodium pyruvate) attenuated the activity of plasma on cells to a large extent. In contrast, radicals generated by specific chemical systems enhanced cell death drastically in cancer as well as normal cell lines in a dose-dependent fashion but not specific with regard to the cell type as compared to plasma.

  12. Application of voltammetric techniques at microelectrodes to the study of the chemical stability of highly reactive species.

    Science.gov (United States)

    Laborda, Eduardo; Olmos, José-Manuel; Torralba, Encarnación; Molina, Angela

    2015-02-03

    The application of voltammetric techniques to the study of chemical speciation and stability is addressed both theoretically and experimentally in this work. In such systems, electrode reactions are coupled to homogeneous chemical equilibria (complexations, protonations, ion associations, ...) that can be studied in a simple, economical, and accurate way by means of electrochemical methods. These are of particular interest when some of the participating species are unstable given that the generation and characterization of the species are performed in situ and on a short time scale. With the above aim, simple explicit solutions are presented in this article for quantitative characterization with any voltammetric technique and with the most common electrode geometries. From the theoretical results obtained, it is pointed out that the use of square-wave voltammetry in combination with microelectrodes is very suitable. Finally, the theory is applied to the investigation of the ion association between the anthraquinone radical monoanion and the tetrabutylammonium cation in acetonitrile medium.

  13. Speciation and reactivity of lead and zinc in heavily and poorly contaminated soils: Stable isotope dilution, chemical extraction and model views.

    Science.gov (United States)

    Ren, Zong-Ling; Sivry, Yann; Tharaud, Mickaël; Cordier, Laure; Li, Yongtao; Dai, Jun; Benedetti, Marc F

    2017-06-01

    Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1-38% of total Pb and 3-45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies. Copyright © 2017. Published by Elsevier Ltd.

  14. In Chemico Evaluation of Tea Tree Essential Oils as Skin Sensitizers: Impact of the Chemical Composition on Aging and Generation of Reactive Species.

    Science.gov (United States)

    Avonto, Cristina; Chittiboyina, Amar G; Wang, Mei; Vasquez, Yelkaira; Rua, Diego; Khan, Ikhlas A

    2016-07-18

    Tea tree oil (TTO) is an essential oil obtained from the leaves of Melaleuca alternifolia, M. linariifolia, or M. dissitiflora. Because of the commercial importance of TTO, substitution or adulteration with other tea tree species (such as cajeput, niaouli, manuka, or kanuka oils) is common and may pose significant risks along with perceived health benefits. The distinctive nature, qualitative and quantitative compositional variation of these oils, is responsible for the various pharmacological as well as adverse effects. Authentic TTOs (especially aged ones) have been identified as potential skin sensitizers, while reports of adverse allergic reactions to the other tea trees essential oils are less frequent. Chemical sensitizers are usually electrophilic compounds, and in chemico methods have been developed to identify skin allergens in terms of their ability to bind to biological nucleophiles. However, little information is available on the assessment of sensitization potential of mixtures, such as essential oils, due to their complexity. In the present study, 10 "tea tree" oils and six major TTO constituents have been investigated for their sensitization potential using a fluorescence in chemico method. The reactivity of authentic TTOs was found to correlate with the age of the oils, while the majority of nonauthentic TTOs were less reactive, even after aging. Further thio-trapping experiments with DCYA and characterization by UHPLC-DAD-MS led to the identification of several possible DCYA-adducts which can be used to deduce the structure of the candidate reactive species. The major TTO components, terpinolene, α-terpinene, and terpinene-4-ol, were unstable under accelerated aging conditions, which led to the formation of several DCYA-adducts.

  15. Steepest-entropy-ascent quantum thermodynamic framework for describing the non-equilibrium behavior of a chemically reactive system at an atomistic level

    CERN Document Server

    Beretta, Gian Paolo

    2015-01-01

    Steepest-Entropy-Ascent Quantum Thermodynamics (SEAQT) provides a general framework for the description of non-equilibrium phenomena at any level, particularly the atomistic one. This theory and its dynamical postulate are used here to develop a general mathematical framework, which at an atomistic level, in particular, can be used to predict the non-equilibrium evolution in state of a closed, chemically reactive mixture such as the one examined here, i.e., a mixture of hydrogen (H2) and flourine (F) contained in an isolated tank of fixed volume. The general framework provided, however, is written for a reactive system subject to multiple reaction mechanisms. To predict this evolution in state, both the energy and particle number eigenvalue problems for a dilute gas are set up and solved analytically. Wall and non-ideal-gas behavior effects are neglected, although the extension to dense gases is straightforward but left for a future paper. The system-level energy and particle number eigenvalues and eigenstate...

  16. Lattice-Boltzmann simulation methods for chemically reactive systems in the micro area; Lattice Boltzmann Simulationsmethoden fuer chemisch reaktive Systeme im Microbereich - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Karlin, I.; Frouzakis, Ch.; Boulouchos, K.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE) reports on work done in 2007 at the Swiss Federal Institute of Technology ETH in Zurich on simulation methods for chemically reactive systems at the micrometer scale. The Lattice-Boltzmann method using lattice models is examined and the results obtained are discussed. A three-dimensional thermal model was developed and used to analyse flows with considerable temperature and density variations. The model was also used for the analysis of flows in diluted gases. A method for the reduction of complex reaction mechanisms was developed and tested for future combustion applications. 30 publications are noted and new possibilities for the analysis of flows in micro-channels and porous media - as used in reformers, catalyzers and fuel cells - are discussed.

  17. Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part II--mechanism.

    Science.gov (United States)

    Newcombe, R L; Strawn, D G; Grant, T M; Childers, S E; Möller, G

    2008-03-01

    The removal mechanism of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE) was examined. A 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a 3-month tertiary effluent average of 0.011 mg/L phosphorus. In addition to aqueous geochemical modeling, experiments with surface charge, scanning electron microscopy, adsorptive capacity, thermal desorption, and most probable number of iron(III)-reducing bacteria were performed on samples from the system, to determine the major phosphorus-removal pathways. Results suggest that, in addition to filtration of particulate phosphorus, the low tertiary effluent total phosphorus result was achieved by adsorption.

  18. A novel combined chemical kinetic and trapping method for probing the relationships between chemical reactivity and interfacial H2O, Br(-) and H(+) ion molarities in CTAB/C12E6 mixed micelles.

    Science.gov (United States)

    Dar, Aijaz Ahmad; Romsted, Laurence S; Nazir, Nighat; Zhang, Yongliang; Gao, Xiang; Gu, Qing; Liu, Changyao

    2017-09-13

    A delicate balance-of-forces governs the interactions responsible for surfactant self-assembly and chemical reactivity within them. Chemical reactions in micellar media generally occur in the interfacial region of micelles that is a complex mixture of: water, headgroups, counterions, co-ions, acids or bases, organic solvents, and the reactants themselves. We have carried out a detailed study of a complex chemical reaction in mixed CTAB/C12E6 micelles by using the chemical kinetic (CK) and chemical trapping (CT) methods. The results provide a detailed quantitative treatment of the reaction of the anion of the antioxidant t-butylhydroquinone, TBHQ(-), with 4-hexadecylbenzenediazonium, 16-ArN2(+), within the interfacial region of the mixed micelles in the C12E6 mole fraction range of 0 to 1 at three different total surfactant concentrations. CK experiments showed that this reaction is monophasic in C12E6 micelles, but biphasic in mixed micelles. The results were fully consistent with a complex mechanism in which TBHQ(-) reacts with 16-ArN2(+) to give a transient diazoether intermediate that competitively breaks down into products and or reverts to starting materials. The kinetics are the same in mixed micelles of CTAB/C12E6 (grow) and CTAB/C12E8 (don't grow) showing that the rates only depend on micelle composition, not shape. CT results provided estimates of interfacial molarities of H2O are approximately constant at ca. 39 and Br(-) decreases from ca. 2.75 to 0.05 moles per liter of interfacial volume as C12E6 mole fraction increases from 0 to 1. Combined CK/CT results provided values for interfacial pH, ranging from ca. 4.25 in cationic micelles to 1.5 in nonionic micelles despite a constant bulk pH of 1.5 and the TBHQ interfacial pKa = 3.8 at all C12E6 molar fractions. In totality, these results yielded an extraordinary amount of quantitative information about the relationships between the chemical reactivity and interfacial compositions of the mixed micelles.

  19. 具有高比表面积的稻壳灰的制备及其化学活性的研究%Study on Preparation of Rice Husk Ash with High Specific Surface Area and Its Chemical Reactivity

    Institute of Scientific and Technical Information of China (English)

    冯庆革; 林清宇; 童张法; S.Sugita

    2004-01-01

    Preparation of rice husk ash with high specific surface area and chemical reactivity of the product are reported in this paper. The amorphous rice husk ash with high specific surface area of 311 m2·g-1 was produced by heating acid treated rice husk at 700℃ for 4 h. The isotherms of rice husk ash are similar in shape to type Ⅱof Brunaner's classification with mesopores being predominant. The rice husk ash has a high chemical reactivity,especially that pretreated with acid. This chemical reactivity depends on ashing temperature and pretreatment conditions. There is an exponential relation between the specific surface area of rice husk ash and the change in the conductivity of saturated Ca(OH)2 solution with rice husk ash, from which the specific surface area can be known according to the conductivity change.

  20. Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

    Directory of Open Access Journals (Sweden)

    Alejandro Morales-Bayuelo

    2014-01-01

    Full Text Available In molecular similarity there is a premise “similar molecules tend to behave similarly”; however in the actual quantum similarity field there is no clear methodology to describe the similarity in chemical reactivity, and with this end an analysis of charge-transfer (CT processes in a series of Diels-Alder (DA reactions between cyclopentadiene (Cp and cyano substitutions on ethylene has been studied. The CT analysis is performed in the reagent assuming a grand canonical ensemble and the considerations for an electrophilic system using B3LYP/6-31G(d and M06-2X/6-311 + G(d,p methods. An analysis for CT was performed in agreement with the experimental results with a good statistical correlation (R2=0.9118 relating the polar character to the bond force constants in DA reactions. The quantum distortion analysis on the transition states (TS was performed using molecular quantum similarity indexes of overlap and coulomb showing good correlation (R2=0.8330 between the rate constants and quantum similarity indexes. In this sense, an electronic reorganization based on molecular polarization in terms of CT is proposed; therefore, new interpretations on the electronic systematization of the DA reactions are presented, taking into account that today such electronic systematization is an open problem in organic physical chemistry. Additionally, one way to quantify the similarity in chemical reactivity was shown, taking into account the dependence of the molecular alignment on properties when their position changes; in this sense a possible way to quantify the similarity of the CT in systematic form on these DA cycloadditions was shown.

  1. A quantum chemical study of the reactivity of acetaminophen (paracetamol) toxic metabolite N-acetyl-p-benzoquinone imine with deoxyguanosine and glutathione.

    Science.gov (United States)

    Klopčič, Ivana; Poberžnik, Matic; Mavri, Janez; Dolenc, Marija Sollner

    2015-12-05

    Acetaminophen (APAP) forms some reactive metabolites that can react with DNA. APAP is a potentially genotoxic drug and is classified as a Group 3 drug according to International Agency for Research on Cancer (IARC). One of the possible mechanisms of APAP genotoxicity after long term of use is that its reactive quinone imine (QI) metabolite of acetaminophen (NAPQI), can chemically react with DNA after glutathione (GSH) depletion. A quantum chemical study of the reactions between the NAPQI and deoxyguanosine (dG) or GSH was performed. Activation energies (ΔG(ǂ)) for the reactions associated with the 1, 4-Michael addition were calculated on the M062X/6-311++G (d,p) level of theory. We modeled the reaction with dG as a multi-step process. The first step is rate-limiting (ΔG(ǂ) = 26.7 kcal/mol) and consists of formation of a C-N bond between the C3 atom of the QI moiety and the N7 atom of dG. The second step involves proton transfer from the C3 moiety to the nitrogen atom of the QI with ΔG(ǂ) of 13.8 kcal/mol. The depurination reaction that follows has a ΔG(ǂ) of 25.7 kcal/mol. The calculated ΔG(ǂ) for the nucleophilic attack of the deprotonated S atom of GSH on the C3 atom of the NAPQI is 12.9 kcal/mol. Therefore, the QI will react with GSH much faster than with DNA. Our study gives mechanistic insight into the genotoxicity of the APAP metabolite and will be useful for estimating the genotoxic potential of existing drugs with a QI moiety. Our results show that clinical application of APAP is safe, while in the case of severely depleted GSH levels APAP should be administered with caution. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  2. Determination of Human Hemoglobin Derivatives.

    Science.gov (United States)

    Attia, Atef M M; Ibrahim, Fatma A A; Abd El-Latif, Noha A; Aziz, Samir W; Abdelmottaleb Moussa, Sherif A; Elalfy, Mohsen S

    2015-01-01

    The levels of the inactive hemoglobin (Hb) pigments [such as methemoglobin (metHb), carboxyhemoglobin (HbCO) and sulfohemoglobin (SHb)] and the active Hb [in the oxyhemoglobin (oxyHb) form] as well as the blood Hb concentration in healthy non pregnant female volunteers were determined using a newly developed multi-component spectrophotometric method. The results of this method revealed values of SHb% in the range (0.0727-0.370%), metHb% (0.43-1.0%), HbCO% (0.4-1.52%) and oxyHb% (97.06-98.62%). Furthermore, the results of this method revealed values of blood Hb concentration in the range (12.608-15.777 g/dL). The method is highly sensitive, accurate and reproducible.

  3. THE BIOCHEMISTRY OF VITREOSCILLA HEMOGLOBIN

    Directory of Open Access Journals (Sweden)

    Benjamin C. Stark

    2012-10-01

    Full Text Available The hemoglobin (VHb from Vitreoscilla was the first bacterial hemoglobin discovered. Its structure and function have been extensively investigated, and engineering of a wide variety of heterologous organisms to express VHb has been performed to increase their growth and productivity. This strategy has shown promise in applications as far-ranging as the production of antibiotics and petrochemical replacements by microorganisms to increasing stress tolerance in plants. These applications of “VHb technology” have generally been of the “black box” variety, wherein the endpoint studied is an increase in the levels of a certain product or improved growth and survival. Their eventual optimization, however, will require a thorough understanding of the various functions and activities of VHb, and how VHb expression ripples to affect metabolism more generally. Here we review the current knowledge of these topics. VHb's functions all involve oxygen binding (and often delivery in one way or another. Several biochemical and structure-function studies have provided an insight into the molecular details of this binding and delivery. VHb activities are varied. They include supply of oxygen to oxygenases and the respiratory chain, particularly under low oxygen conditions; oxygen sensing and modulation of transcription factor activity; and detoxification of NO, and seem to require interactions of VHb with “partner proteins”. VHb expression affects the levels of ATP and NADH, although not enormously. VHb expression may affect the level of many compounds of intermediary metabolism, and, apparently, alters the levels of expression of many genes. Thus, the metabolic changes in organisms engineered to express VHb are likely to be numerous and complicated.

  4. Clinical study on the changes of serum brain natriuretic peptide,C reactive protein and glycosylated hemoglobin in patients with diabetes and hypertension complicated with heart failure with preserved ejection fraction%糖尿病合并高血压射血分数保留的心力衰竭患者血清脑钠肽、C反应蛋白、糖化血红蛋白变化的临床研究

    Institute of Scientific and Technical Information of China (English)

    赵英丽; 李志娟

    2016-01-01

    Objective:To investigate the significance of the changes of serum brain natriuretic peptide,C reactive protein and glycosylated hemoglobin in patients with diabetes and hypertension complicated with heart failure with preserved ejection fraction. Methods:241 cases of HFPEF patients with hypertension and (or) diabetes were divided into the diabetic group and the non-diabetic group.The HbA1c,C reactive protein,NT-proBNP of the two groups were compared.Results:The HbA1c,C reactive protein,NT-proBNP and the incidence of major adverse cardial events(MACE) in the diabetic group were significantly higher than those in the non-diabetic group(P<0.05).There were positive correlation between HbA1cC reactive protein,NT-proBNP and the incidence of MACE.Conclusion:NT-proBNP, HbA1c,C reactive protein had higher clinical application value in predicting the incidence of diabetes and hypertension complicated with heart failure with preserved ejection fraction.%目的:探讨糖尿病合并高血压射血分数保留的心力衰竭(HFPEF)患者血清脑钠肽、C反应蛋白、糖化血红蛋白变化的意义。方法:收治合并高血压和(或)糖尿病的 HFPEF 患者241例,分为糖尿病组和非糖尿病组。比较两组HbA1c、C反应蛋白、NT-proBNP。结果:糖尿病组的HbA1c、C反应蛋白、NT-proBNP、MACE发生率显著高于非糖尿病组(P<0.05)。HbA1c、C反应蛋白、NT-proBNP与MACE发生率呈正相关。结论:NT-proBNP、HbA1c、C反应蛋白对糖尿病合并高血压HFPEF发生率的预测具有较高的临床应用价值。

  5. Led Astray by Hemoglobin A1c

    Directory of Open Access Journals (Sweden)

    Jean Chen MD

    2016-01-01

    Full Text Available Hemoglobin A1c (A1c is used frequently to diagnose and treat diabetes mellitus. Therefore, it is important be aware of factors that may interfere with the accuracy of A1c measurements. This is a case of a rare hemoglobin variant that falsely elevated a nondiabetic patient’s A1c level and led to a misdiagnosis of diabetes. A 67-year-old male presented to endocrine clinic for further management after he was diagnosed with diabetes based on an elevated A1c of 10.7%, which is approximately equivalent to an average blood glucose of 260 mg/dL. Multiple repeat A1c levels remained >10%, but his home fasting and random glucose monitoring ranged from 92 to 130 mg/dL. Hemoglobin electrophoresis and subsequent genetic analysis diagnosed the patient with hemoglobin Wayne, a rare hemoglobin variant. This variant falsely elevates A1c levels when A1c is measured using cation-exchange high-performance liquid chromatography. When the boronate affinity method was applied instead, the patient’s A1c level was actually 4.7%. Though hemoglobin Wayne is clinically silent, this patient was erroneously diagnosed with diabetes and started on an antiglycemic medication. Due to this misdiagnosis, the patient was at risk of escalation in his “diabetes management” and hypoglycemia. Therefore, it is important that providers are aware of factors that may result in hemoglobin A1c inaccuracy including hemoglobin variants.

  6. Structural alterations of hemoglobin and myoglobin by glyoxal: a comparative study.

    Science.gov (United States)

    Banerjee, Sauradipta; Chakraborti, Abhay Sankar

    2014-05-01

    Glyoxal, a highly reactive oxoaldehyde, increases in diabetic condition. It reacts with different proteins to form advanced glycation end products (AGEs). Here we have studied the structural alterations as well as the sites and nature of amino acid modifications of two heme proteins, hemoglobin and myoglobin on incubation with glyoxal for seven days at 25°C. In comparison with normal hemoglobin (HbA0), glyoxal-treated hemoglobin (GHbA0) exhibits decreased absorbance around 280 nm, reduced intrinsic fluorescence and lower surface hydrophobicity. However, glyoxal-treated myoglobin (GMb) exhibits the opposite effects in these respects when compared to normal myoglobin (Mb). Glyoxal increases the thermal stability of hemoglobin, while it decreases the stability of myoglobin. Matrix-assisted laser desorption ionization-time of flight (MALDI-TOF)-mass spectrometry reveals modifications of Arg-31α, Arg-40β and Arg-104β of hemoglobin by glyoxal to hydroimidazolone adducts. On the other hand, glyoxal modifies Lys-133 and Lys-145 to carboxymethyllysine and Arg-31 to hydroimidazolone adducts in myoglobin. Thus the same oxoaldehyde exerts different effects on hemoglobin and myoglobin and may be associated with different structural properties of the proteins.

  7. Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

    Science.gov (United States)

    Loew, G. H.; Berkowitz, D.; Chang, S.

    1975-01-01

    Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

  8. Molecular perspectives on solid-state phase transformation and chemical reactivity of drugs: metoclopramide as an example.

    Science.gov (United States)

    Lin, Shan-Yang

    2015-02-01

    Here, I provide an overview of the solid-state characteristics, phase transformations and chemical reactions of metoclopramide hydrochloride monohydrate (MCP HCl H2O). Three unique techniques, including thermoanalytical methods, one-step simultaneous differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) microspectroscopy, and hot-stage microscopic (HSM) imaging, have been applied to study the solid-state phase transitions of MCP HCl H2O in continuous dehydration, amorphization and recrystallization processes. I also review the effects of grinding or heating on ion-exchange reactions, milling, compression or colyophilization on Maillard reactions, and γ-ray irradiation or electron beams on radiolysis in the solid state. I also report the exposure of MCP HCl H2O in solution to light, irradiation, oxidants or π-acceptors. This review will serve as a useful keynote for the evolving realm of solid-state chemistry research.

  9. Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

    Science.gov (United States)

    Loew, G. H.; Berkowitz, D.; Chang, S.

    1975-01-01

    Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

  10. CHEMICALS

    CERN Document Server

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  11. Direct atomic-level observation and chemical analysis of ZnSe synthesized by in situ high-throughput reactive fiber drawing.

    Science.gov (United States)

    Hou, Chong; Jia, Xiaoting; Wei, Lei; Stolyarov, Alexander M; Shapira, Ofer; Joannopoulos, John D; Fink, Yoel

    2013-03-13

    We demonstrate a high-throughput method for synthesizing zinc selenide (ZnSe) in situ during fiber drawing. Central to this method is a thermally activated chemical reaction occurring across multiple interfaces between alternately layered elemental zinc- (Zn-) and selenium- (Se-) rich films embedded in a preform and drawn into meters of fiber at a temperature well below the melting temperature of either Zn or ZnSe. By depositing 50 nm thick layers of Zn interleaved between 1 μm thick Se layers, a controlled breakup of the Zn sheet is achieved, thereby enabling a complete and controlled chemical reaction. The thermodynamics and kinetics of this synthesis process are studied using thermogravimetric analysis and differential scanning calorimetry, and the in-fiber compound is analyzed by a multiplicity of materials characterization tools, including transmission electron microscopy, Raman microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction, all resulting in unambiguous identification of ZnSe as the compound produced from the reactive fiber draw. Furthermore, we characterize the in-fiber ZnSe/Se97S3 heterojunction to demonstrate the prospect of ZnSe-based fiber optoelectronic devices. The ability to synthesize new compounds during fiber drawing at nanometer scale precision and to characterize them at the atomic-level extends the architecture and materials selection compatible with multimaterial fiber drawing, thus paving the way toward more complex and sophisticated functionality.

  12. Molecular weight and chemical reactivity of dissolved trace metals (Cd, Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

    Science.gov (United States)

    Wen, Liang-Saw; Santschi, Peter H.; Warnken, Kent W.; Davison, William; Zhang, Hao; Li, Hsiu-Ping; Jiann, Kuo-Tung

    2011-05-01

    It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal-organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were "inert" averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of 'inert' and 'anionic' metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.

  13. Dose-dependent intracellular reactive oxygen and nitrogen species (ROS/RNS) production from particulate matter exposure: comparison to oxidative potential and chemical composition

    Science.gov (United States)

    Tuet, Wing Y.; Fok, Shierly; Verma, Vishal; Tagle Rodriguez, Marlen S.; Grosberg, Anna; Champion, Julie A.; Ng, Nga L.

    2016-11-01

    Elevated particulate matter (PM) concentrations have been associated with cardiopulmonary risks. In this study, alveolar macrophages and ventricular myocytes were exposed to PM extracts from 104 ambient filters collected in multiple rural and urban sites in the greater Atlanta area. PM-induced reactive oxygen/nitrogen species (ROS/RNS) were measured to investigate the effect of chemical composition and determine whether chemical assays are representative of cellular responses. For summer samples, the area under the ROS/RNS dose-response curve per volume of air (AUCvolume) was significantly correlated with dithiothreitol (DTT) activity, water-soluble organic carbon (WSOC), brown carbon, titanium, and iron, while a relatively flat response was observed for winter samples. EC50 was also correlated with max response for all filters investigated, which suggests that certain PM constituents may be involved in cellular protective pathways. Although few metal correlations were observed, exposure to laboratory-prepared metal solutions induced ROS/RNS production, indicating that a lack of correlation does not necessarily translate to a lack of response. Collectively, these results suggest that complex interactions may occur between PM species. Furthermore, the strong correlation between organic species and ROS/RNS response highlights a need to understand the contribution of organic aerosols, especially photochemically driven secondary organic aerosols (SOA), to PM-induced health effects.

  14. Reactive Extrusion for In-situ Chemical Modification of Cellulose with De-Octenyl succinic anhydride (DDSA in presence of Ionic liquid

    Directory of Open Access Journals (Sweden)

    Magdi Elamin Gibril

    2012-07-01

    Full Text Available Modification of microcrystalline cellulose by means of DDSA through the reactive extrusion process was preformed. The process was carried out by twin screw extruder in the presence of ionic liquids (IL, 1-butyl-3- methylimidazolium chloride [Bmim]Cl. The suitable composition for cellulose/IL mixture and optimum conditions for extrusion process were determined. Degree of substitution (DS for modified cellulose was found to be in the range of 0.100- 0.284. In order to study the chemical structure and the physical properties of the modified cellulose, characterization was done by FT-IR, solid-state CP/MAS 13CNMR, and theromgravimetric analysis. FT-IR data were found to have a new peak in contrast to original reactant which clearly indicated the presence of a chemical group. CP/MAS 13CNMR analysis approved the existence of succinylation between cellulose and DDSA. The TGA analysis showed that the thermal stability of modified cellulose was decreased upon increasing of the degree of substitution (DS or the increasing of the amount of DDSA in the samples.

  15. Nadir Hemoglobin Levels after Discontinuation of Epoetin in Hemodialysis Patients

    OpenAIRE

    Calvo, Jose A.; Miskulin, Dana C.; Meyer, Klemens B.; Weiner, Daniel E.

    2010-01-01

    Background and objectives: In hemodialysis patients, both hemoglobin variability and targeting normalization of hemoglobin may have adverse consequences. There are few data on epoetin management in patients achieving high hemoglobin levels.

  16. Cobalt (hydr)oxide/graphite oxide composites: importance of surface chemical heterogeneity for reactive adsorption of hydrogen sulfide.

    Science.gov (United States)

    Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

    2012-07-15

    Composites of cobalt (hydr)oxide and graphite oxide (GO) were obtained and evaluated as adsorbents of hydrogen sulfide at ambient conditions. The surface properties of the initial and exhausted samples were studied by FTIR, TEM, SEM/EDX, XRD, adsorption of nitrogen, potentiometric titration, and thermal analysis. The results obtained show a significant improvement in their adsorption capacities compared to parent compounds. The importance of the OH groups of cobalt (hydr)oxide/GO composites and new interface chemistry for the adsorption of hydrogen sulfide on these materials is revealed. The oxygen activation by the carbonaceous component resulted in formation of sulfites. Water enhanced the removal process. This is the result of the basic environment promoting dissociation of H(2)S and acid-base reactions. Finally, the differences in the performance of the materials with different mass ratios of GO were linked to the availability of active sites on the surface of the adsorbents, dispersion of these sites, their chemical heterogeneity, and location in the pore system.

  17. Hybrid graphene oxide/DAB-Am-16 dendrimer: Preparation, characterization chemical reactivity and their electrocatalytic detection of L-Dopamine

    Science.gov (United States)

    Do Carmo, Devaney Ribeiro; Fernandes, Daniela Silvestrini

    2017-09-01

    Graphene oxide (GO) was chemically modified with a poly(propylene)imine Generation 3.0 dendrimer (DAB-Am-16). The characterization, structure and properties of hybrid graphene oxide/DAB-Am-16 dendrimer was studied by Raman spectroscopy, Fourier-Transforming Infrared Spectroscopy (FT-IR), X-Ray Photoelectron Spectroscopic (XPS), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis. After functionalized the hybrid material (GOD) can interact with copper and subsequently with hexacyanoferrate (III) ions (GODHCu). The GODHCu incorporated into a graphite paste electrode (20% w/w) was applied to an electrocatalytic detection of neurotransmitter L-dopamine using differential pulse voltammetry. The analytical curve showed a linear response in the concentration range from 1.0 × 10-7 to 1.0 × 10-5 mol L-1 with a corresponding equation Y(A) = 1.706 × 10-5 + 0.862 [L-dopamine] and a correlation coefficient r2 = 0.998. The detection limit was 6.36 × 10-7 mol L-1 with a relative standard deviation of ±4% (n = 3) and an amperometric sensitivity of 0.862 A/mol L-1.

  18. A chemical test of critical point isomorphism: reactive dissolution of ionic solids in isobutyric acid + water near the consolute point.

    Science.gov (United States)

    Baird, James K; Baker, Jonathan D; Hu, Baichuan; Lang, Joshua R; Joyce, Karen E; Sides, Alison K; Richey, Randi D

    2015-03-12

    Binary liquid mixtures having a consolute point can be used as solvents for chemical reactions. When excess cerium(IV) oxide is brought into equilibrium with a mixture of isobutyric acid + water, and the concentration of cerium in the liquid phase is plotted in van't Hoff form, a straight line results for temperatures sufficiently in excess of the critical solution temperature. Within 1 K of the critical temperature, however, the concentration becomes substantially suppressed, and the van't Hoff slope diverges toward negative infinity. According to the phase rule, one mole fraction can be fixed. Given this restriction, the temperature behavior of the data is in exact agreement with the predictions of both the principle of critical point isomorphism and the Gibbs-Helmholtz equation. In addition, we have determined the concentration of lead in the liquid phase when crystalline lead(II) sulfate reacts with potassium iodide in isobutyric acid + water. When plotted in van't Hoff form, the data lie on a straight line for all temperatures including the critical region. The phase rule indicates that two mole fractions can be fixed. With this restriction, the data are in exact agreement with the principle of critical point isomorphism.

  19. Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins

    Science.gov (United States)

    Junginger, Andrej; Duvenbeck, Lennart; Feldmaier, Matthias; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

    2017-08-01

    In chemical or physical reaction dynamics, it is essential to distinguish precisely between reactants and products for all times. This task is especially demanding in time-dependent or driven systems because therein the dividing surface (DS) between these states often exhibits a nontrivial time-dependence. The so-called transition state (TS) trajectory has been seen to define a DS which is free of recrossings in a large number of one-dimensional reactions across time-dependent barriers and thus, allows one to determine exact reaction rates. A fundamental challenge to applying this method is the construction of the TS trajectory itself. The minimization of Lagrangian descriptors (LDs) provides a general and powerful scheme to obtain that trajectory even when perturbation theory fails. Both approaches encounter possible breakdowns when the overall potential is bounded, admitting the possibility of returns to the barrier long after the trajectories have reached the product or reactant wells. Such global dynamics cannot be captured by perturbation theory. Meanwhile, in the LD-DS approach, it leads to the emergence of additional local minima which make it difficult to extract the optimal branch associated with the desired TS trajectory. In this work, we illustrate this behavior for a time-dependent double-well potential revealing a self-similar structure of the LD, and we demonstrate how the reflections and side-minima can be addressed by an appropriate modification of the LD associated with the direct rate across the barrier.

  20. The impact of snow nitrate photolysis on boundary layer chemistry and the recycling and redistribution of reactive nitrogen across Antarctica and Greenland in a global chemical transport model

    Science.gov (United States)

    Zatko, Maria; Geng, Lei; Alexander, Becky; Sofen, Eric; Klein, Katarina

    2016-03-01

    The formation and recycling of reactive nitrogen (NO, NO2, HONO) at the air-snow interface has implications for air quality and the oxidation capacity of the atmosphere in snow-covered regions. Nitrate (NO3-) photolysis in snow provides a source of oxidants (e.g., hydroxyl radical) and oxidant precursors (e.g., nitrogen oxides) to the overlying boundary layer, and alters the concentration and isotopic (e.g., δ15N) signature of NO3- preserved in ice cores. We have incorporated an idealized snowpack with a NO3- photolysis parameterization into a global chemical transport model (Goddard Earth Observing System (GEOS) Chemistry model, GEOS-Chem) to examine the implications of snow NO3- photolysis for boundary layer chemistry, the recycling and redistribution of reactive nitrogen, and the preservation of ice-core NO3- in ice cores across Antarctica and Greenland, where observations of these parameters over large spatial scales are difficult to obtain. A major goal of this study is to examine the influence of meteorological parameters and chemical, optical, and physical snow properties on the magnitudes and spatial patterns of snow-sourced NOx fluxes and the recycling and redistribution of reactive nitrogen across Antarctica and Greenland. Snow-sourced NOx fluxes are most influenced by temperature-dependent quantum yields of NO3- photolysis, photolabile NO3- concentrations in snow, and concentrations of light-absorbing impurities (LAIs) in snow. Despite very different assumptions about snowpack properties, the range of model-calculated snow-sourced NOx fluxes are similar in Greenland (0.5-11 × 108 molec cm-2 s-1) and Antarctica (0.01-6.4 × 108 molec cm-2 s-1) due to the opposing effects of higher concentrations of both photolabile NO3- and LAIs in Greenland compared to Antarctica. Despite the similarity in snow-sourced NOx fluxes, these fluxes lead to smaller factor increases in mean austral summer boundary layer mixing ratios of total nitrate (HNO3+ NO3-), NOx, OH

  1. PSI's 1kW imaging furnace-A tool for high-temperature chemical reactivity studies

    Energy Technology Data Exchange (ETDEWEB)

    Guesdon, C.; Alxneit, I.; Tschudi, H.R.; Wuillemin, D.; Brunner, Y.; Winkel, L.; Sturzenegger, M. [Laboratory for High-Temperature Solar Technology, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Petrasch, J. [Professorship for Renewable Energy Carriers, ETHZ Zentrum, 8092 Zurich (Switzerland)

    2006-10-15

    A new experiment has been installed to conduct studies at temperatures as high as 2500K on chemical reactions that involve solids or melts and the release of condensable gases. The sample is radiatively heated by a 1kW xenon short arc lamp placed in the upper focus of a vertically oriented ellipsoid of revolution. The optimal optical configuration has been determined by a Monte-Carlo Ray tracing method. Several methods to machine the reflector have been evaluated by experimentally determining the optical quality of the surface of plane test pieces. In the imaging furnace the sample is placed on a water-cooled support and heated by the concentrated radiation. This arrangement allows for fast heating and impedes the reaction of the sample with crucible material. A remotely controlled hammer allows for freezing the high-temperature composition of the sample by a fast quench. Thus, the sample can be later analyzed by conventional methods such as XRD or TEM. To allow for measurements under defined atmospheres and to protect the ellipsoidal reflector from liberated condensable products, the entire sample stage is enclosed by a hemispherical glass dome. The dome itself is protected from condensable compounds by a laminar flow of inert gas. Experiments with an incense cone at the place of the sample to visualize the gas flow showed that a steady layer of inert gas protects the dome from smoke, if the inert gas flow is properly adjusted. Measured peak flux densities clearly exceed 500Wcm{sup -2} required to access temperatures of at least 2500K. Decomposition experiments on copper sulfides confirmed the operation of the furnace. In the near future flash assisted multi-wavelength pyrometry (FAMP) will be implemented to measure sample temperatures online. Though the imaging furnace was developed to study the decomposition of metal sulfides it is obviously suited to conduct high-temperature studies on most materials relevant for high-temperature solar technology. (author)

  2. Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

    Science.gov (United States)

    Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

    2017-06-01

    Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn2Al-Met-LDHs, identified with the formula of Zn0.7Al0.3(OH)2(Met)0.3·0.32H2O, has good thermal stability. Adsorption experiments with Zn2Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn2Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn2Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs.

  3. Characterizing the chemical evolution of air masses via multi-platform measurements of volatile organic compounds (VOCs) during CalNEX: Composition, OH reactivity, and potential SOA formation

    Science.gov (United States)

    Gilman, J. B.; Kuster, W. C.; Bon, D.; Warneke, C.; Lerner, B. M.; Williams, E. J.; Holloway, J. S.; Pollack, I. B.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Herndon, S. C.; Zahniser, M. S.; Vlasenko, A. L.; Li, S.; Alvarez, S. L.; Rappenglueck, B.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; De Gouw, J. A.

    2011-12-01

    Volatile organic compounds (VOCs) are critical components in the photochemical production of ozone (O3) and secondary organic aerosol (SOA). During the CalNex 2010 field campaign, an extensive set of VOCs were measured at the Pasadena ground site, and aboard the NOAA WP-3D aircraft and the WHOI Research Vessel Atlantis. The measurements from each platform provide a unique perspective into the emissions, transport, and atmospheric processing of VOCs within the South Coast Air Basin (SoCAB). The observed enhancement ratios of the hydrocarbons measured on all three platforms are in good agreement and are generally well correlated with carbon monoxide (CO), indicating the prevalence of on-road VOC emission sources throughout the SoCAB. Offshore measurements aboard the ship and aircraft are used to characterize the air mass composition as a function of the land/sea-breeze effect. VOC ratios and other trace gases are used to identify air masses containing relatively fresh emissions that were often associated with offshore flow and re-circulated continental air associated with onshore flow conditions. With the prevailing southwesterly airflow pattern in the LAB throughout the daytime, the Pasadena ground site effectively functions as a receptor site and is used to characterize primary VOC emissions from downtown Los Angeles and to identify the corresponding secondary oxidation products. The chemical evolution of air masses as a function of the time of day is investigated in order to determine the relative impacts of primary emissions vs. secondary VOC products on OH reactivity and potential SOA formation. The reactivity of VOCs with the hydroxyl radical (OH) at the Pasadena site was dominated by the light hydrocarbons, isoprene, and oxygenated VOCs including aldehydes (secondary products) and alcohols (primary anthropogenic emissions). Toluene and benzaldehyde, both of which are associated with primary anthropogenic emissions, are the predominant VOC precursors to the

  4. Reactive Nitrogen in Asian Continental Outflow over the Western Pacific: Results from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P)Airborne Mission

    Science.gov (United States)

    Talbot, R.; Dibb, J.; Scheuer, E.; Seid, G.; Russo, R.; Sandholm, S.; Tan, D.; Blake, D.; Blake, N.; Singh, H.

    2003-01-01

    We present here results for reactive nitrogen species measured aboard the NASA DC-8 aircraft during the Transport and Chemical Evolution over the Pacific TRACE-P) mission. The large-scale distributions total reactive nitrogen (NO(sub y,sum) = NO + NO2 + HNO3 + PAN + C(sub 1)-C(sub 5) alkyl nitrates) and O3 and CO were better defined in the boundary layer with significant degradation of the relationships as altitude increased. Typically, NO(sub y,sum) was enhanced over background levels of approx.260 pptv by 20-to-30-fold. The ratio C2H2/CO had values of 1-4 at altitudes up to 10 km and as far eastward as 150degE, implying significant vertical mixing of air parcels followed by rapid advection across the Pacific. Analysis air parcels originating from five principal Asian source regions showed that HNO3 and PAN dominated NO(sub y,sum). Correlations of NO(sub y,sum) with C2Cl4 (urban tracer) were not well defined in any of the source regions, and they were only slightly better with CH3Cl (biomass tracer). Air parcels over the western Pacific contained a complex mixture of emission sources that are not easily resolvable as shown by analysis of the Shanghai mega-city plume. It contained an intricate mixture of pollution emissions and exhibited the highest mixing ratios of NO(sub y,sum) species observed during TRACE-P. Comparison of tropospheric chemistry between the earlier PEM-West B mission and the recent TRACE-P data showed that in the boundary layer significant increases in the mixing ratios of NO(sub y,sum)species have occurred, but the middle and upper troposphere seems to have been affected minimally by increasing emissions on the Asian continent over the last 7 years.

  5. Relative Reactivity Measurements of Stabilized CH2OO, Produced by Ethene Ozonolysis, Toward Acetic Acid and Water Vapor Using Chemical Ionization Mass Spectrometry.

    Science.gov (United States)

    Yajima, Ryoji; Sakamoto, Yosuke; Inomata, Satoshi; Hirokawa, Jun

    2017-08-31

    We investigated the relative reactivity of stabilized CH2OO, produced by ethene ozonolysis, toward acetic acid and water vapor at a temperature of 298 ± 2 K and atmospheric pressure. Hydroperoxymethyl acetate produced through the reaction between stabilized CH2OO and acetic acid was monitored using a chemical ionization mass spectrometer as a function of the acetic acid concentration at different relative humidities. The rate of the reaction between CH2OO and water vapor depended quadratically on the water vapor concentration, suggesting that CH2OO reacted with water dimers in preference to water monomers. We obtained the bimolecular rate constant for the reaction between CH2OO and water dimer relative to the rate constant for the reaction between CH2OO and acetic acid, k3/k1, of (6.3 ± 0.4) × 10(-2). The k3 value of (8.2 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1) was derived by combining with a k1 value of (1.3 ± 0.1) × 10(-10) cm(3) molecule(-1) s(-1), which has been previously reported by direct kinetic studies. The k3 value thus obtained is consistent with the absolute rate constants measured directly, suggesting that the reactivity of CH2OO is irrespective of the CH2OO generation method, namely, ethene ozonolysis or diiodomethane photolysis. We indirectly determined the yield of stabilized CH2OO from the ozonolysis of ethene of 0.59 ± 0.17 and 0.55 ± 0.16 under dry and humid (relative humidity 23-24%) conditions, respectively, suggesting that the yield is independent of the water vapor concentration. Our results suggest that hydroperoxymethyl acetate is the sole product of the reaction between stabilized CH2OO and acetic acid. The approach presented here can likely be extended to studies of the reactivities of more complicated and atmospherically relevant stabilized Criegee intermediates.

  6. Mutational analysis of hemoglobin binding and heme utilization by a bacterial hemoglobin receptor.

    Science.gov (United States)

    Fusco, W G; Choudhary, N R; Council, S E; Collins, E J; Leduc, I

    2013-07-01

    Iron is an essential nutrient for most living organisms. To acquire iron from their environment, Gram-negative bacteria use TonB-dependent transporters that bind host proteins at the bacterial surface and transport iron or heme to the periplasm via the Ton machinery. TonB-dependent transporters are barrel-shaped outer membrane proteins with 22 transmembrane domains, 11 surface-exposed loops, and a plug domain that occludes the pore. To identify key residues of TonB-dependent transporters involved in hemoglobin binding and heme transport and thereby locate putative protective epitopes, the hemoglobin receptor of Haemophilus ducreyi HgbA was used as a model of iron/heme acquisition from hemoglobin. Although all extracellular loops of HgbA are required by H. ducreyi to use hemoglobin as a source of iron/heme, we previously demonstrated that hemoglobin binding by HgbA only involves loops 5 and 7. Using deletion, substitution, and site-directed mutagenesis, we were able to differentiate hemoglobin binding and heme acquisition by HgbA. Deletion or substitution of the GYEAYNRQWWA region of loop 5 and alanine replacement of selected histidines affected hemoglobin binding by HgbA. Conversely, mutation of the phenylalanine in the loop 7 FRAP domain or substitution of the NRQWWA motif of loop 5 significantly abrogated utilization of heme from hemoglobin. Our findings show that hemoglobin binding and heme utilization by a bacterial hemoglobin receptor involve specific motifs of HgbA.

  7. A hemoglobin A1C immunoassay method not affected by carbamylated hemoglobin.

    Science.gov (United States)

    Rose, A M; Tongate, C; Valdes, R

    1995-01-01

    Hemoglobin A1C (HbA1C) methods based on charge separation of Hb species are subject to interference from carbamylated Hb (carb Hb). Carb Hb adducts are formed via interaction of terminal amino groups of HbA with isocyanic acid, after the spontaneous dissociation of urea to cyanate. It is hypothesized that a new immunoassay method, using a monoclonal antibody that recognizes the N-terminus of the Hb beta-chain and its sugar moiety, should be refractory to cross-reactive interference from carb Hb. To test this hypothesis, Hb was carbamylated in vitro and co-migration of carb Hb assessed with HbA1C using an electrophoretic method. Densitometric scans - post sodium cyanate incubation and electrophoretic separation - showed a 5 to 7 fold elevation of the HbA1C peak only, while HbA1C values obtained using immunoassay were unaffected. Also assessed was carbamylation interference in vivo, and a positive proportional bias with the electrophoretic system (Y) was observed compared to the immunoassay system (X) (y = 1.2x - 0.21 percent). Others have shown that carb Hb may cause a clinically significant false elevation in patient HbA1C values, when methods based on charge separation of Hb species are used. It is our conclusion, however, that while carb Hb may play a role, the differences observed in this study are largely due to calibration.

  8. Modulation of oxygen binding to insect hemoglobins: the structure of hemoglobin from the botfly Gasterophilus intestinalis.

    Science.gov (United States)

    Pesce, Alessandra; Nardini, Marco; Dewilde, Sylvia; Hoogewijs, David; Ascenzi, Paolo; Moens, Luc; Bolognesi, Martino

    2005-12-01

    Hemoglobins (Hbs) reversibly bind gaseous diatomic ligands (e.g., O2) as the sixth heme axial ligand of the penta-coordinate deoxygenated form. Selected members of the Hb superfamily, however, display a functionally relevant hexa-coordinate heme Fe atom in their deoxygenated state. Endogenous heme hexa-coordination is generally provided in these Hbs by the E7 residue (often His), which thus modulates accessibility to the heme distal pocket and reactivity of the heme toward exogenous ligands. Such a pivotal role of the E7 residue is prominently shown by analysis of the functional and structural properties of insect Hbs. Here, we report the 2.6 A crystal structure of oxygenated Gasterophilus intestinalis Hb1, a Hb known to display a penta-coordinate heme in the deoxygenated form. The structure is analyzed in comparison with those of Drosophila melanogaster Hb, exhibiting a hexa-coordinate heme in its deoxygenated derivative, and of Chironomus thummi thummi HbIII, which displays a penta-coordinate heme in the deoxygenated form. Despite evident structural differences in the heme distal pockets, the distinct molecular mechanisms regulating O2 binding to the three insect Hbs result in similar O(2 affinities (P50 values ranging between 0.12 torr and 0.46 torr).

  9. Selection of aptamers specific for glycated hemoglobin and total hemoglobin using on-chip SELEX.

    Science.gov (United States)

    Lin, Hsin-I; Wu, Ching-Chu; Yang, Ching-Hsuan; Chang, Ko-Wei; Lee, Gwo-Bin; Shiesh, Shu-Chu

    2015-01-21

    Blood glycated hemoglobin (HbA1c) levels reflecting average glucose concentrations over the past three months are fundamental for the diagnosis, monitoring, and risk assessment of diabetes. It has been hypothesized that aptamers, which are single-stranded DNAs or RNAs that demonstrate high affinity to a large variety of molecules ranging from small drugs, metabolites, or proteins, could be used for the measurement of HbA1c. Aptamers are selected through an in vitro process called systematic evolution of ligands by exponential enrichment (SELEX), and they can be chemically synthesized with high reproducibility at relatively low costs. This study therefore aimed to select HbA1c- and hemoglobin (Hb)-specific single-stranded DNA aptamers using an on-chip SELEX protocol. A microfluidic SELEX chip was developed to continuously and automatically carry out multiple rounds of SELEX to screen specific aptamers for HbA1c and Hb. HbA1c and Hb were first coated onto magnetic beads. Following several rounds of selection and enrichment with a randomized 40-mer DNA library, specific oligonucleotides were selected. The binding specificity and affinity were assessed by competitive and binding assays. Using the developed microfluidic system, the incubation and partitioning times were greatly decreased, and the entire process was shortened dramatically. Both HbA1c- and Hb-specific aptamers selected by the microfluidic system showed high specificity and affinity (dissociation constant, Kd = 7.6 ± 3.0 nM and 7.3 ± 2.2 nM for HbA1c and Hb, respectively). With further refinements in the assay, these aptamers may replace the conventional antibodies for in vitro diagnostics applications in the near future.

  10. Characterization of Drosophila hemoglobin. Evidence for hemoglobin-mediated respiration in insects.

    Science.gov (United States)

    Hankeln, Thomas; Jaenicke, Viviane; Kiger, Laurent; Dewilde, Sylvia; Ungerechts, Guy; Schmidt, Marc; Urban, Joachim; Marden, Michael C; Moens, Luc; Burmester, Thorsten

    2002-08-09

    In contrast to previous assumptions, the fruit fly Drosophila melanogaster possesses hemoglobin. This respiratory protein forms a monomer of about 17 kDa that is not exported into the hemolymph. Recombinant Drosophila hemoglobin displays a typical hexacoordinated deoxy spectrum and binds oxygen with an affinity of 0.12 torr. Four different hemoglobin transcripts have been identified, which are generated by two distinct promoters of the hemoglobin (glob1) gene but are identical in their coding regions. Putative binding sites for hypoxia-regulated transcription factors have been identified in the gene. Hemoglobin synthesis in Drosophila is mainly associated with the tracheal system and the fat body. This suggests that oxygen supply in insects may be more complex than thought previously and may depend on hemoglobin-mediated oxygen transport and storage in addition to simple diffusion.

  11. Nanobiotechnology for hemoglobin-based blood substitutes.

    Science.gov (United States)

    Chang, T M S

    2009-04-01

    Nanobiotechnology is the assembling of biological molecules into nanodimension complexes. This has been used for the preparation of polyhemoglobin formed by the assembling of hemoglobin molecules into a soluble nanodimension complex. New generations of this approach include the nanobiotechnological assembly of hemoglobin, catalase, and superoxide dismutase into a soluble nanodimension complex. This acts as an oxygen carrier and an antioxidant for those conditions with potential for ischemiareperfusion injuries. Another recent novel approach is the assembling of hemoglobin and fibrinogen into a soluble nanodimension polyhemoglobin-fibrinogen complex that acts as an oxygen carrier with platelet-like activity. This is potentially useful in cases of extensive blood loss requiring massive replacement using blood substitutes, resulting in the need for the replacement of platelets and clotting factors. A further step is the preparation of nanodimension artificial red blood cells that contain hemoglobin and all the enzymes present in red blood cells.

  12. Undetectable Glycosylated Hemoglobin in Autoimmune Hemolytic Anemia

    OpenAIRE

    Mitani, Noriyuki; Taguchi, Akihiko; Sakuragi, Shizu; Matsui, Kumiko; Tanaka, Yoshinori; Matsuda, Kazuhiro; Shinohara, Kenji

    2005-01-01

    We encountered two cases of autoimmune hemolytic anemia (AIHA) with undetectable glycosylated hemoglobin (HbA1C) level at diagnosis. Hemolytic anemia improved by administration of prednisolone (PSL) and HbA1C became measurable after response.

  13. Optical Marking of Alcohol Induced Hemoglobin Modification

    CERN Document Server

    Vlokh, R; Moroz, O; Nastishin, Yu; Dudok, K; Dudok, T; Grinchishin, N; Nechiporenko, I; Hul, A

    2007-01-01

    It has been shown that conformational modifications of Hb induced by ethanol consumption can be visualized in optical spectra studying oxygenation kinetics of hemoglobin or mixing hemoglobin with Cibacron blue dye. Better dye affinity of blood proteins extracted from alcoholised rats with respect to those from non-alcoholised ones confirms that ethanol and its metabolites induce structural pathologies in blood protein molecules. The detected changes for the case of the posterity of intoxicated animals may be explained as a post-translation modification, as well as a disturbance of the structure and function of tissue cellular gene mechanism for the blood creation. It is established that alcohol intake during first four months leads to the decrease of fractional weight of oxyhemoglobin and to the increase of methemoglobin amount in blood. Further alcohol consumption is accompanied by recovering of the normal level of hemoglobin derivatives in blood. Normalization of the fractional weight of hemoglobin derivati...

  14. Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part I--performance.

    Science.gov (United States)

    Newcombe, R L; Rule, R A; Hart, B K; Möller, G

    2008-03-01

    This work examines the performance of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE). A 3-month, 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a tertiary effluent average of 0.011 mg/L phosphorus. Iron doses to the plant were low, at 5 mg/L. Inline recycling of HFO solution rejects to the plant influent resulted in a maximum 90.3%, dose-dependent reduction of phosphorus in the secondary effluent at 4.5 ML/d (1.2 mgd). Other results included reduction of total suspended solids and turbidity. A mass balance analysis was performed. We conclude that HFO-RF-RECYCLE may allow very low levels of phosphorus discharge from municipal wastewater treatment plants with a ferric-iron-based tertiary filtration process and residual recycling.

  15. Exploring the Chemical Reactivity between Carbon Dioxide and Three Transition Metals (Au, Pt, and Re) at High-Pressure, High-Temperature Conditions.

    Science.gov (United States)

    Santamaría-Pérez, David; McGuire, Chris; Makhluf, Adam; Kavner, Abby; Chuliá-Jordán, Raquel; Pellicer-Porres, Julio; Martinez-García, Domingo; Doran, Andrew; Kunz, Martin; Rodríguez-Hernández, Plácida; Muñoz, Alfonso

    2016-10-06

    The role of carbon dioxide, CO2, as oxidizing agent at high pressures and temperatures is evaluated by studying its chemical reactivity with three transition metals: Au, Pt, and Re. We report systematic X-ray diffraction measurements up to 48 GPa and 2400 K using synchrotron radiation and laser-heating diamond-anvil cells. No evidence of reaction was found in Au and Pt samples in this pressure-temperature range. In the Re + CO2 system, however, a strongly-driven redox reaction occurs at P > 8 GPa and T > 1500 K, and orthorhombic β-ReO2 is formed. This rhenium oxide phase is stable at least up to 48 GPa and 2400 K and was recovered at ambient conditions. Raman spectroscopy data confirm graphite as a reaction product. Ab-initio total-energy structural and compressibility data of the β-ReO2 phase shows an excellent agreement with experiments, altogether accurately confirming CO2 reduction P-T conditions in the presence of rhenium metal and the β-ReO2 equation of state.

  16. Role of Noninvasive Hemoglobin Monitoring in Trauma

    Science.gov (United States)

    2015-03-25

    AFRL-SA-WP-SR-2015-0002 Role of Noninvasive Hemoglobin Monitoring in Trauma Betty J. Tsuei, MD; Dennis J. Hanseman, PhD...W. Gerlach, USAF, MC U.S. Air Force School of Aerospace Medicine, Center for the Sustainment of Trauma and Readiness Skills March 2015...August 2012 – August 2013 4. TITLE AND SUBTITLE Role of Noninvasive Hemoglobin Monitoring in Trauma 5a. CONTRACT NUMBER FA8650-12-2-6B14 5b

  17. Tangential flow filtration of hemoglobin.

    Science.gov (United States)

    Palmer, Andre F; Sun, Guoyong; Harris, David R

    2009-01-01

    Bovine and human hemoglobin (bHb and hHb, respectively) was purified from bovine and human red blood cells via tangential flow filtration (TFF) in four successive stages. TFF is a fast and simple method to purify Hb from RBCs using filtration through hollow fiber (HF) membranes. Most of the Hb was retained in stage III (100 kDa HF membrane) and displayed methemoglobin levels less than 1%, yielding final concentrations of 318 and 300 mg/mL for bHb and hHb, respectively. Purified Hb exhibited much lower endotoxin levels than their respective RBCs. The purity of Hb was initially assessed via SDS-PAGE, and showed tiny impurity bands for the stage III retentate. The oxygen affinity (P(50)) and cooperativity coefficient (n) were regressed from the measured oxygen-RBC/Hb equilibrium curves of RBCs and purified Hb. These results suggest that TFF yielded oxygen affinities of bHb and hHb that are comparable to values in the literature. LC-MS was used to measure the molecular weight of the alpha (alpha) and beta (beta) globin chains of purified Hb. No impurity peaks were present in the HPLC chromatograms of purified Hb. The mass of the molecular ions corresponding to the alpha and beta globin chains agreed well with the calculated theoretical mass of the alpha- and beta- globin chains. Taken together, our results demonstrate that HPLC-grade Hb can be generated via TFF. In general, this method can be more broadly applied to purify Hb from any source of RBCs. This work is significant, since it outlines a simple method for generating Hb for synthesis and/or formulation of Hb-based oxygen carriers.

  18. Evaluation of the Efficiency of the Reticulocyte Hemoglobin Content on Diagnosis for Iron Deficiency Anemia in Chinese Adults

    Directory of Open Access Journals (Sweden)

    Jie Cai

    2017-05-01

    Full Text Available Our aim was to evaluate the cut-off value and efficiency of using reticulocyte hemoglobin content as a marker to diagnose iron deficiency anemia in Chinese adults. 140 adults who needed bone marrow aspiration for diagnosis at the hematology department of the Peking Union Medical College Hospital were enrolled according to the inclusive and exclusive criteria. Venous blood samples were collected to detect complete blood count, including hemoglobin, reticulocyte hemoglobin content, hematocrit, mean cellular volume, corpuscular hemoglobin concentration, hemoglobin content, free erythrocyte protoporphyrin; iron indexes of serum ferritin, serum transferrin receptor, and unsaturated iron-binding capacity; and inflammation markers of C-reactive protein and α-acid glycoprotein. Bone marrow samples were obtained for the bone marrow iron staining, which was used as the standard for the evaluation of iron status in this study. Subjects were divided into three groups according to hemoglobin levels and bone marrow iron staining results: the IDA (iron deficiency anemia group, the NIDA (non-iron deficiency anemia group, and the control group. The differences of the above-mentioned indexes were compared among the three groups and the effect of inflammation was also considered. The cut-off value of reticulocyte hemoglobin content was determined by receiver operation curves. The IDA group (n = 56 had significantly lower reticulocyte hemoglobin content, mean cellular volume, corpuscular hemoglobin concentration, hemoglobin content, and serum ferritin; and higher free erythrocyte protoporphyrin, unsaturated iron-binding capacity, and serum transferrin receptor (p < 0.05 compared with the NIDA group (n = 38 and control group (n = 46. Hematocrit, serum ferritin, and unsaturated iron-binding capacity were significantly affected by inflammation while reticulocyte hemoglobin content and other parameters were not. The cut-off value of reticulocyte hemoglobin content for

  19. Hemoglobin levels in normal Filipino pregnant women.

    Science.gov (United States)

    Kuizon, M D; Natera, M G; Ancheta, L P; Platon, T P; Reyes, G D; Macapinlac, M P

    1981-09-01

    The hemoglobin concentrations during pregnancy in Filipinos belonging to the upper income group, who were prescribed 105 mg elemental iron daily, and who had acceptable levels of transferrin saturation, were examined in an attempt to define normal levels. The hemoglobin concentrations for each trimester followed a Gaussian distribution. The hemoglobin values equal to the mean minus one standard deviation were 11.4 gm/dl for the first trimester and 10.4 gm/dl for the second and third trimesters. Using these values as the lower limits of normal, in one group of pregnant women the prevalence of anemia during the last two trimesters was found lower than that obtained when WHO levels for normal were used. Groups of women with hemoglobin of 10.4 to 10.9 gm/dl (classified anemic by WHO criteria but normal in the present study) and those with 11.0 gm/dl and above could not be distinguished on the basis of their serum ferritin levels nor on the degree of decrease in their hemoglobin concentration during pregnancy. Many subjects in both groups, however, had serum ferritin levels less than 12 ng/ml which indicate poor iron stores. It might be desirable in future studies to determine the hemoglobin cut-off point that will delineate subjects who are both non-anemic and adequate in iron stores using serum ferritin levels as criterion for the latter.

  20. Noninvasive hemoglobin monitoring: how accurate is enough?

    Science.gov (United States)

    Rice, Mark J; Gravenstein, Nikolaus; Morey, Timothy E

    2013-10-01

    Evaluating the accuracy of medical devices has traditionally been a blend of statistical analyses, at times without contextualizing the clinical application. There have been a number of recent publications on the accuracy of a continuous noninvasive hemoglobin measurement device, the Masimo Radical-7 Pulse Co-oximeter, focusing on the traditional statistical metrics of bias and precision. In this review, which contains material presented at the Innovations and Applications of Monitoring Perfusion, Oxygenation, and Ventilation (IAMPOV) Symposium at Yale University in 2012, we critically investigated these metrics as applied to the new technology, exploring what is required of a noninvasive hemoglobin monitor and whether the conventional statistics adequately answer our questions about clinical accuracy. We discuss the glucose error grid, well known in the glucose monitoring literature, and describe an analogous version for hemoglobin monitoring. This hemoglobin error grid can be used to evaluate the required clinical accuracy (±g/dL) of a hemoglobin measurement device to provide more conclusive evidence on whether to transfuse an individual patient. The important decision to transfuse a patient usually requires both an accurate hemoglobin measurement and a physiologic reason to elect transfusion. It is our opinion that the published accuracy data of the Masimo Radical-7 is not good enough to make the transfusion decision.

  1. Chemical Characterization and Formation of Reactive Oxygen Species by PM2.5 during Summer in North China Plain of China

    Science.gov (United States)

    Zheng, M.; Li, X.; Kuang, X.; Yan, C.; Guo, X.; Paulson, S. E.

    2015-12-01

    Ambient particulate matter (PM) could cause adverse health effects by generating reactive oxygen species (ROS) including superoxide (·O2-), hydrogen peroxide (HOOH), and hydroxyl radical (·OH). A number of studies have shown that transition metals, quinones, as well as other unknown organics in particles, may contribute to ROS formation. North China Plain (NCP) is one of the most populated and polluted areas in the world, where Beijing, the capital of China, is located. NCP have been suffering from severe air pollution, and health effects of fine PM have drawn great attentions of both the government and the public. To study the chemical characterization and ROS generation of PM, airborne PM2.5 was collected at two sites, with one urban site on the campus of Peking University in Beijing and one suburban site in Wangdu, Hebei Province, which is located in the south of Beijing and was significantly influenced by biomass burning during the study period. Previous studies have shown that Beijing can be more influenced by regional transport when the prevailing wind is from the south. PM2.5 samples were collected on 47 mm Teflon filter and Quartz filter using the four-channel low-volume sampler, and organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), soluble ions and trace metals have been analyzed. The formation of ·OH induced by PM2.5 was also measured to characterize the chemical generation of ROS from ambient particles in a cell-free solution. Preliminary analysis showed that during biomass burning periods, OC and EC concentrations in Wangdu were significantly higher than that in Beijing. The average concentration of WSOC in Beijing was comparable to that in Wangdu, while during biomass burning period, that in Wangdu was much higher than that in Beijing. Positive matrix factorization (PMF) was applied to identify the major contributing sources of PM2.5. More detailed information about chemical compositions, sources and ROS generation of

  2. 21 CFR 864.7470 - Glycosylated hemoglobin assay.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Glycosylated hemoglobin assay. 864.7470 Section... Glycosylated hemoglobin assay. (a) Identification. A glycosylated hemoglobin assay is a device used to measure the glycosylated hemoglobins (A1a, A1b, and A1c) in a patient's blood by a column...

  3. 21 CFR 864.7400 - Hemoglobin A2 assay.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hemoglobin A2 assay. 864.7400 Section 864.7400...) MEDICAL DEVICES HEMATOLOGY AND PATHOLOGY DEVICES Hematology Kits and Packages § 864.7400 Hemoglobin A2 assay. (a) Identification. A hemoglobin A2 assay is a device used to determine the hemoglobin A2...

  4. 21 CFR 864.7440 - Electrophoretic hemoglobin analysis system.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Electrophoretic hemoglobin analysis system. 864....7440 Electrophoretic hemoglobin analysis system. (a) Identification. An electrophoretic hemoglobin... hemoglobin types as an aid in the diagnosis of anemia or erythrocytosis (increased total red cell mass)...

  5. 21 CFR 864.7500 - Whole blood hemoglobin assays.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Whole blood hemoglobin assays. 864.7500 Section... blood hemoglobin assays. (a) Identification. A whole blood hemoglobin assay is a device consisting or... hemoglobin content of whole blood for the detection of anemia. This generic device category does not...

  6. 21 CFR 864.5620 - Automated hemoglobin system.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Automated hemoglobin system. 864.5620 Section 864....5620 Automated hemoglobin system. (a) Identification. An automated hemoglobin system is a fully... hemoglobin content of human blood. (b) Classification. Class II (performance standards)....

  7. 21 CFR 864.7415 - Abnormal hemoglobin assay.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Abnormal hemoglobin assay. 864.7415 Section 864... hemoglobin assay. (a) Identification. An abnormal hemoglobin assay is a device consisting of the reagents... hemoglobin types. (b) Classification. Class II (performance standards)....

  8. 21 CFR 866.5470 - Hemoglobin immunological test system.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hemoglobin immunological test system. 866.5470... Hemoglobin immunological test system. (a) Indentification. A hemoglobin immunological test system is a device... hemoglobin (the oxygen-carrying pigment in red blood cells) in blood, urine, plasma, or other body...

  9. The renal handling of hemoglobin. I. Glomerular filtration.

    Science.gov (United States)

    Bunn, H F; Esham, W T; Bull, R W

    1969-05-01

    The glomerular filtration of hemoglobin (alpha(2)beta(2)) was studied under conditions in which its dissociation into alphabeta dimers was experimentally altered. Rats receiving hemoglobin treated with the sulfhydryl reagent bis(N-maleimidomethyl) ether (BME) showed a much lower renal excretion and prolonged plasma survival as compared with animals injected with untreated hemoglobin. Plasma disappearance was also prolonged in dogs receiving BME hemoglobin. Gel filtration data indicated that under physiological conditions, BME hemoglobin had impaired subunit dissociation. In addition, BME hemoglobin showed a very high oxygen affinity and a decreased rate of auto-oxidation. Glomerular filtration was enhanced under conditions which favor the dissociation of hemoglobin into dimers. Cat hemoglobin, which forms subunits much more extensively than canine hemoglobin, was excreted more readily by the rat kidney. The renal uptake of (59)Fe hemoglobin injected intra-arterially into rabbits varied inversely with the concentration of the injected dose.

  10. Polyethylene Glycol Camouflaged Earthworm Hemoglobin

    Science.gov (United States)

    Moges, Selamawit; Nacharaju, Parimala; Roche, Camille; Dantsker, David; Palmer, Andre; Friedman, Joel M.

    2017-01-01

    Nearly 21 million components of blood and whole blood and transfused annually in the United States, while on average only 13.6 million units of blood are donated. As the demand for Red Blood Cells (RBCs) continues to increase due to the aging population, this deficit will be more significant. Despite decades of research to develop hemoglobin (Hb) based oxygen (O2) carriers (HBOCs) as RBC substitutes, there are no products approved for clinical use. Lumbricus terrestris erythrocruorin (LtEc) is the large acellular O2 carrying protein complex found in the earthworm Lumbricus terrestris. LtEc is an extremely stable protein complex, resistant to autoxidation, and capable of transporting O2 to tissue when transfused into mammals. These characteristics render LtEc a promising candidate for the development of the next generation HBOCs. LtEc has a short half-life in circulation, limiting its application as a bridge over days, until blood became available. Conjugation with polyethylene glycol (PEG-LtEc) can extend LtEc circulation time. This study explores PEG-LtEc pharmacokinetics and pharmacodynamics. To study PEG-LtEc pharmacokinetics, hamsters instrumented with the dorsal window chamber were subjected to a 40% exchange transfusion with 10 g/dL PEG-LtEc or LtEc and followed for 48 hours. To study the vascular response of PEG-LtEc, hamsters instrumented with the dorsal window chamber received multiple infusions of 10 g/dL PEG-LtEc or LtEc solution to increase plasma LtEc concentration to 0.5, then 1.0, and 1.5 g/dL, while monitoring the animals’ systemic and microcirculatory parameters. Results confirm that PEGylation of LtEc increases its circulation time, extending the half-life to 70 hours, 4 times longer than that of unPEGylated LtEc. However, PEGylation increased the rate of LtEc oxidation in vivo. Vascular analysis verified that PEG-LtEc showed the absence of microvascular vasoconstriction or systemic hypertension. The molecular size of PEG-LtEc did not change the

  11. Hemoglobin Syracuse (alpha2beta2-143(H21)His leads to Pro), a new high-affinity variant detected by special electrophoretic methods. Observations on the auto-oxidation of normal and variant hemoglobins.

    Science.gov (United States)

    Jensen, M; Oski, F A; Nathan, D G; Bunn, H F

    1975-01-01

    hemoglobin Syracuse had markedly impaired reactivity with 2,3-DPG. Hemoglobin Syracuse auto-oxidized more slowly than hemoglobin A, probably reflecting a slower rate of dissociation of oxygen from fully liganded hemoglobin. Images PMID:234980

  12. A new hemoglobin gene from soybean: a role for hemoglobin in all plants

    DEFF Research Database (Denmark)

    Anderson, C R; Jensen, E O; LLewellyn, D J

    1996-01-01

    indicate that this new gene is a nonsymbiotic legume hemoglobin. The finding of this gene in legumes and similar genes in other species strengthens our previous suggestion that genomes of all plants contain hemoglobin genes. The specialized leghemoglobin gene family may have arisen from a preexisting...

  13. Convergent evolution of hemoglobin switching in jawed and jawless vertebrates.

    Science.gov (United States)

    Rohlfing, Kim; Stuhlmann, Friederike; Docker, Margaret F; Burmester, Thorsten

    2016-02-01

    During development, humans and other jawed vertebrates (Gnathostomata) express distinct hemoglobin genes, resulting in different hemoglobin tetramers. Embryonic and fetal hemoglobin have higher oxygen affinities than the adult hemoglobin, sustaining the oxygen demand of the developing organism. Little is known about the expression of hemoglobins during development of jawless vertebrates (Agnatha). We identified three hemoglobin switches in the life cycle of the sea lamprey. Three hemoglobin genes are specifically expressed in the embryo, four genes in the filter feeding larva (ammocoete), and nine genes correspond to the adult hemoglobin chains. During the development from the parasitic to the reproductive adult, the composition of hemoglobin changes again, with a massive increase of chain aHb1. A single hemoglobin chain is expressed constitutively in all stages. We further showed the differential expression of other globin genes: Myoglobin 1 is most highly expressed in the reproductive adult, myoglobin 2 expression peaks in the larva. Globin X1 is restricted to the embryo; globin X2 was only found in the reproductive adult. Cytoglobin is expressed at low levels throughout the life cycle. Because the hemoglobins of jawed and jawless vertebrates evolved independently from a common globin ancestor, hemoglobin switching must also have evolved convergently in these taxa. Notably, the ontogeny of sea lamprey hemoglobins essentially recapitulates their phylogeny, with the embryonic hemoglobins emerging first, followed by the evolution of larval and adult hemoglobins.

  14. A cis-proline in alpha-hemoglobin stabilizing protein directs the structural reorganization of alpha-hemoglobin.

    Science.gov (United States)

    Gell, David A; Feng, Liang; Zhou, Suiping; Jeffrey, Philip D; Bendak, Katerina; Gow, Andrew; Weiss, Mitchell J; Shi, Yigong; Mackay, Joel P

    2009-10-23

    alpha-Hemoglobin (alphaHb) stabilizing protein (AHSP) is expressed in erythropoietic tissues as an accessory factor in hemoglobin synthesis. AHSP forms a specific complex with alphaHb and suppresses the heme-catalyzed evolution of reactive oxygen species by converting alphaHb to a conformation in which the heme is coordinated at both axial positions by histidine side chains (bis-histidyl coordination). Currently, the detailed mechanism by which AHSP induces structural changes in alphaHb has not been determined. Here, we present x-ray crystallography, NMR spectroscopy, and mutagenesis data that identify, for the first time, the importance of an evolutionarily conserved proline, Pro(30), in loop 1 of AHSP. Mutation of Pro(30) to a variety of residue types results in reduced ability to convert alphaHb. In complex with alphaHb, AHSP Pro(30) adopts a cis-peptidyl conformation and makes contact with the N terminus of helix G in alphaHb. Mutations that stabilize the cis-peptidyl conformation of free AHSP, also enhance the alphaHb conversion activity. These findings suggest that AHSP loop 1 can transmit structural changes to the heme pocket of alphaHb, and, more generally, highlight the importance of cis-peptidyl prolyl residues in defining the conformation of regulatory protein loops.

  15. A cis-Proline in α-Hemoglobin Stabilizing Protein Directs the Structural Reorganization of α-Hemoglobin*

    Science.gov (United States)

    Gell, David A.; Feng, Liang; Zhou, Suiping; Jeffrey, Philip D.; Bendak, Katerina; Gow, Andrew; Weiss, Mitchell J.; Shi, Yigong; Mackay, Joel P.

    2009-01-01

    α-Hemoglobin (αHb) stabilizing protein (AHSP) is expressed in erythropoietic tissues as an accessory factor in hemoglobin synthesis. AHSP forms a specific complex with αHb and suppresses the heme-catalyzed evolution of reactive oxygen species by converting αHb to a conformation in which the heme is coordinated at both axial positions by histidine side chains (bis-histidyl coordination). Currently, the detailed mechanism by which AHSP induces structural changes in αHb has not been determined. Here, we present x-ray crystallography, NMR spectroscopy, and mutagenesis data that identify, for the first time, the importance of an evolutionarily conserved proline, Pro30, in loop 1 of AHSP. Mutation of Pro30 to a variety of residue types results in reduced ability to convert αHb. In complex with αHb, AHSP Pro30 adopts a cis-peptidyl conformation and makes contact with the N terminus of helix G in αHb. Mutations that stabilize the cis-peptidyl conformation of free AHSP, also enhance the αHb conversion activity. These findings suggest that AHSP loop 1 can transmit structural changes to the heme pocket of αHb, and, more generally, highlight the importance of cis-peptidyl prolyl residues in defining the conformation of regulatory protein loops. PMID:19706593

  16. Mathematical Analysis of a Series of 4-Acetylamino-2-(3,5-dimethylpyrazol-1-yl-6-pyridylpyrimidines: A Simple Way to Relate Quantum Similarity to Local Chemical Reactivity Using the Gaussian Orbitals Localized Theory

    Directory of Open Access Journals (Sweden)

    Alejandro Morales-Bayuelo

    2014-01-01

    Full Text Available Molecular Quantum Similarity (MQS descriptors and Density Functional Theory (DFT based reactivity descriptors were studied for a series of 4-Acetylamino-2-(3,5-dimethylpyrazol-1-yl-6-pyridylpyrimidines compounds used for Parkinson’s disease (PD treatment. The quantification of the steric and electronic effects was shown through scales of quantitative convergence; such scales allow us to establish a methodology to quantify the similarity from the local chemical reactivity (Fukui Functions point of view. This procedure provides new considerations in the local reactivity of the A2A Adenosine receptor antagonists in a disease of difficult control as PD. In addition, we present new considerations to the localized bonding theory and show a new methodology for quantum similarity on the Fukui Functions. Considering that the Fukui functions under a condensation scheme may have ambiguities in the (DFT context.

  17. Chemical, modulus and cell attachment studies of reactive calcium phosphate filler-containing fast photo-curing, surface-degrading, polymeric bone adhesives.

    Science.gov (United States)

    Abou Neel, E A; Palmer, G; Knowles, J C; Salih, V; Young, A M

    2010-07-01

    The initial structure, setting and degradation processes of a poly(lactide-co-propylene glycol-co-lactide) dimethacrylate adhesive filled with 50, 60 or 70 wt.% reactive calcium phosphates (monocalcium phosphate monohydrate (MCPM)/beta-tricalcium phosphate (beta-TCP)) have been assessed using nuclear magnetic resonance, Fourier transform infrared spectroscopy, Raman, X-ray powder diffraction and gravimetric studies. Filler incorporation reduced the rapid light-activated monomer polymerization rates slightly, but not the final levels. Upon immersion in water for 24h, the set composite mass and volume increased due to water sorption. This promoted initial soluble MCPM loss from the composite surfaces, but also its reaction and monetite precipitation within the specimen bulk. After 48 h, composite gravimetric and chemical studies were consistent with surface erosion of polymer with reacted/remaining filler. The filled formulations exhibited more rapid early water sorption and subsequent surface erosion than the unfilled polymer. Calcium and phosphate release profiles and solution pH measurements confirmed early loss of surface MCPM with protons from polymer degradation products. At later times, the slower release of monetite/beta-TCP buffered composite storage solutions at approximately 5 instead of 3.2 for the unfilled polymer. Incorporation of filler increased both the early and later time material modulus. At intermediate times this effect was lost, presumably as a result of enhanced water sorption. The early modulus values obtained fell within the range reported for cancellous bone. Despite surface degradation, initial human mesenchymal cell attachment to both composites and polymer could be comparable with a non-degrading positive Thermanox control. These studies indicate that the filled formulations may be good candidates for bone repair. Release of calcium and phosphate ions provides components essential for such repair.

  18. Índices de reatividade química a partir da teoria do funcional de densidade: formalismo e perspectivas Chemical reactivity indexes from density functional theory: formalism and perspectives

    Directory of Open Access Journals (Sweden)

    Hélio Anderson Duarte

    2001-08-01

    Full Text Available The fundaments of the modern Density Functional Theory (DFT, its basic theorems, principles and methodology are presented. This review also discuss important and widely used concepts in chemistry but that had not been precisely defined until the development of the DFT. These concepts were proposed and used from an empirical base, but now their precise definition are well established in the DFT formalism. Concepts such as chemical potential (electronegativity, hardness, softness and Fukui function are presented and their consequences to the understanding of chemical reactivity are discussed.

  19. Nitrosyl hemoglobins: EPR above 80 K

    Energy Technology Data Exchange (ETDEWEB)

    Wajnberg, E.; Bemski, G.; El-Jaick, L.J.; Alves, O.C.

    1995-03-01

    The EPR spectra of nitrosyl hemoglobin and myoglobin in different conditions (native, denatured and lyophilized), as well as of hematin-NO were obtained in the temperature range of 80 K-280 K. There is a substantial and reversible.decrease of the areas of the EPR spectra of all the hemoglobin samples above 150 K. The interpretation of the results implies the existence of two conformational states in thermal equilibrium only one of which is EPR detectable. Thermodynamical parameters are determined for the hexa and penta-coordinated cases. (author). 25 refs, 3 figs.

  20. Mass Spectra and Ion Collision Cross Sections of Hemoglobin

    Science.gov (United States)

    Kang, Yang; Terrier, Peran; Douglas, D. J.

    2011-02-01

    Mass spectra of commercially obtained hemoglobin (Hb) show higher levels of monomer and dimer ions, heme-deficient dimer ions, and apo-monomer ions than hemoglobin freshly prepared from blood. This has previously been attributed to oxidation of commercial Hb. Further, it has been reported that that dimer ions from commercial bovine Hb have lower collision cross sections than low charge state monomer ions. To investigate these effects further, we have recorded mass spectra of fresh human Hb, commercial human and bovine Hb, fresh human Hb oxidized with H2O2, lyophilized fresh human Hb, fresh human Hb both lyophilized and chemically oxidized, and commercial human Hb oxidized with H2O2. Masses of α-monomer ions of all hemoglobins agree with the masses expected from the sequences within 3 Da or better. Mass spectra of the β chains of commercial Hb and oxidized fresh human Hb show a peak or shoulder on the high mass side, consistent with oxidation of the protein. Both commercial proteins and oxidized fresh human Hb produce heme-deficient dimers with masses 32 Da greater than expected and higher levels of monomer and dimer ions than fresh Hb. Lyophilization or oxidation of Hb both produce higher levels of monomer and dimer ions in mass spectra. Fresh human Hb, commercial human Hb, commercial bovine Hb, and oxidized commercial human Hb all give dimer ions with cross sections greater than monomer ions. Thus, neither oxidation of Hb or the difference in sequence between human and bovine Hb make substantial differences to cross sections of ions.

  1. The role of nitric oxide and hemoglobin in plant development and morphogenesis

    DEFF Research Database (Denmark)

    Hebelstrup, Kim; Shah, Jay K; Igamberdiev, Abir U

    2013-01-01

    Plant morphogenesis is regulated endogenously through phytohormones and other chemical signals, which may act either locally or distant from their place of synthesis. Nitric oxide (NO) is formed by a number of controlled processes in plant cells. It is a central signaling molecule with several...... the local cellular NO concentration. In this review, we analyze available data on the role of NO and plant hemoglobins in morphogenetic processes in plants. The comparison of the data suggests that hemoglobin gene expression in plants modulates development and morphogenesis of organs, such as roots...... and shoots, through the localized control of NO, and that hemoglobin gene expression should always be considered a modulating factor in processes controlled directly or indirectly by NO in plants....

  2. Hemoglobin adducts of N-substituted aryl compounds in exposure control and risk assessment.

    Science.gov (United States)

    Neumann, H G; Birner, G; Kowallik, P; Schütze, D; Zwirner-Baier, I

    1993-03-01

    Arylamines, nitroarenes, and azo dyes yield a common type of metabolite, the nitroarene, which produces a hydrolyzable adduct with protein and is closely related to the critical, ultimate toxic and genotoxic metabolite. The target dose as measured by hemoglobin adducts in erythrocytes reflects not only the actual uptake from the environment but also an individual's capacity for metabolic activation and is therefore an improved dosimeter for human exposure. The usefulness of hemoglobin adducts in molecular epidemiology is now widely recognized. With regard to risk assessment, many questions need to be answered. The described experiments in rats address some of these questions. The relationship between binding to hemoglobin in erythrocytes and to proteins in plasma has been found to vary considerably for a number of diamines. The fraction of hydrolyzable adducts out of the total protein adducts formed also varies in both compartments. This indicates that the kind of circulating metabolites and their availability in different compartments is compound specific. This has to do with the complex pattern of competing metabolic pathways, and the role of N-acetylation and deacetylation is emphasized. An example of nonlinear dose dependence adds to the complexity. Analysis of hemoglobin adducts reveals interesting insights into prevailing pathways, which not only apply to the chemical, but may also be useful to assess an individual's metabolic properties. In addition, it is demonstrated that the greater part of erythrocytes and benzidine-hemoglobin adducts are eliminated randomly in rats, i.e., following first-order kinetics.

  3. High-altitude adaptations in vertebrate hemoglobins

    DEFF Research Database (Denmark)

    Weber, Roy E.

    2007-01-01

    Vertebrates at high altitude are subjected to hypoxic conditions that challenge aerobic metabolism. O2 transport from the respiratory surfaces to tissues requires matching between the O2 loading and unloading tensions and theO2-affinity of blood, which is an integrated function of hemoglobin......, birds and ectothermic vertebrates at high altitude....

  4. Hemoglobin: A Nitric-Oxide Dioxygenase

    Directory of Open Access Journals (Sweden)

    Paul R. Gardner

    2012-01-01

    Full Text Available Members of the hemoglobin superfamily efficiently catalyze nitric-oxide dioxygenation, and when paired with native electron donors, function as NO dioxygenases (NODs. Indeed, the NOD function has emerged as a more common and ancient function than the well-known role in O2 transport-storage. Novel hemoglobins possessing a NOD function continue to be discovered in diverse life forms. Unique hemoglobin structures evolved, in part, for catalysis with different electron donors. The mechanism of NOD catalysis by representative single domain hemoglobins and multidomain flavohemoglobin occurs through a multistep mechanism involving O2 migration to the heme pocket, O2 binding-reduction, NO migration, radical-radical coupling, O-atom rearrangement, nitrate release, and heme iron re-reduction. Unraveling the physiological functions of multiple NODs with varying expression in organisms and the complexity of NO as both a poison and signaling molecule remain grand challenges for the NO field. NOD knockout organisms and cells expressing recombinant NODs are helping to advance our understanding of NO actions in microbial infection, plant senescence, cancer, mitochondrial function, iron metabolism, and tissue O2 homeostasis. NOD inhibitors are being pursued for therapeutic applications as antibiotics and antitumor agents. Transgenic NOD-expressing plants, fish, algae, and microbes are being developed for agriculture, aquaculture, and industry.

  5. Insulin-induced lipid binding to hemoglobin

    NARCIS (Netherlands)

    Tomasevic, N; Klappe, K; Hoekstra, D; Niketic, [No Value; Nikolic, M.

    2003-01-01

    Under hypoglycemic conditions, concomitant hyperinsulinism causes an apparent modification of hemoglobin (Hb) which is manifested by its a aggregation (Niketic et al.. Clin. Chim. Acia 197 (1991) 47). In the present work the causes and mechanisms underlying this Hb modification were Studied. Hemoglo

  6. High-altitude adaptations in vertebrate hemoglobins

    DEFF Research Database (Denmark)

    Weber, Roy E.

    2007-01-01

    Vertebrates at high altitude are subjected to hypoxic conditions that challenge aerobic metabolism. O2 transport from the respiratory surfaces to tissues requires matching between the O2 loading and unloading tensions and theO2-affinity of blood, which is an integrated function of hemoglobin......, birds and ectothermic vertebrates at high altitude....

  7. Kadar Hemoglobin dan Kecerdasan Intelektual Anak

    Directory of Open Access Journals (Sweden)

    Yuni Kusmiyati

    2013-10-01

    Full Text Available Kualitas sumber daya manusia dipengaruhi oleh inteligensi anak. Skor kecerdasan intelektual yang tidak menetap pada usia tertentu dapat berubah karena faktor genetik, gizi, dan lingkungan. Tujuan penelitian ini adalah mengetahui hubungan kadar hemoglobin dengan kecerdasan intelektual anak. Penelitian observasional dengan desain potong lintang ini dilakukan pada populasi siswa kelas VI Sekolah Dasar Negeri Giwangan Yogyakarta, tahun 2013. Penarikan sampel dilakukan dengan metode simple random sampling terhadap 37 sampel siswa. Instrumen untuk mengukur kecerdasan intelektual dengan Cultural Fair Intelligence Quotient Test yang dirancang untuk meminimalkan pengaruh kultural dengan memperhatikan prosedur evaluasi, instruksi, konten isi, dan respons peserta. Tes dilakukan oleh Biro Psikologi Universitas Ahmad Dahlan Yogyakarta, kadar hemoglobin diukur menggunakan Portable Hemoglobin Digital Analyzer Easy Touch secara digital.Variabel luar indeks massa tubuh diukur langsung menggunakan parameter tinggi badan dan berat badan. Analisis menggunakan uji regresi linier. Hasil penelitian menunjukkan indeks massa tubuh tidak berhubungan dengan kecerdasan intelektual (nilai p = 0,052. Anemia berhubungan cukup dengan kecerdasan anak (r = 0,491 dan berpola positif, semakin tinggi kadar hemoglobin semakin tinggi kecerdasan intelektual anak. Nilai koefisien determinasi 0,241 menerangkan bahwa 24,1% variasi anemia cukup baik untuk menjelaskan variabel kecerdasan intelektual. Ada hubungan antara kadar hemoglobin dengan kecerdasan intelektual (nilai p = 0,002. Quality of human resources is influenced by the child’s intelligent. Intelligence Quotient (IQ score will not settle at a certain age and can change due to genetic factors, nutrition, and the environment. The objective is known relationship of anemia with IQ to child. Method of observational study with cross sectional design. Population are students of class VI elementary school of Giwangan Yogyakarta in

  8. Hemoglobin C, S-C, and E Diseases

    Science.gov (United States)

    ... Anemia Vitamin Deficiency Anemia Anemia of Chronic Disease Aplastic Anemia Autoimmune Hemolytic Anemia Sickle Cell Disease Hemoglobin C, S- ... Anemia Vitamin Deficiency Anemia Anemia of Chronic Disease Aplastic Anemia Autoimmune Hemolytic Anemia Sickle Cell Disease Hemoglobin C, S- ...

  9. The influence of socioeconomic status on the hemoglobin level and ...

    African Journals Online (AJOL)

    The influence of socioeconomic status on the hemoglobin level and ... using anthropometric measurements and steady-state hemoglobin, of children with ... Social class was assessed using educational attainment and occupation of parents.

  10. Alpha chain hemoglobins with electrophoretic mobility similar to that of hemoglobin S in a newborn screening program

    Directory of Open Access Journals (Sweden)

    Marcilene Rezende Silva

    2013-01-01

    Full Text Available OBJECTIVE: To characterize alpha-chain variant hemoglobins with electric mobility similar to that of hemoglobin S in a newborn screening program. METHODS: βS allele and alpha-thalassemia deletions were investigated in 14 children who had undefined hemoglobin at birth and an electrophoretic profile similar to that of hemoglobin S when they were six months old. Gene sequencing and restriction enzymes (DdeI, BsaJI, NlaIV, Bsu36I and TaqI were used to identify hemoglobins. Clinical and hematological data were obtained from children who attended scheduled medical visits. RESULTS: The following alpha chain variants were found: seven children with hemoglobin Hasharon [alpha2 47(CE5 Asp>His, HbA2:c.142G>C], all associated with alpha-thalassemia, five with hemoglobin Ottawa [alpha1 15(A13 Gly>Arg, HBA1:c.46G>C], one with hemoglobin St Luke's [alpha1 95(G2 Pro>Arg, HBA1:c.287C>G] and another one with hemoglobin Etobicoke [alpha212 84(F5 Ser>Arg, HBA212:c.255C>G]. Two associations with hemoglobin S were found: one with hemoglobin Ottawa and one with hemoglobin St Luke's. The mutation underlying hemoglobin Etobicoke was located in a hybrid α212 allele in one child. There was no evidence of clinically relevant hemoglobins detected in this study. CONCLUSION: Apparently these are the first cases of hemoglobin Ottawa, St Luke's, Etobicoke and the α212 gene described in Brazil. The hemoglobins detected in this study may lead to false diagnosis of sickle cell trait or sickle cell disease when only isoelectric focusing is used in neonatal screening. Additional tests are necessary for the correct identification of hemoglobin variants.

  11. In vitro study of the direct effect of extracellular hemoglobin on myelin components.

    Science.gov (United States)

    Bamm, Vladimir V; Lanthier, Danielle K; Stephenson, Erin L; Smith, Graham S T; Harauz, George

    2015-01-01

    There is a relationship between cerebral vasculature and multiple sclerosis (MS) lesions: abnormal accumulations of iron have been found in the walls of dilated veins in MS plaques. The sources of this iron can be varied, but capillary and venous hemorrhages leading to blood extravasation have been recorded, and could result in the release of hemoglobin extracellularly. Extracellular hemoglobin oxidizes quickly and is known to become a reactive molecule that triggers low-density lipoprotein oxidation and plays a pivotal role in atherogenesis. In MS, it could lead to local oxidative stress, inflammation, and tissue damage. Here, we investigated whether extracellular hemoglobin and its breakdown products can cause direct oxidative damage to myelin components in a peroxidative environment such as occurs in inflamed tissue. Oxidation of lipids was assessed by the formation of fluorescent peroxidized lipid-protein covalent adducts, by the increase in conjugated diene and malondialdehyde. Oxidation of proteins was analyzed by the change in protein mass. The results suggest that the globin radical could be a trigger of myelin basic protein oxidative cross-linking, and that heme transferred to the lipids is involved in lipid peroxidation. This study provides new insight into the mechanism by which hemoglobin exerts its pathological oxidative activity towards myelin components. This work supports further research into the vascular pathology in MS, to gain insight into the origin and role of iron deposits in disease pathogenesis, or in stimulation of different comorbidities such as cardiovascular disease.

  12. 21 CFR 522.1125 - Hemoglobin glutamer-200 (bovine).

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hemoglobin glutamer-200 (bovine). 522.1125 Section... § 522.1125 Hemoglobin glutamer-200 (bovine). (a) Specifications. Each 125 milliliter bag contains 13 grams per deciliter of polymerized hemoglobin of bovine origin in modified Lactated Ringer's...

  13. Truncated hemoglobins in actinorhizal nodules of Datisca glomerata

    NARCIS (Netherlands)

    Pawlowski, K.; Jacobsen, K.R.; Alloisio, N.; Denison, R.F.; Klein, M.; Tjepkema, J.D.; Winzer, T.; Sirrenberg, A.; Guan, C.; Berry, A.M.

    2007-01-01

    Three types of hemoglobins exist in higher plants, symbiotic, non-symbiotic, and truncated hemoglobins. Symbiotic (class II) hemoglobins play a role in oxygen supply to intracellular nitrogen-fixing symbionts in legume root nodules, and in one case ( Parasponia Sp.), a non-symbiotic (class I) hemogl

  14. Truncated hemoglobins in actinorhizal nodules of Datisca glomerata

    NARCIS (Netherlands)

    Pawlowski, K.; Jacobsen, K.R.; Alloisio, N.; Denison, R.F.; Klein, M.; Tjepkema, J.D.; Winzer, T.; Sirrenberg, A.; Guan, C.; Berry, A.M.

    2007-01-01

    Three types of hemoglobins exist in higher plants, symbiotic, non-symbiotic, and truncated hemoglobins. Symbiotic (class II) hemoglobins play a role in oxygen supply to intracellular nitrogen-fixing symbionts in legume root nodules, and in one case ( Parasponia Sp.), a non-symbiotic (class I)

  15. Bioimaging techniques for subcellular localization of plant hemoglobins and measurement of hemoglobin-dependent nitric oxide scavenging in planta.

    Science.gov (United States)

    Hebelstrup, Kim H; Østergaard-Jensen, Erik; Hill, Robert D

    2008-01-01

    Plant hemoglobins are ubiquitous in all plant families. They are expressed at low levels in specific tissues. Several studies have established that plant hemoglobins are scavengers of nitric oxide (NO) and that varying the endogenous level of hemoglobin in plant cells negatively modulates bioactivity of NO generated under hypoxic conditions or during cellular signaling. Earlier methods for determination of hemoglobin-dependent scavenging in planta were based on measuring activity in whole plants or organs. Plant hemoglobins do not contain specific organelle localization signals; however, earlier reports on plant hemoglobin have demonstrated either cytosolic or nuclear localization, depending on the method or cell type investigated. We have developed two bioimaging techniques: one for visualization of hemoglobin-catalyzed scavenging of NO in specific cells and another for visualization of subcellular localization of green fluorescent protein-tagged plant hemoglobins in transformed Arabidopsis thaliana plants.

  16. Lyophilized bovine hemoglobin as a possible reference material for the determination of hemoglobin derivatives in human blood

    NARCIS (Netherlands)

    Maas, BHA; Buursma, A; Ernst, RAJ; Maas, AHJ; Zijlstra, WG

    1998-01-01

    We investigated the suitability of a lyophilized bovine hemoglobin (LBH) preparation containing various fractions of oxyhemoglobin (O(2)Hb), carboxyhemoglobin (COHb), and methemoglobin (MetHb) for quality assessment in multicomponent analysis (MCA) of hemoglobin derivatives. It was demonstrated that

  17. Covalent Modifiers: A Chemical Perspective on the Reactivity of α,β-Unsaturated Carbonyls with Thiols via Hetero-Michael Addition Reactions.

    Science.gov (United States)

    Jackson, Paul A; Widen, John C; Harki, Daniel A; Brummond, Kay M

    2017-02-09

    Although Michael acceptors display a potent and broad spectrum of bioactivity, they have largely been ignored in drug discovery because of their presumed indiscriminate reactivity. As such, a dearth of information exists relevant to the thiol reactivity of natural products and their analogues possessing this moiety. In the midst of recently approved acrylamide-containing drugs, it is clear that a good understanding of the hetero-Michael addition reaction and the relative reactivities of biological thiols with Michael acceptors under physiological conditions is needed for the design and use of these compounds as biological tools and potential therapeutics. This Perspective provides information that will contribute to this understanding, such as kinetics of thiol addition reactions, bioactivities, as well as steric and electronic factors that influence the electrophilicity and reversibility of Michael acceptors. This Perspective is focused on α,β-unsaturated carbonyls given their preponderance in bioactive natural products.

  18. Mass spectrometric identification of hemoglobin modifications induced by nitrosobenzene.

    Science.gov (United States)

    Di Girolamo, Francesco; Campanella, Luigi; Samperi, Roberto; Bachi, Angela

    2009-07-01

    Aniline and nitrobenzene (NB) are widely used industrial chemicals. Early effects of aniline toxicity include methemoglobin formation and damage to erythrocytes (Jenkins, F.P., 1972. The no-effect dose of anilne in human subjects and a comparison of aniline toxicity in man and rat. Food Cosmet. Toxicol. 10, 671-679; Bus, J.S., Popp, J.A., 1987. Perspectives on the mechanism of action of the splenic toxicity of aniline and structurally-related. Food Chem. Toxicol. 25, 619-627). In this report, we describe an analytical method, based on LC techniques and mass spectrometry, which could help in monitoring the exposure to aniline and NB. In particular, we describe and characterize the formation of specific adducts during an in vitro reaction of nitrosobenzene (NOB), the main metabolite of aniline and NB, and human hemoglobin.

  19. Sodium nitrite induces acute central nervous system toxicity in guinea pigs exposed to systemic cell-free hemoglobin.

    Science.gov (United States)

    Buehler, Paul W; Butt, Omer I; D'Agnillo, Felice

    2011-06-10

    Systemic cell-free hemoglobin (Hb) released via hemolysis disrupts vascular homeostasis, in part, through the scavenging of nitric oxide (NO). Sodium nitrite (NaNO(2)) therapy can attenuate the hypertensive effects of Hb. However, the chemical reactivity of NaNO(2) with Hb may enhance heme- or iron-mediated toxicities. Here, we investigate the effect of NaNO(2) on the central nervous system (CNS) in guinea pigs exposed to systemic cell-free Hb. Intravascular infusion of NaNO(2), at doses sufficient to alleviate Hb-mediated blood pressure changes, reduced the expression of occludin, but not zona occludens-1 (ZO-1) or claudin-5, in cerebral tight junctions 4h after Hb infusion. This was accompanied by increased perivascular heme oxygenase-1 expression, neuronal iron deposition, increased astrocyte and microglial activation, and reduced expression of neuron-specific nuclear protein (NeuN). These CNS changes were not observed in animals treated with Hb or NaNO(2) alone. Taken together, these findings suggest that the use of nitrite salts to treat systemic Hb exposure may promote acute CNS toxicity.

  20. Measurement of glycidol hemoglobin adducts in humans who ingest edible oil containing small amounts of glycidol fatty acid esters.

    Science.gov (United States)

    Honda, Hiroshi; Onishi, Masayuki; Fujii, Kenkichi; Ikeda, Naohiro; Yamaguchi, Tohru; Fujimori, Taketoshi; Nishiyama, Naohiro; Kasamatsu, Toshio

    2011-10-01

    Hemoglobin (Hb) adducts are frequently used to address and/or monitor exposure to reactive chemicals. Glycidol (G), a known animal carcinogen, has been reported to form Hb adducts. Here, we measure G adduct levels in humans who daily ingest DAG oil, an edible oil consisting mainly of diacylglycerol. Since DAG oil contains a small amount of glycidol fatty acid esters (GEs), possible exposure to G released from GEs has been raised as a possible concern. For measurement of Hb adducts, we employed the N-alkyl Edman method reported by Landin et al. (1996) using gas chromatography-tandem mass spectrometry with minor modifications to detect G-Hb adducts as N-(2,3-dihydroxy-propyl)valine (diHOPrVal). Blood samples were collected from 7 DAG oil users and 6 non-users, and then G-Hb adduct levels were measured. G-Hb adducts were detected in all samples. The average level of diHOPrVal was 3.5±1.9pmol/g globin in the DAG oil users and 7.1±3.1pmol/g globin in the non-users. We conclude that there is no increased exposure to G in individuals who daily ingest DAG oil.

  1. Hemoglobin expression in rat experimental granulation tissue

    Institute of Scientific and Technical Information of China (English)

    Miretta Tommila; Christoffer Stark; Anne Jokilammi; Ville Peltonen; Risto Penttinen; Erika Ekholm

    2011-01-01

    The general opinion that hemoglobin is only a carrier protein for oxygen and carbon dioxide has been challenged by several recent studies showing hemoglobin expression in other cells than those of the erythroid series, for example, in macrophages. We discovered β-globin expression in rat experimental granulation tissue induced by subcutaneously implanted cellulose sponges. Closer investigation revealed also α-globin expression. The first peak of the biphasic globin expression noticed during granulation tissue formation correlated with the invasion of monocytes/macrophages, whereas the second one seemed to be connected to the appearance of hematopoietic progenitors. Data presented in this study indicate globin expression both in macrophages and in immature erythroid cells as validated by erythroid-specific markers.

  2. Insulin-induced lipid binding to hemoglobin

    Directory of Open Access Journals (Sweden)

    VESNA NIKETIC

    2003-01-01

    Full Text Available Under hypoglycemic conditions, concomitant hyperinsulinism causes an apparent modification of hemoglobin (Hb which is manifested by its aggregation (Niketi} et al., Clin. Chim. Acta 197 (1991 47. In the present work the causes and mechanisms underlying this Hb modification were studied. Hemoglobin isolated from normal erythrocytes incubated with insulin was analyzed by applying 31P-spectrometry and lipid extraction and analysis. To study the dynamics of the plasma membrane during hyperinsulinism, a fluorescent lipid-analog was applied. In the presence of insulin, phosphatidylserine (PS, phosphatidylethanolamine (PE and cholesterol were found to bind to Hb. Lipid binding resulted in Hb aggregation, a condition that can be reproduced when phospholipids are incubated with Hb in vitro. Using a fluorescent lipid-analog, it was also shown that exposing erythrocytes to supraphysiological concentrations of insulin in vitro resulted in the internalization of lipids. The results presented in this work may have relevance to cases of diabetes mellitus and hypoglycemia.

  3. [Abnormal hemoglobins in Negroid Ecuadorian populations].

    Science.gov (United States)

    Jara, N O; Guevara Espinoza, A; Guderian, R H

    1989-02-01

    The prevalence of hemoglobinopathies was determined in the black race located in two distinct geographical areas in Ecuador; in the coastal province of Esmeraldas, particularly the Santiago basin (Rio Cayapas and Rio Onzoles) and in the province of Imbabura, particularly in the intermoutain valley, Valle de Chota. A total of 2038 blood samples were analyzed, 1734 in Esmeraldas and 304 in Inbabura, of which 23.2% (473 individuals) were found to be carriers of abnormal hemoglobins, 25.4% (441) in Esmeraldas and 10.5% (32) in Imbabura. The abnormal hemoglobins found in Esmeraldas were Hb AS (19.2%), Hb AC (5.0%), Hb SS (0.6%) and Hb SC (0.5%) while in Imbabura only Hb AS (9.5%) and Hb AC (0.9%) were found. The factors that could influence the difference in prevalence found in the two geographical areas are discussed.

  4. Induction of nano pore in Agrobacterial hemoglobin

    OpenAIRE

    Mojtaba Tousheh; Giti Emtiazi; Peyman Derikvand

    2014-01-01

    Introduction: A variety of oxygen-transport and -binding proteins exist in organisms including bacteria, protozoans, and fungi all have hemoglobin-like proteins. In addition to dealing with transport and sensing of oxygen, they may also deal with NO2, CO2, sulfide compounds, and even O2 scavenging in environments. Also they detoxified chlorinated materials like P450 enzymes and peroxidases and use as a detector of nitrate and hydrogen peroxide. Pore-forming bacterial globins are interested fo...

  5. Free heme and sickle hemoglobin polymerization

    Science.gov (United States)

    Uzunova, Veselina V.

    This work investigates further the mechanism of one of the most interesting of the protein self-assembly systems---the polymerization of sickle hemoglobin and the role of free heme in it. Polymerization of sickle hemoglobin is the primary event in the pathology of a chronic hemolytic condition called sickle cell anemia with complex pathogenesis, unexplained variability and symptomatic treatment. Auto-oxidation develops in hemoglobin solutions exposed to room temperature and causes release of ferriheme. The composition of such solutions is investigated by mass spectrometry. Heme dimers whose amount corresponds to the initial amounts of heme released from the protein are followed. Differences in the dimer peak height are established for hemoglobin variants A, S and C and depending on the exposure duration. The effects of free heme on polymerization kinetics are studied. Growth rates and two characteristic parameters of nucleation are measured for stored Hb S. After dialysis of polymerizing solutions, no spherulites are detected at moderately high supersaturation and prolonged exposure times. The addition of 0.16-0.26 mM amounts of heme to dialyzed solutions leads to restoration of polymerization. The measured kinetic parameters have higher values compared to the ones before dialysis. The amount of heme in non-dialyzed aged solution is characterized using spectrophotometry. Three methods are used: difference in absorbance of dialyzed and non-dialyzed solutions, characteristic absorbance of heme-albumin complex and absorbance of non-dialyzed solutions with added potassium cyanide. The various approaches suggest the presence of 0.12 to 0.18 mM of free ferriheme in such solutions. Open questions are whether the same amounts of free heme are present in vivo and whether the same mechanism operates intracellulary. If the answer to those questions is positive, then removal of free heme from erythrocytes can influence their readiness to sickle.

  6. Serum ferritin levels in hemoglobin H disease.

    Science.gov (United States)

    Galanello, R; Melis, M A; Paglietti, E; Cornacchia, G; de Virgiliis, S; Cao, A

    1983-01-01

    This study shows that hemoglobin H disease patients aged between 0.5 and 44 years, usually (27 out of 30) have normal serum ferritin levels according to age. This reconfirms that in this disease there are usually normal iron stores. However, in a few patients (3 out of 30) increased levels were found. This may be due to inappropriate iron medication, transfusions or associated idiopathic hereditary hemocromatosis gene.

  7. Induction of nano pore in Agrobacterial hemoglobin

    Directory of Open Access Journals (Sweden)

    Mojtaba Tousheh

    2014-01-01

    Full Text Available Introduction: A variety of oxygen-transport and -binding proteins exist in organisms including bacteria, protozoans, and fungi all have hemoglobin-like proteins. In addition to dealing with transport and sensing of oxygen, they may also deal with NO2, CO2, sulfide compounds, and even O2 scavenging in environments. Also they detoxified chlorinated materials like P450 enzymes and peroxidases and use as a detector of nitrate and hydrogen peroxide. Pore-forming bacterial globins are interested for filtration. Materials and methods: Although there are data for bacterial toxin as a filter, here we used Agrobacterial hem to induce nano pore in the heme structure using point mutation. Results: Investigations showed that three amino acids leucine 76, alanine 83 and histidine 80 are important for pore formation in Agrobacterium hemoglobin. A point mutation on leucine 76 to glycine, histidine 80 to asparagine and alanine 83 to lysine step by step led to create the nano pore 0.7- 0.8 nm in the globin. Discussion and conclusion: These mutations in bacterial hemoglobin increase the stability when mutation is with it’s at pH7. This mutation decreases the aliphatic index however increase the stability index.

  8. Hemoglobin profiles of siblings of thalassemia patients

    Directory of Open Access Journals (Sweden)

    Muhammad Riza

    2015-03-01

    Full Text Available Background Thalassemia and hemoglobinopathies are the most common inherited disorders in many areas of the world, including South East Asia. The siblings of thalassemia major is a group of high risk to carry the gene of thalassemia. Determining the carrier is useful for early treatment planning and prevention to the next child. Objective To determine carrier status among siblings of thalassemia patients using a capillary electrophoresis system. Methods A cross-sectional study on the siblings of thalassemia major patients was performed from January 2011 to February 2012 at Dr. Moewardi Hospital. Complete blood counts were performed in the siblings. Subjects with mean corpuscular volume (MCV <80 fl and mean corpuscular hemoglobin (MCH <27 pg were subjected to analize hemoglobin fraction by capillary electrophoresis. Results Of the 26 subjects, there were 12 males and 14 females. The mean age was 9.38 (SD 6.8 years (range 1 to 29 years. From the siblings, 10 were identified as normal, 5 were identified as ß thalassemia carriers and 5 were hemoglobin E (HbE carriers. Six siblings were diagnosed with ß thalassemia/ HbE. Conclusion There are high occurrence of the two common types of thalassemia carriers (ß and HbE in our small group of subjects who had a family history of thalassemia. Most of the siblings of thalassemia had low MCV and MCH. [Paediatr Indones. 2015;55:70-3.].

  9. Fetal hemoglobin in sickle cell anemia.

    Science.gov (United States)

    Akinsheye, Idowu; Alsultan, Abdulrahman; Solovieff, Nadia; Ngo, Duyen; Baldwin, Clinton T; Sebastiani, Paola; Chui, David H K; Steinberg, Martin H

    2011-07-07

    Fetal hemoglobin (HbF) is the major genetic modulator of the hematologic and clinical features of sickle cell disease, an effect mediated by its exclusion from the sickle hemoglobin polymer. Fetal hemoglobin genes are genetically regulated, and the level of HbF and its distribution among sickle erythrocytes is highly variable. Some patients with sickle cell disease have exceptionally high levels of HbF that are associated with the Senegal and Saudi-Indian haplotype of the HBB-like gene cluster; some patients with different haplotypes can have similarly high HbF. In these patients, high HbF is associated with generally milder but not asymptomatic disease. Studying these persons might provide additional insights into HbF gene regulation. HbF appears to benefit some complications of disease more than others. This might be related to the premature destruction of erythrocytes that do not contain HbF, even though the total HbF concentration is high. Recent insights into HbF regulation have spurred new efforts to induce high HbF levels in sickle cell disease beyond those achievable with the current limited repertory of HbF inducers.

  10. Cross diffusion and MHD effects on a high order chemically reactive micropolar fluid of naturally convective heat and mass transfer past through an infinite vertical porous medium with a constant heat sink

    Science.gov (United States)

    Arifuzzaman, S. M.; Rana, B. M. Jewel; Ahmed, R.; Ahmmed, S. F.

    2017-06-01

    High order chemically reactive micropolar fluid flow through an infinite vertical porous medium with thermal diffusion, mass diffusion, MHD, thermal radiation and heat sink has been studied. A flow model is established by employing the well-known boundary layer approximations. In order to obtain non-dimensional system of equations, a similarity transformation is applied on the flow model. The stability and convergence analysis have been analyzed. The obtained non-dimensional equations have been solved by explicit finite difference method. The effects of various parameters entering into the problem on velocity, angular velocity, temperature and concentration are shown graphically.

  11. D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical Reactivity in the Photolysis of Diazirine.

    Science.gov (United States)

    Yamada, Michio; Tanabe, Yukiko; Dang, Jing-Shuang; Sato, Satoru; Mizorogi, Naomi; Hachiya, Makoto; Suzuki, Mitsuaki; Abe, Tsuneyuki; Kurihara, Hiroki; Maeda, Yutaka; Zhao, Xiang; Lian, Yongfu; Nagase, Shigeru; Akasaka, Takeshi

    2016-12-21

    We compared the chemical reactivity of D2d(23)-C84 and that of Sc2C2@D2d(23)-C84, both having the same carbon cage geometry, in the photolysis of 2-adamantane-2,3'-[3H]-diazirine, to clarify metal-atom doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies have revealed that the chemical reactivity of the D2d(23)-C84 carbon cage is altered drastically by endohedral Sc2C2 doping. The reaction of empty D2d(23)-C84 with the diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR spectroscopic studies revealed that the major Ad monoadduct (C84(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C84(Ad)-B) has a methanofullerene structure. The latter was also characterized using X-ray crystallography. C84(Ad)-A is stable under photoirradiation, but it interconverted to C84(Ad)-B by heating at 80 °C. In contrast, the reaction of endohedral Sc2C2@D2d(23)-C84 with diazirine under photoirradiation affords four Ad monoadducts (Sc2C2@C84(Ad)-A, Sc2C2@C84(Ad)-B, Sc2C2@C84(Ad)-C, and Sc2C2@C84(Ad)-D). The structure of Sc2C2@C84(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of Sc2C2@C84(Ad)-A and Sc2C2@C84(Ad)-B to Sc2C2@C84(Ad)-C was also observed. The reaction mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations. Calculation results suggest that C84(Ad)-B and Sc2C2@C84(Ad)-C are thermodynamically favorable products. Their different chemical reactivities derive from Sc2C2 doping, which raises the HOMO and LUMO levels of the D2d(23)-C84 carbon cage.

  12. Communication: Ro-vibrational control of chemical reactivity in H+CH{sub 4}→ H{sub 2}+CH{sub 3} : Full-dimensional quantum dynamics calculations and a sudden model

    Energy Technology Data Exchange (ETDEWEB)

    Welsch, Ralph, E-mail: rwelsch@uni-bielefeld.de; Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de [Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld (Germany)

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  13. Nanosecond absorption study of kinetics associated with carbon monoxide rebinding to hemoglobin S and hemoglobin C following ligand photolysis.

    Science.gov (United States)

    Shapiro, D B; Paquette, S J; Esquerra, R M; Che, D; Goldbeck, R A; Hirsch, R E; Mohandas, N; Kliger, D S

    1994-11-30

    The absorption spectra of photolysis intermediates of the CO complex of hemoglobin S and hemoglobin C, in the tetramer form, have been measured between 10 ns and 200 ms after excitation. These data were analyzed using singular value decomposition (SVD) and global analysis to determine kinetic lifetimes associated with various processes involved in CO recombination. The results of this analysis show that, in the tetramer (non-aggregated) form, hemoglobin S and hemoglobin C exhibit the same kinetics associated with CO recombination as hemoglobin A.

  14. Reactive Hypoglycemia

    Science.gov (United States)

    ... from low blood sugar (hypoglycemia) that occurs while fasting. Signs and symptoms of reactive hypoglycemia may include ... and very important. It's also important to include physical activity in your daily routine. Your doctor can help ...

  15. Reactive Arthritis

    Directory of Open Access Journals (Sweden)

    Eren Erken

    2013-06-01

    Full Text Available Reactive arthritis is an acute, sterile, non-suppurative and inflammatory arthropaty which has occured as a result of an infectious processes, mostly after gastrointestinal and genitourinary tract infections. Reiter syndrome is a frequent type of reactive arthritis. Both reactive arthritis and Reiter syndrome belong to the group of seronegative spondyloarthropathies, associated with HLA-B27 positivity and characterized by ongoing inflammation after an infectious episode. The classical triad of Reiter syndrome is defined as arthritis, conjuctivitis and urethritis and is seen only in one third of patients with Reiter syndrome. Recently, seronegative asymmetric arthritis and typical extraarticular involvement are thought to be adequate for the diagnosis. However, there is no established criteria for the diagnosis of reactive arthritis and the number of randomized and controlled studies about the therapy is not enough. [Archives Medical Review Journal 2013; 22(3.000: 283-299

  16. A coordination polymer based magnetic adsorbent material for hemoglobin isolation from human whole blood, highly selective and recoverable

    Science.gov (United States)

    Zhang, Xiaoxing; Tan, Jipeng; Xu, Xinxin; Shi, Fanian; Li, Guanglu; Yang, Yiqiao

    2017-09-01

    A composite material has been obtained successfully through the loading of nanoscale coordination polymer on magnetic Fe3O4@SiO2 core-shell particle. In this composite material, coordination polymer nanoparticles distribute uniformly on Fe3O4@SiO2 and these two components are ;tied; together firmly with chemical bonds. Adsorption experiments suggest this composite material exhibits very excellent selectivity to hemoglobin. But under the same condition, its adsorption to bovine serum albumin can almost be ignored. This selectivity can be attributed to the existence of hydrophobic interactions between coordination polymer nanoparticle and hemoglobin. For composite material, the hemoglobin adsorption process follows Langmuir model perfectly with high speed. The adsorbed hemoglobin can be eluted easily by sodium dodecyl sulfate stripping reagent with structure and biological activity of hemoglobin keeps well. The composite material was also employed to separate hemoglobin from human whole blood, which receives a very satisfactory result. Furthermore, magnetic measurement reveals ferromagnetic character of this composite material with magnetization saturation 3.56 emu g-1 and this guarantees its excellent magnetic separation performance from the treated solution.

  17. Assessment of surface reactivity of thorium oxide in conditions close to chemical equilibrium by isotope exchange {sup 229}Th/{sup 232}Th method

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki-Muresan, Tomo; Perrigaud, Katy; Vandenborre, Johan; Ribet, Solange; Grambow, Bernd [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Takamasa, Inai [TOKAI Univ., Kanagawa (Japan)

    2017-08-01

    This work aims to assess the solubility and the surface reactivity of crystallized thorium at pH 3.0 in presence of three types of solids: synthesized powder at 1300 C, crushed kernel, and intact kernel. In this study, the kernel is composed by the core solid from high temperature reactors (HTR) sphere particles. The originality of this work consisted in following in a sequential order the kinetic of dissolution, the surface reactivity in presence of isotope tracer {sup 229}Th, and its desorption process. Long time experiments (634 days) allowed to get deeper understanding on the behavior of the surface reactivity in contact with the solution. Solubility values are ranging from 0.3 x 10{sup -7} mol.L{sup -1} to 3 x 10{sup -7} mol.L{sup -1} with a dissolution rate of 10{sup -6}-10{sup -4} g.m{sup -2} day{sup -1}. PHREEQC modeling showed that crystallized ThO{sub 2}(cr, 20 nm) phase controls the equilibrium in solution. Isotope exchange between {sup 229}Th and {sup 232}Th indicated that well-crystallized phase exist as an inert surface regarding to the absence of exchange between surface solid and solution.

  18. Scale Alpha and Beta of Quantitative Convergence and Chemical Reactivity Analysis in Dual Cholinesterase/Monoamine Oxidase Inhibitors for the Alzheimer Disease Treatment Using Density Functional Theory (DFT

    Directory of Open Access Journals (Sweden)

    Alejandro Morales-Bayuelo

    2013-01-01

    Full Text Available Molecular quantum similarity descriptors and Density Functional Theory (DFT based reactivity descriptors were studied for a series of cholinesterase/monoamine oxidase inhibitors used for the Alzheimer's disease treatment (AD. This theoretical study is expected to shed some light onto some molecular aspects that could contribute to the knowledge of the molecular mechanics behind interactions of these molecules with acetylcholinesterase (AChE and butyrylcholinesterase (BuChE, as well as with monoamine oxidase (MAO A and B. The Topogeometrical Superposition Algorithm to handle flexible molecules (TGSA-Flex alignment method was used to solve the problem of the relative orientation in the quantum similarity (QS field. Using the molecular quantum similarity (MQS field and reactivity descriptors supported in the DFT was possible the quantification of the steric and electrostatic effects through of the Coulomb and Overlap quantitative convergence scales (alpha and beta. In addition, an analysis of reactivity indexes is development, using global and local descriptors, identifying the binding sites and selectivity in the (cholinesterase/monoamine oxidase inhibitors, understanding the retrodonor process, and showing new insight for drugs design in a disease of difficult control as Alzheimer.

  19. Assessing the relative stabilities of engineered hemoglobins using electrospray mass spectrometry.

    Science.gov (United States)

    Apostol, I

    1999-07-15

    An ion trap mass spectrometer equipped with an electrospray source was used to examine the relative thermodynamic stabilities of various hemoglobins with respect to both tetramer dissociation and hemin dissociation. The results demonstrated that the stability of hemoglobin molecules can be differentiated by the amount of applied collision-induced dissociation (CID) energy necessary to break up the intact tetramer into its constituent globins. The stability of the intact tetramer was affected by single mutations in the beta-globins. The stabilities of the constituent hologlobins were assessed via trap CID of selected ions. The results demonstrated the importance of the contributions of the hologlobin components to the stability of the intact tetramer. Genetic fusion of two alpha-globins, through the introduction of a single glycine residue between the C-terminus of one alpha-chain and the N-terminus of the second, significantly increased the stability of the hemoglobin pseudo-tetramer. Chemical crosslinking of the beta-globins in addition to genetic fusion of alpha-globins further stabilized the hemoglobin molecule. A dihemoglobin molecule produced by the genetic fusion of two di-alpha-globins with a flexible linker demonstrated a decreased stability relative to the corresponding monohemoglobin.

  20. Adair-based hemoglobin equilibrium with oxygen, carbon dioxide and hydrogen ion activity.

    Science.gov (United States)

    Mateják, Marek; Kulhánek, Tomáš; Matoušek, Stanislav

    2015-04-01

    As has been known for over a century, oxygen binding onto hemoglobin is influenced by the activity of hydrogen ions (H⁺), as well as the concentration of carbon dioxide (CO₂). As is also known, the binding of both CO₂and H⁺ on terminal valine-1 residues is competitive. One-parametric situations of these hemoglobin equilibria at specific levels of H⁺, O₂or CO₂are also well described. However, we think interpolating or extrapolating this knowledge into an 'empirical' function of three independent variables has not yet been completely satisfactory. We present a model that integrates three orthogonal views of hemoglobin oxygenation, titration, and carbamination at different temperatures. The model is based only on chemical principles, Adair's oxygenation steps and Van't Hoff equation of temperature dependences. Our model fits the measurements of the Haldane coefficient and CO₂hemoglobin saturation. It also fits the oxygen dissociation curve influenced by simultaneous changes in H⁺, CO₂and O₂, which makes it a strong candidate for integration into more complex models of blood acid-base with gas transport, where any combination of mentioned substances can appear.

  1. Theoretical study of some aspects of the nucleo-bases reactivity: definition of new theoretical tools for the study of chemical reactivity; Etude theorique de quelques aspects de la reactivite des bases de l'ADN: definition de nouveaux outils theoriques d'etude de la reactivite chimique

    Energy Technology Data Exchange (ETDEWEB)

    Labet, V.

    2009-09-15

    In this work, three kinds of nucleo-base damages were studied from a theoretical point of view with quantum chemistry methods based on the density-functional theory: the spontaneous deamination of cytosine and its derivatives, the formation of tandem lesion induced by hydroxyl radicals in anaerobic medium and the formation of pyrimidic dimers under exposition to an UV radiation. The complementary use of quantitative static methods allowing the exploration of the potential energy surface of a chemical reaction, and of 'conceptual DFT' principles, leads to information concerning the mechanisms involved and to the rationalization of the differences in the nucleo-bases reactivity towards the formation of a same kind of damage. At the same time, a reflexion was undertaken on the asynchronous concerted mechanism concept, in terms of physical meaning of the transition state, respect of the Maximum Hardness Principle, and determination of the number of primitive processes involved. Finally, a new local reactivity index was developed, relevant to understand the reactivity of a molecular system in an excited state. (author)

  2. Hemoglobin allostery: new views on old players.

    Science.gov (United States)

    Miele, Adriana Erica; Bellelli, Andrea; Brunori, Maurizio

    2013-05-13

    Proteins are dynamic molecular machines whose structure and function are modulated by environmental perturbations and natural selection. Allosteric regulation, discovered in 1963 as a novel molecular mechanism of enzymatic adaptation [Monod, Changeux & Jacob (1963). J. Mol. Biol.6, 306-329], seems to be the leit motiv of enzymes and metabolic pathways, enabling fine and quick responses toward external perturbations. Hemoglobin (Hb), the oxygen transporter of all vertebrates, has been for decades the paradigmatic system to test the validity of the conformational selection mechanism, the conceptual innovation introduced by Monod, Wyman and Changeux. We present hereby the results of a comparative analysis of structure, function and thermodynamics of two extensively investigated hemoglobins: human HbA and trout HbI. They represent a unique and challenging comparison to test the general validity of the stereochemical model proposed by Perutz. Indeed both proteins are ideal for the purpose being very similar yet very different. In fact, T-HbI is a low-ligand-affinity cooperative tetrameric Hb, insensitive to all allosteric effectors. This remarkable feature, besides being physiologically sound, supports the stereochemical model, given that the six residues identified in HbA as responsible for the Bohr and the 2,3-di-phosphoglycerate effects are all mutated. Comparison of the three-dimensional structures of HbA and T-HbI allows unveiling the molecular mechanism whereby the latter has a lower O2 affinity. Moreover, the energetic balance sheet shows that the salt bridges breaking upon allosteric quaternary transition are important yet insufficient to account for the free energy of heme-heme interactions in both hemoglobins.

  3. Mini-hemoglobins from nemertean worms.

    Science.gov (United States)

    Vandergon, Thomas L; Riggs, Austen F

    2008-01-01

    Hemoglobins (Hbs) found in members of the phylum Nemertea are smaller than any other known Hb molecules. These mini-Hbs have been of great interest because of their unique three-dimensional structure and their stable ligand-binding properties. Also of interest is the expression of mini-Hb in neural tissue, body wall muscle tissue, and red blood cells. This chapter outlines methods that may be used to isolate and purify functional mini-Hbs from all three tissue types in nemertean worms.

  4. Interaction of thyroid hormone and hemoglobin: nature of the interaction and effect of hemoglobin on thyroid hormone radioimmunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Davis, P.J.; Yoshida, K.; Schoenl, M.

    1980-05-01

    Gel filtration of human erythrocyte (RBC) lysate incubated with labeled thyroxine (Tu) or triiodothyronine (Tt) revealed co-elution of a major iodothyronine-binding fraction (R-2) and hemoglobin. Solutions of purified human hemoglobin and Tt also showed co-elution of hormone and hemoglobin. Because hematin and protoporphyrin were shown to bind labeled Tt, the oxygen-binding site on hemoglobin was excluded as the site of iodothyronine-hemoglobin interaction. Analysis of hormone binding by heme and globin moieties showed Tt binding to be limited to the heme fraction. Addition of excess unlabeled Tt to hemoglobin or heme incubated with labeled Tt indicated 75% to 90% of hormone binding was poorly dissociable. These observations suggested that the presence of hemoglobin in RBC lysate or in serum could influence the measurement of Tu and Tt by specific radioimmunoassay (RIA). Subsequent studies of the addition to serum of human hemoglobin revealed a significant reduction in Tt and Tu detectable by RIA in the presence of this protein. The effect was influenced by the concentration of hemoglobin and by duration and temperature of incubations of hemoglobin and serum prior to RIA.

  5. Relationship of Baseline Hemoglobin Level with Serum Ferritin, Postphlebotomy Hemoglobin Changes, and Phlebotomy Requirements among HFE C282Y Homozygotes

    Directory of Open Access Journals (Sweden)

    Seyed Ali Mousavi

    2015-01-01

    Full Text Available Objectives. We aimed to examine whether baseline hemoglobin levels in C282Y-homozygous patients are related to the degree of serum ferritin (SF elevation and whether patients with different baseline hemoglobin have different phlebotomy requirements. Methods. A total of 196 patients (124 males and 72 females who had undergone therapeutic phlebotomy and had SF and both pre- and posttreatment hemoglobin values were included in the study. Results. Bivariate correlation analysis suggested that baseline SF explains approximately 6 to 7% of the variation in baseline hemoglobin. The results also showed that males who had higher (≥150 g/L baseline hemoglobin levels had a significantly greater reduction in their posttreatment hemoglobin despite requiring fewer phlebotomies to achieve iron depletion than those who had lower (<150 g/L baseline hemoglobin, regardless of whether baseline SF was below or above 1000 µg/L. There were no significant differences between hemoglobin subgroups regarding baseline and treatment characteristics, except for transferrin saturation between male subgroups with SF above 1000 µg/L. Similar differences were observed when females with higher (≥138 g/L baseline hemoglobin were compared with those with lower (<138 g/L baseline hemoglobin. Conclusion. Dividing C282Y-homozygous patients into just two subgroups according to the degree of baseline SF elevation may obscure important subgroup variations.

  6. Quantum mechanical calculations of vibrational population inversion in chemical reactions - Numerically exact L-squared-amplitude-density study of the H2Br reactive system

    Science.gov (United States)

    Zhang, Y. C.; Zhang, J. Z. H.; Kouri, D. J.; Haug, K.; Schwenke, D. W.

    1988-01-01

    Numerically exact, fully three-dimensional quantum mechanicl reactive scattering calculations are reported for the H2Br system. Both the exchange (H + H-prime Br to H-prime + HBr) and abstraction (H + HBR to H2 + Br) reaction channels are included in the calculations. The present results are the first completely converged three-dimensional quantum calculations for a system involving a highly exoergic reaction channel (the abstraction process). It is found that the production of vibrationally hot H2 in the abstraction reaction, and hence the extent of population inversion in the products, is a sensitive function of initial HBr rotational state and collision energy.

  7. Specificity for human hemoglobin enhances Staphylococcus aureus infection

    Science.gov (United States)

    Pishchany, Gleb; McCoy, Amanda L.; Torres, Victor J.; Krause, Jens C.; Crowe, James E.; Fabry, Mary E.; Skaar, Eric P.

    2010-01-01

    SUMMARY Iron is required for bacterial proliferation and Staphylococcus aureus steals this metal from host hemoglobin during invasive infections. This process involves hemoglobin binding to the cell wall of S. aureus, heme extraction, passage through the cell envelope, and degradation to release free iron. Herein we demonstrate an enhanced ability of S. aureus to bind hemoglobin derived from humans as compared to other mammals. Increased specificity for human hemoglobin (hHb) translates into an improved ability to acquire iron and is entirely dependent on the staphylococcal hemoglobin receptor IsdB. This feature affects host-pathogen interaction as demonstrated by the increased susceptibility of hHb expressing mice to systemic staphylococcal infection. Interestingly, enhanced utilization of human hemoglobin is not a uniform property of all bacterial pathogens. These results suggest a step in the evolution of S. aureus to better colonize the human host and establish hHb expressing mice as a model of S. aureus pathogenesis. PMID:21147468

  8. Hemoglobin Moabit: alpha 86 (F7) Leu leads to Arg: a new unstable abnormal hemoglobin.

    Science.gov (United States)

    Knuth, A; Pribilla, W; Marti, H R; Winterhalter, K H

    1979-01-01

    A new alpha chain abnormal hemoglobin variant was found in a Turkish patient with a mild Heinz body hemolytic anemia and splenomegaly. The substitution alpha 86 Leu leads to Arg, which is next to the heme binding proximal histidine, is responsible for a marked instability of the molecule. The oxygen affinity of the erythrocytes was found to be slightly decreased.

  9. Physico-chemical properties and gasification reactivity of co-pyrolysis char from different rank of coal blended with lignocellulosic biomass: Effects of the cellulose.

    Science.gov (United States)

    Wu, Zhiqiang; Wang, Shuzhong; Luo, Zhengyuan; Chen, Lin; Meng, Haiyu; Zhao, Jun

    2017-07-01

    In this paper, the influence of cellulose on the physicochemical properties and the gasification reactivity of co-pyrolysis char was investigated. A specific surface area analyzer and an X-ray diffraction system were used to characterize the pore structure and the micro-crystalline structure of char. Fractal theory and deconvolution method were applied to quantitatively investigate the influence of cellulose on the structure of co-pyrolysis char. The results indicate that the improvements in the pore structure due to the presence of cellulose are more pronounced in the case of anthracite char with respect to bituminous char. Cellulose promotes the ordering of micro-scale structure and the uniformity of both anthracite and bituminous char, while the negative synergetic effect was observed during gasification of co-pyrolysis char. The exponential relationships between fractal dimension and specific surface area were determined, along with the relations between the gasification reactivity index and the microcrystalline structure parameter. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Molecular Quantum Similarity, Chemical Reactivity and Database Screening of 3D Pharmacophores of the Protein Kinases A, B and G from Mycobacterium tuberculosis.

    Science.gov (United States)

    Morales-Bayuelo, Alejandro

    2017-06-21

    Mycobacterium tuberculosis remains one of the world's most devastating pathogens. For this reason, we developed a study involving 3D pharmacophore searching, selectivity analysis and database screening for a series of anti-tuberculosis compounds, associated with the protein kinases A, B, and G. This theoretical study is expected to shed some light onto some molecular aspects that could contribute to the knowledge of the molecular mechanics behind interactions of these compounds, with anti-tuberculosis activity. Using the Molecular Quantum Similarity field and reactivity descriptors supported in the Density Functional Theory, it was possible to measure the quantification of the steric and electrostatic effects through the Overlap and Coulomb quantitative convergence (alpha and beta) scales. In addition, an analysis of reactivity indices using global and local descriptors was developed, identifying the binding sites and selectivity on these anti-tuberculosis compounds in the active sites. Finally, the reported pharmacophores to PKn A, B and G, were used to carry out database screening, using a database with anti-tuberculosis drugs from the Kelly Chibale research group (http://www.kellychibaleresearch.uct.ac.za/), to find the compounds with affinity for the specific protein targets associated with PKn A, B and G. In this regard, this hybrid methodology (Molecular Mechanic/Quantum Chemistry) shows new insights into drug design that may be useful in the tuberculosis treatment today.

  11. Stability of Blood Samples for Hemoglobin Electrophoresis

    Directory of Open Access Journals (Sweden)

    Yadira Valdés Fraser

    2013-07-01

    Full Text Available Background: the National Medical Genetics Center has conducted the prenatal screening for hemoglobinopathies in the province of Artemisa and the quality control of this program nationwide; reliability of the results is determined by the quality of the samples used. Objective: to describe the stability of whole blood samples using EDTAK2 and heparin as anticoagulants. Methods: a descriptive study of 100 samples of whole blood from pregnant women and their husbands was conducted at the National Medical Genetics Center. Hemoglobin electrophoresis with Hydrasis technology was performed using 10 % EDTAK2, 2.2 % and 5 % heparin, temperature at 4-8 0C and shelf-life of 7.15 and 30 days. Results: samples with EDTAK2 showed stability for a month with accuracy and repeatability in the electrophoresis runs. By using 5 % and 2.2 % heparin, problems were found in all periods analyzed. Conclusions: 10 % EDTAK2 anticoagulant is appropriate to ensure the reliability of the results in the screening for hemoglobinopathies. The results obtained in this study can be applied in all clinical, hematological and hemoglobin electrophoresis laboratories.

  12. A review of variant hemoglobins interfering with hemoglobin A1c measurement.

    Science.gov (United States)

    Little, Randie R; Roberts, William L

    2009-05-01

    Hemoglobin A1c (HbA1c) is used routinely to monitor long-term glycemic control in people with diabetes mellitus, as HbA1c is related directly to risks for diabetic complications. The accuracy of HbA1c methods can be affected adversely by the presence of hemoglobin (Hb) variants or elevated levels of fetal hemoglobin (HbF). The effect of each variant or elevated HbF must be examined with each specific method. The most common Hb variants worldwide are HbS, HbE, HbC, and HbD. All of these Hb variants have single amino acid substitutions in the Hb beta chain. HbF is the major hemoglobin during intrauterine life; by the end of the first year, HbF falls to values close to adult levels of approximately 1%. However, elevated HbF levels can occur in certain pathologic conditions or with hereditary persistence of fetal hemoglobin. In a series of publications over the past several years, the effects of these four most common Hb variants and elevated HbF have been described. There are clinically significant interferences with some methods for each of these variants. A summary is given showing which methods are affected by the presence of the heterozygous variants S, E, C, and D and elevated HbF. Methods are divided by type (immunoassay, ion-exchange high-performance liquid chromatography, boronate affinity, other) with an indication of whether the result is artificially increased or decreased by the presence of a Hb variant. Laboratorians should be aware of the limitations of their method with respect to these interferences.

  13. Properties of Hemoglobin Decolorized with a Histidine-Specific Protease.

    Science.gov (United States)

    Shi, Jing; de Roos, Andre; Schouten, Olaf; Zheng, Chaoya; Vink, Collin; Vonk, Brenda; Kliphuis, Annette; Schaap, Albert; Edens, Luppo

    2015-06-01

    This study investigated the application of Aspergilloglutamic peptidase (AGP) on porcine hemoglobin decolorization. AGP from fungus Aspergillus niger is identified to possess a high preference towards the histidine residues. As histidine residues in hemoglobin are known to coordinate the heme group within the globin molecule, we therefore hypothesized that incubating hemoglobin with a histidine-specific protease would efficiently separate the non-heme peptides from the heme-enriched peptides with a minimum degree of hydrolysis. AGP-decolored porcine hemoglobin hydrolysates were assessed on their functional (for example, color, emulsification, foaming, and water binding) and sensory properties. The results were compared with commercially available blood-derived proteins (subtilisin-decolored hemoglobin hydrolysates and plasma protein). It was observed that AGP is able to effectively decolor hemoglobin. The degree of hydrolysis (DH) increased less than 3% using AGP to achieve 90% color reduction of hemoglobin, whereas a DH increase of more than 20% is needed using subtilisin. The AGP-decolored hemoglobin hydrolysates (AGP-Hb) possess good emulsification, foaming, and water binding properties, which are better or comparable with the plasma protein, and much better than the subtilisin-decolored hemoglobin hydrolysates (subtilisin-Hb). The model canned meat with addition of AGP-Hb showed the highest value in hardness, springiness, and chewiness from the texture analysis. Furthermore, the canned meat with AGP-Hb was found to have a better sensory profile than the ones with addition of subtilisin-Hb and plasma protein.

  14. Hemoglobin screening: response of a Brazilian community to optional programs

    Directory of Open Access Journals (Sweden)

    Antonio Sérgio Ramalho

    1999-09-01

    Full Text Available The efficiency and the viability of three hemoglobin screening programs were investigated. They were offered on a voluntary basis to a Brazilian population and started with the analysis of blood donors, pregnant women and students. The hemoglobin screening was done through optional exams which included electrophoresis of hemoglobin and complementary hematological tests. A total of 13,670 people were tested over a period of 39 months and a total of 644 individuals with hereditary hemoglobin disorders were detected - 4.7% of the samples examined. The programs showed satisfactory indicators of viability and efficiency, expressed by the significative proportion of exams performed among the probands and their relatives.

  15. The investigation of resveratrol and analogs as potential inducers of fetal hemoglobin.

    Science.gov (United States)

    Theodorou, Andria; Phylactides, Marios; Forti, Luca; Cramarossa, Maria Rita; Spyrou, Pantelis; Gambari, Roberto; Thein, Swee Lay; Kleanthous, Marina

    2016-05-01

    Βeta-thalassemia, is a hemoglobinopathy characterized by reduced beta-globin chain synthesis, leading to imbalanced globin chain production, ineffective erythropoiesis and anemia. Increasing gamma-globin gene expression is a promising therapeutic approach as it reduces this imbalance by combining with the excess alpha globin chains and producing fetal hemoglobin (HbF). Furthermore, increased iron absorption and repeated blood transfusions lead to iron overload and tissue damage secondary to reactive oxygen species. Compounds exhibiting both antioxidant and HbF inducing activities are, therefore, highly desirable therapeutic agents. Resveratrol, a natural phytoalexin, combines these two activities but is also cytotoxic. Nine hydroxystilbenic resveratrol derivatives were synthesized in an attempt to identify compounds that retain the HbF-inducing and antioxidant activities of resveratrol but exhibit reduced cytotoxicity. Three derivatives (P1, P4 and P11) exhibited similar hemoglobin-inducing properties to resveratrol in K562 cells, however, only P11 showed reduced cytotoxicity. All three derivatives demonstrated variable HbF-inducing activity in primary erythroid progenitor cells from healthy donors. Resveratrol and P11 increased HbF induction significantly, with P11 having the highest activity. Additionally, P4 significantly increased progenitor numbers. A combinatorial treatment in K562 cells using resveratrol and decitabine resulted in a statistically significant increase in hemoglobin-inducing activity only above the level shown by resveratrol alone.

  16. Can hydroxylamine be a more potent nucleophile for the reactivation of tabun-inhibited AChE than prototype oxime drugs? An answer derived from quantum chemical and steered molecular dynamics studies.

    Science.gov (United States)

    Lo, Rabindranath; Ganguly, Bishwajit

    2014-07-29

    Organophosphorus nerve agents are highly toxic compounds which strongly inhibit acetylcholinesterase (AChE) in the blood and in the central nervous system (CNS). Tabun is one of the highly toxic organophosphorus (OP) compounds and is resistant to many oxime drugs formulated for the reactivation of AChE. The reactivation mechanism of tabun-conjugated AChE with various drugs has been examined with density functional theory and ab initio quantum chemical calculations. The presence of a lone-pair located on the amidic group resists the nucleophilic attack at the phosphorus center of the tabun-conjugated AChE. We have shown that the newly designed drug candidate N-(pyridin-2-yl)hydroxylamine, at the MP2/6-31+G*//M05-2X/6-31G* level in the aqueous phase with the polarizable continuum solvation model (PCM), is more effective in reactivating the tabun-conjugated AChE than typical oxime drugs. The rate determining activation barrier with N-(pyridin-2-yl)hydroxylamine was found to be ∼1.7 kcal mol(-1), which is 7.2 kcal mol(-1) lower than the charged oxime trimedoxime (one of the most efficient reactivators in tabun poisonings). The greater nucleophilicity index (ω(-)) and higher CHelpG charge of pyridinylhydroxylamine compared to TMB4 support this observation. Furthermore, we have also examined the reactivation process of tabun-inhibited AChE with some other bis-quaternary oxime drug candidates such as methoxime (MMB4) and obidoxime. The docking analysis suggests that charged bis-quaternary pyridinium oximes have greater binding affinity inside the active-site gorge of AChE compared to the neutral pyridinylhydroxylamine. The peripheral ligand attached to the neutral pyridinylhydroxylamine enhanced the binding with the aromatic residues in the active-site gorge of AChE through effective π-π interactions. Steered molecular dynamics (SMD) simulations have also been performed with the charged oxime (TMB4) and the neutral hydroxylamine. From protein-drug interaction

  17. An expeditious and green synthesis of new enaminones and study their chemical reactivity toward some different amines and binucleophiles under environmentally friendly conditions

    Directory of Open Access Journals (Sweden)

    Khadijah M. Al-Zaydi

    2017-05-01

    Full Text Available The condensation reaction of 3-heteroaromatic-3-oxopropanenitriles 3, 4 and 7 with dimethylformamide–dimethylacetal (DMF–DMA gave the corresponding enaminones 8, 9 and 10, respectively. Nucleophilic substitution of 8 and 9 with different amines resulted in a new derivatives of enaminones 11–18. The reactivity of enaminones 8 and 9 toward some nitrogen nucleophiles was investigated with a view to synthesize new heterocyclic systems. Thus, treatment of compounds 8 and 9 with phenylhydrazine afforded the pyrazole derivatives 19 and 20, respectively. On the other hand, reacting 8 and 9 with guanidine gave the pyrimidines 21 and 22, respectively. Treatment of compound 9 with hydroxylamine hydrochloride afforded the aminoisoxazoles 23. The foregoing reactions were carried out with conventional heating and under green conditions [ultrasound (US irradiations or ionic liquids (ILs] and a comparative study was employed. All the new structures are fully characterized.

  18. On Diffusion of Chemically Reactive Species in a Convective Flow Past an Inclined Plate with Variable Surface Temperature and Variable Mass Diffusion

    Directory of Open Access Journals (Sweden)

    Kirubavathi J.D.

    2016-12-01

    Full Text Available A numerical solution of a transient natural convection flow past a semi-infinite inclined plate under the combined buoyancy effects of heat and mass transfer along with chemical reaction is presented herewith. The governing boundary layer equations for the above flow problem for a first order homogeneous chemical reaction are set up and non-dimensionalised. An implicit finite difference method is employed to solve the unsteady, nonlinear, integro and coupled partial differential equation. Numerical results are presented for various parameters occurring in the problem. The unsteady velocity, temperature and concentration profiles, local and average skin friction, Nusselt number and Sherwood number are studied for both a generative and destructive reaction.

  19. Reactive Systems

    DEFF Research Database (Denmark)

    Aceto, Luca; Ingolfsdottir, Anna; Larsen, Kim Guldstrand

    A reactive system comprises networks of computing components, achieving their goals through interaction among themselves and their environment. Thus even relatively small systems may exhibit unexpectedly complex behaviours. As moreover reactive systems are often used in safety critical systems......, the need for mathematically based formal methodology is increasingly important. There are many books that look at particular methodologies for such systems. This book offers a more balanced introduction for graduate students and describes the various approaches, their strengths and weaknesses, and when...... they are best used. Milner's CCS and its operational semantics are introduced, together with the notions of behavioural equivalences based on bisimulation techniques and with recursive extensions of Hennessy-Milner logic. In the second part of the book, the presented theories are extended to take timing issues...

  20. Combinatorics of giant hexagonal bilayer hemoglobins.

    Science.gov (United States)

    Hanin, L G; Vinogradov, S N

    2000-01-01

    The paper discusses combinatorial and probabilistic models allowing to characterize various aspects of spacial symmetry and structural heterogeneity of the giant hexagonal bilayer hemoglobins (HBL Hb). Linker-dodecamer configurations of HBL are described for two and four linker types (occurring in the two most studied HBL Hb of Arenicola and Lumbricus, respectively), and the most probable configurations are found. It is shown that, for HBL with marked dodecamers, the number of 'normal-marked' pairs of dodecamers in homological position follows a binomial distribution. The group of symmetries of the dodecamer substructure of HBL is identified with the dihedral group D6. Under natural symmetry assumptions, the total dipole moment of the dodecamer substructure of HBL is shown to be zero. Biological implications of the mathematical findings are discussed.