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Sample records for irreversible enzymatic reaction

  1. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  2. Competing irreversible cooperative reactions on polymer chains

    International Nuclear Information System (INIS)

    Evans, J.W.; Hoffman, D.K.; Burgess, D.R.

    1984-01-01

    We analyze model processes involving competition between several irreversible reactions at the sites of a 1D, infinite, uniform polymer chain. These reactions can be cooperative, i.e., the corresponding rates depend on the state of the surrounding sites. An infinite hierarchy of rate equations is readily derived for the probabilities of various subconfigurations. By exploiting a shielding property of suitable blocks of unreacted sites, we show how exact hierarchy truncation and solution is sometimes possible. The behavior of solutions is illustrated in several cases by plotting families of ''reaction trajectories'' for varying ratios of reactant concentrations. As a specific application, we consider competition between coordination of ZnCl 2 to pairs of oxygen atoms and to single oxygen atoms in poly(propylene oxide). The observed glass transition temperature behavior is eludicated

  3. Enzymatic treatment for controlling irreversible membrane fouling in cross-flow humic acid-fed ultrafiltration

    International Nuclear Information System (INIS)

    Yu, Chien-Hwa; Fang, Lung-Chen; Lateef, Shaik Khaja; Wu, Chung-Hsin; Lin, Cheng-Fang

    2010-01-01

    Exploring reasonable ways to remove foulant is of great importance in order to allow sustainable operation of ultrafiltration (UF) membranes in water/wastewater treatment technology. Compounds of organic and inorganic origin largely contribute to irreversible fouling. This study attempted to remove problem of UF membrane fouling by using four different enzymes including α-amylase, lipase, cellulase and protease. This investigation showed that none of the above mentioned enzymes was found to be effective for the removal of foulant when used alone. However, when these enzymes were used in combination with NaOH and citric acid, about 90% cleaning was achieved. The addition of non-ionic surfactant to the enzymatic solution appears to increase the efficiency of flux recovery by reducing the adhesion of foulant species to the membrane surface through the decrease of contact angle. Field emission gun scanning electron microscopy, Fourier transform infrared spectroscopy and atomic force microscopy (AFM) techniques were employed to qualitatively illustrate the foulant characteristics. The surface roughness through AFM was used to explain the potential mechanism for the enzymatic cleaning.

  4. Enzymatic treatment for controlling irreversible membrane fouling in cross-flow humic acid-fed ultrafiltration

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Chien-Hwa [Department of Civil and Environment Engineering, Nanya Institute of Technology, Taoyuan, Taiwan (China); Fang, Lung-Chen; Lateef, Shaik Khaja [Graduate Institute of Environmental Engineering, National Taiwan University, Taipei, Taiwan (China); Wu, Chung-Hsin, E-mail: chunghsinwu@yahoo.com.tw [Department of Chemical and Materials Engineering, National Kaohsiung University of Applied Sciences, 415 Chien Kung Road, Kaohsiung 807, Taiwan (China); Lin, Cheng-Fang [Graduate Institute of Environmental Engineering, National Taiwan University, Taipei, Taiwan (China)

    2010-05-15

    Exploring reasonable ways to remove foulant is of great importance in order to allow sustainable operation of ultrafiltration (UF) membranes in water/wastewater treatment technology. Compounds of organic and inorganic origin largely contribute to irreversible fouling. This study attempted to remove problem of UF membrane fouling by using four different enzymes including {alpha}-amylase, lipase, cellulase and protease. This investigation showed that none of the above mentioned enzymes was found to be effective for the removal of foulant when used alone. However, when these enzymes were used in combination with NaOH and citric acid, about 90% cleaning was achieved. The addition of non-ionic surfactant to the enzymatic solution appears to increase the efficiency of flux recovery by reducing the adhesion of foulant species to the membrane surface through the decrease of contact angle. Field emission gun scanning electron microscopy, Fourier transform infrared spectroscopy and atomic force microscopy (AFM) techniques were employed to qualitatively illustrate the foulant characteristics. The surface roughness through AFM was used to explain the potential mechanism for the enzymatic cleaning.

  5. Novel investigation of enzymatic biodiesel reaction by isothermal calorimetry

    DEFF Research Database (Denmark)

    Søtoft, Lene Fjerbaek; Westh, Peter; Christensen, Knud V.

    2010-01-01

    Isothermal calorimetry (ITC) was used to investigate solvent-free enzymatic biodiesel production. The transesterification of rapeseed oil with methanol and ethanol was catalyzed by immobilized lipase Novozym 435 at 40 °C. The aim of the study was to determine reaction enthalpy for the enzymatic...... transesterification and to elucidate the mass transfer and energetic processes taking place. Based on the measured enthalpy and composition change in the system, the heat of reaction at 40 °C for the two systems was determined as −9.8 ± 0.9 kJ/mole biodiesel formed from rapeseed oil and methanol, and −9.3 ± 0.7 k...

  6. Biosensing strategies based on enzymatic reactions and nanoparticles.

    Science.gov (United States)

    Díez-Buitrago, Beatriz; Briz, Nerea; Liz-Marzán, Luis M; Pavlov, Valeri

    2018-04-16

    Enzymes are pivotal elements in bioanalysis due to their specificity and extremely high catalytic activity. The sensitivity of bioanalytical assays depends mainly on the capacity of an observer to detect the product(s) of a biocatalytic reaction. Both natural and artificial compounds have been traditionally used to evaluate enzymatic activities. The drawbacks of chromogenic and fluorogenic organic enzymatic substrates are their high cost and low stability, resulting in high background signals. We review here state of the art assays in the detection of enzymatic activities using recent advances in nanoscience. Novel methods based on the use of nanoparticles lead to increased sensitivity and decreased costs for bioanalysis based on enzymes as recognition elements and signal amplifiers in Enzyme-Linked Immunosorbent Assays (ELISA). Novel approaches toward the detection of enzymatic activities are based on biocatalytic synthesis, modulation, etching, and aggregation of nanoparticles under physiological conditions.

  7. Formation of Irreversible H-bonds in Cellulose Materials

    Science.gov (United States)

    Umesh P. Agarwal; Sally A. Ralph; Rick S. Reiner; Nicole M. Stark

    2015-01-01

    Understanding of formation of irreversible Hbonds in cellulose is important in a number of fields. For example, fields as diverse as pulp and paper and enzymatic saccharification of cellulose are affected. In the present investigation, the phenomenon of formation of irreversible H-bonds is studied in a variety of celluloses and under two different drying conditions....

  8. Chemical modeling of irreversible reactions in nuclear waste-water-rock systems

    International Nuclear Information System (INIS)

    Wolery, T.J.

    1981-02-01

    Chemical models of aqueous geochemical systems are usually built on the concept of thermodynamic equilibrium. Though many elementary reactions in a geochemical system may be close to equilibrium, others may not be. Chemical models of aqueous fluids should take into account that many aqueous redox reactions are among the latter. The behavior of redox reactions may critically affect migration of certain radionuclides, especially the actinides. In addition, the progress of reaction in geochemical systems requires thermodynamic driving forces associated with elementary reactions not at equilibrium, which are termed irreversible reactions. Both static chemical models of fluids and dynamic models of reacting systems have been applied to a wide spectrum of problems in water-rock interactions. Potential applications in nuclear waste disposal range from problems in geochemical aspects of site evaluation to those of waste-water-rock interactions. However, much further work in the laboratory and the field will be required to develop and verify such applications of chemical modeling

  9. Cascade enzymatic reactions for efficient carbon sequestration.

    Science.gov (United States)

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Apple phenolics and their contribution to enzymatic browning reactions

    Directory of Open Access Journals (Sweden)

    Wiesław Oleszek

    2014-01-01

    Full Text Available Chlorogenic acid, epicatechin, procyanidin B2 and C1 were isolated from apple skin. These compounds as well as quercetine and phloretine glycosides isolated from apples were studied individually and as mixtures for their participation in the enzymatic browning reactions. The importance of quercetine glycosides and the synergistic effect of phloridzin and phloretine xyloglucoside with chlorogenic acid and flavans in the browning reaction are reported.

  11. Irreversible thermodynamics of Poisson processes with reaction.

    Science.gov (United States)

    Méndez, V; Fort, J

    1999-11-01

    A kinetic model is derived to study the successive movements of particles, described by a Poisson process, as well as their generation. The irreversible thermodynamics of this system is also studied from the kinetic model. This makes it possible to evaluate the differences between thermodynamical quantities computed exactly and up to second-order. Such differences determine the range of validity of the second-order approximation to extended irreversible thermodynamics.

  12. Isothermal calorimetry of enzymatic biodiesel reaction

    DEFF Research Database (Denmark)

    Fjerbæk Søtoft, Lene; Westh, Peter; Christensen, Knud Villy

    2010-01-01

      Isothermal calorimetry ITC has been used to investigate enzymatic biodiesel production. The transesterification of rapeseed oil with methanol and ethanol was catalyzed by the immobilized lipase Novozym 435 at 40°C. The ITC-experiments clearly demonstrate the possibilities of investigating complex...... and composition change in the system, the heat of reaction at 40°C for the two systems has been determined to -9.8 ± 0.9 kJ/mole biodiesel formed from rapeseed oil and methanol, and - 9.3 ± 0.7 kJ/mole when rapeseed oil and ethanol is used....

  13. Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2016-04-01

    Full Text Available In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-d-glucuronic acid and α-d-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-d-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named

  14. Method of reduction of nitroaromatics by enzymatic reaction with redox enzymes

    Science.gov (United States)

    Shah, Manish M.

    2000-01-01

    A method for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with redox enzymes, such as Oxyrase (Trademark of Oxyrase, Inc., Mansfield, Ohio).

  15. The In Situ Enzymatic Screening (ISES) Approach to Reaction Discovery and Catalyst Identification.

    Science.gov (United States)

    Swyka, Robert A; Berkowitz, David B

    2017-12-14

    The importance of discovering new chemical transformations and/or optimizing catalytic combinations has led to a flurry of activity in reaction screening. The in situ enzymatic screening (ISES) approach described here utilizes biological tools (enzymes/cofactors) to advance chemistry. The protocol interfaces an organic reaction layer with an adjacent aqueous layer containing reporting enzymes that act upon the organic reaction product, giving rise to a spectroscopic signal. ISES allows the experimentalist to rapidly glean information on the relative rates of a set of parallel organic/organometallic reactions under investigation, without the need to quench the reactions or draw aliquots. In certain cases, the real-time enzymatic readout also provides information on sense and magnitude of enantioselectivity and substrate specificity. This article contains protocols for single-well (relative rate) and double-well (relative rate/enantiomeric excess) ISES, in addition to a colorimetric ISES protocol and a miniaturized double-well procedure. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  16. A Method for the Determination of Bi-substrate Kinetic Coefficients: the Example of the b-D-glucose- NAD-GDH Enzymatic Reaction

    Directory of Open Access Journals (Sweden)

    Jean BERTHIER

    2015-08-01

    Full Text Available Colorimetric detection of glucose in sample liquids such as human plasma is made by using enzymatic reactions. Either glucose oxidase (GOX or glucose dehydrogenase (GDH can be used to convert glucose. In the multi reactional scheme, the first enzymatic reaction is determinant. We focused here on the study of the enzyme GDH together with the enzymatic cofactor NAD (nicotinamide adenine dinucleotide. This reaction falls in the category of ternary enzymatic reactions. Such reactions depend on four parameters. A method to determine these four parameters is presented in this work, based on a comparison between a series of experiments and the theory. The best values of the parameters are indicated.

  17. Relativistic thermodynamics of irreversible processes I. Heat conduction, diffusion, viscous flow and chemical reactions; formal part

    NARCIS (Netherlands)

    Kluitenberg, G.A.; Groot, S.R. de; Mazur, P.

    1953-01-01

    The relativistic thermodynamics of irreversible processes is developed for an isotropic mixture in which heat conduction, diffusion, viscous flow, chemical reactions and their cross-phenomena may occur. The four-vectors, representing the relative flows of matter, are defined in such a way that, in

  18. The Effect of Irradiation Treatment on the Non-Enzymatic Browning Reaction in Legume Seeds

    International Nuclear Information System (INIS)

    El-Niely, H.F.G.

    2013-01-01

    The present study was conducted to evaluate the effects of gamma irradiation treatment, at room temperature, on the non-enzymatic browning reaction (Millerd reaction products, MRPs) generated in soybeans, broad beans and dried peas seeds at dose levels of 10, 30 and 60 kGy and their effects on the chemical constituents, soluble protein, available lysine and in vitro protein digestibility. The formation of MRPs in the studied legumes was assayed by monitoring the formation of brown pigments (browning intensity) by spectrophotometric method. The results revealed that the chemical composition of irradiated legumes showed non-significant differences relative to the raw one. A dose dependent decrease in soluble proteins and available lysine in the three legumes were observed. The non-enzymatic browning reaction was significantly increased with increasing the radiation dose, which was proved by changes in browning index tests. At the same time, the in vitro protein digestibility was increased after irradiation up to 60 kGy. Irradiation of dried peas with 60 kGy produced higher browning index than the other legumes. A positive correlation was observed between the radiation dose and the browning index for soybeans (R2= 0.96), broad beans (R2 = 0.81) and dried peas (R2 = 0.97) which means that 96%, 81% and 97 of the variation in the incidence of non-enzymatic browning reaction in soybean, broad bean and dried peas, respectively, are due to the effect of irradiation treatments. The present study suggests that the formation of non-enzymatic browning reaction did not impair the nutritional quality of legumes, therefore, the process of irradiation was helpful in increasing the in vitro protein digestibility of studied legumes. These results clearly indicated that gamma irradiation processing at the studied doses can add valuable effects to the studied legumes

  19. The browning kinetics of the non-enzymatic browning reaction in L-ascorbic acid/basic amino acid systems

    Directory of Open Access Journals (Sweden)

    Ai-Nong YU

    Full Text Available Abstract Under the conditions of weak basis and the reaction temperature range of 110-150 °C, lysine, arginine and histidine were reacted with L-ascorbic acid at equal amount for 30-150 min, respectively and the formation of browning products was monitored with UV–vis spectrometry. The kinetic characteristics of their non-enzymatic browning reaction were investigated. The study results indicated that the non-enzymatic browning reaction of these three amino acids with L-ascorbic acid to form browning products was zero-order reaction. The apparent activation energies for the formation of browning products from L-ascorbic acid/lysine, L-ascorbic acid/arginine and L-ascorbic acid/histidine systems were 54.94, 50.08 and 35.31kJ/mol. The activation energy data indicated the degree of effects of reaction temperature on non-enzymatic browning reaction. Within the temperature range of 110-150 °C, the reaction rate of L-ascorbic acid/lysine system was the fastest one, followed by that of the L-ascorbic acid/arginine system. The reaction rate of L-ascorbic acid/histidine system was the slowest one. Based on the observed kinetic data, the formation mechanisms of browning products were proposed.

  20. Carpatizine, a novel bridged oxazine derivative generated by non-enzymatic reactions.

    Science.gov (United States)

    Fu, Peng; MacMillan, John B

    2017-06-27

    Carpatizine (1), a new bridged oxazine derivative, was isolated from a marine-derived Streptomyces strain SNE-011. The structure was fully determined by spectroscopic analysis, ECD calculations and chemical methods. A plausible non-enzymatic reaction mechanism from daryamide D leading to carpatizine was presented, which was confirmed by chemical transformation.

  1. Solvent Optimization for Efficient Enzymatic Monoacylglycerol Production Based on a Glycerolysis Reaction

    DEFF Research Database (Denmark)

    Damstrup, Marianne; Jensen, Tine; Sparsø, Flemming V.

    2005-01-01

    This study was aimed at screening solvent systems of varying polarities to identify suitable solvents for efficient and practical enzymatic glycerolysis. Several pure solvents and solvent mixtures were screened in a batch reaction system consisting of glycerol, sunflower oil, and Novozymo (R) 435...

  2. Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

    Science.gov (United States)

    Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

    2016-01-01

    Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

  3. Technical Report for a Study on the Mechanism and Control of Non-Enzymatic Browning Reaction in Gamma-Irradiated Food

    Energy Technology Data Exchange (ETDEWEB)

    Byun, Myung Woo; Lee, Ju Woon; Kim, Jae Hun

    2007-01-15

    Gamma irradiation leads to a non-enzymatic browning reaction (carbonyl -amine reaction) in an aqueous system similar to those induced in a heated one. This reaction may influence the changes of the color in irradiated foods. The intensity of the reaction was dependent on the type of the sugar, if the occurrence is by irradiation or by heating. There was a difference in the browning reaction between irradiation and heating. Although no browning was observed in the heated solution of the non-reducing sugar, the formation of colored products was observed in the irradiated sucrose-lysine solution. It could be explained on the basis that irradiation promotes the breakdown of the glycosidic linkages of the disaccharide, sucrose and the produce of a reducing power. The high molecular weight melanoidin (> MW 12,000-14,000 Da) was produced by gamma irradiation from the non-enzymatic browning reaction between glucose and glycine. The structure of melanoidin was similar to melanodin from heat processing. The results suggested that gamma-irradiation occurred the non-enzymatic browning reaction that is similar the reaction by heat processing. Non-enzymatic browning reaction during gamma-irradiation processing was greatly influenced by pH and medium of reaction system. The brown color development of irradiated sugar solutions with and without glycine is more increased in buffer system especially with alkaline pH than DDW. When food is irradiated, off-color such as browning can be produced due to the non-enzymatic browning reaction and it is influenced by other ions and/or pH of system. This suggests that the browning of irradiated food might be retarded by lowering the pH of the system. Gamma-irradiation produce the free radical and the radiolysis products of sugar and glycine and then they may be condensed to colored products during post-irradiation. However, when the food is irradiated in frozen state, the production of free radical and radiolysis product is inhibited and it

  4. Technical Report for a Study on the Mechanism and Control of Non-Enzymatic Browning Reaction in Gamma-Irradiated Food

    International Nuclear Information System (INIS)

    Byun, Myung Woo; Lee, Ju Woon; Kim, Jae Hun

    2007-01-01

    Gamma irradiation leads to a non-enzymatic browning reaction (carbonyl -amine reaction) in an aqueous system similar to those induced in a heated one. This reaction may influence the changes of the color in irradiated foods. The intensity of the reaction was dependent on the type of the sugar, if the occurrence is by irradiation or by heating. There was a difference in the browning reaction between irradiation and heating. Although no browning was observed in the heated solution of the non-reducing sugar, the formation of colored products was observed in the irradiated sucrose-lysine solution. It could be explained on the basis that irradiation promotes the breakdown of the glycosidic linkages of the disaccharide, sucrose and the produce of a reducing power. The high molecular weight melanoidin (> MW 12,000-14,000 Da) was produced by gamma irradiation from the non-enzymatic browning reaction between glucose and glycine. The structure of melanoidin was similar to melanodin from heat processing. The results suggested that gamma-irradiation occurred the non-enzymatic browning reaction that is similar the reaction by heat processing. Non-enzymatic browning reaction during gamma-irradiation processing was greatly influenced by pH and medium of reaction system. The brown color development of irradiated sugar solutions with and without glycine is more increased in buffer system especially with alkaline pH than DDW. When food is irradiated, off-color such as browning can be produced due to the non-enzymatic browning reaction and it is influenced by other ions and/or pH of system. This suggests that the browning of irradiated food might be retarded by lowering the pH of the system. Gamma-irradiation produce the free radical and the radiolysis products of sugar and glycine and then they may be condensed to colored products during post-irradiation. However, when the food is irradiated in frozen state, the production of free radical and radiolysis product is inhibited and it

  5. Recent Trends in Quantum Chemical Modeling of Enzymatic Reactions.

    Science.gov (United States)

    Himo, Fahmi

    2017-05-24

    The quantum chemical cluster approach is a powerful method for investigating enzymatic reactions. Over the past two decades, a large number of highly diverse systems have been studied and a great wealth of mechanistic insight has been developed using this technique. This Perspective reviews the current status of the methodology. The latest technical developments are highlighted, and challenges are discussed. Some recent applications are presented to illustrate the capabilities and progress of this approach, and likely future directions are outlined.

  6. Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

    International Nuclear Information System (INIS)

    Amemiya, Kenta

    2015-01-01

    A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

  7. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.

    2014-01-01

    was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature......The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40°C) for 28 or 42 days. The oxidative stability of krill oil...

  8. Specific inflammatory response of Anemonia sulcata (Cnidaria) after bacterial injection causes tissue reaction and enzymatic activity alteration.

    Science.gov (United States)

    Trapani, M R; Parisi, M G; Parrinello, D; Sanfratello, M A; Benenati, G; Palla, F; Cammarata, M

    2016-03-01

    The evolution of multicellular organisms was marked by adaptations to protect against pathogens. The mechanisms for discriminating the ''self'' from ''non-self" have evolved into a long history of cellular and molecular strategies, from damage repair to the co-evolution of host-pathogen interactions. We investigated the inflammatory response in Anemonia sulcata (Cnidaria: Anthozoa) following injection of substances that varied in type and dimension, and observed clear, strong and specific reactions, especially after injection of Escherichia coli and Vibrio alginolyticus. Moreover, we analyzed enzymatic activity of protease, phosphatase and esterase, showing how the injection of different bacterial strains alters the expression of these enzymes and suggesting a correlation between the appearance of the inflammatory reaction and the modification of enzymatic activities. Our study shows for the first time, a specific reaction and enzymatic responses following injection of bacteria in a cnidarian. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. The dual effects of Maillard reaction and enzymatic hydrolysis on the antioxidant activity of milk proteins.

    Science.gov (United States)

    Oh, N S; Lee, H A; Lee, J Y; Joung, J Y; Lee, K B; Kim, Y; Lee, K W; Kim, S H

    2013-08-01

    The objective of this study was to determine the enhanced effects on the biological characteristics and antioxidant activity of milk proteins by the combination of the Maillard reaction and enzymatic hydrolysis. Maillard reaction products were obtained from milk protein preparations, such as whey protein concentrates and sodium caseinate with lactose, by heating at 55°C for 7 d in sodium phosphate buffer (pH 7.4). The Maillard reaction products, along with untreated milk proteins as controls, were hydrolyzed for 0 to 3h with commercial proteases Alcalase, Neutrase, Protamex, and Flavorzyme (Novozymes, Bagsværd, Denmark). The antioxidant activity of hydrolyzed Maillard reaction products was determined by reaction with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, their 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity, and the ability to reduce ferric ions. Further characteristics were evaluated by the o-phthaldialdehyde method and sodium dodecyl sulfate-PAGE. The degree of hydrolysis gradually increased in a time-dependent manner, with the Alcalase-treated Maillard reaction products being the most highly hydrolyzed. Radical scavenging activities and reducing ability of hydrolyzed Maillard reaction products increased with increasing hydrolysis time. The combined products of enzymatic hydrolysis and Maillard reaction showed significantly greater antioxidant activity than did hydrolysates or Maillard reaction products alone. The hydrolyzed Maillard reaction products generated by Alcalase showed significantly higher antioxidant activity when compared with the other protease products and the antioxidant activity was higher for the whey protein concentrate groups than for the sodium caseinate groups. These findings indicate that Maillard reaction products, coupled with enzymatic hydrolysis, could act as potential antioxidants in the pharmaceutical, food, and dairy industries. Copyright © 2013 American Dairy Science Association

  10. Modeling of uncertainties in biochemical reactions.

    Science.gov (United States)

    Mišković, Ljubiša; Hatzimanikatis, Vassily

    2011-02-01

    Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

  11. Effect of micro-stirring on enzymatic reaction kinetics inside a biomimetic container

    Science.gov (United States)

    Gozen, Irep; Horowitz, Viva; Chambers, Zachary; Manoharan, Vinothan

    The intracellular environment is dynamic, influenced by the motion of active machinery such as cytoskeleton filaments and molecular motors. To understand whether and how such activity affects the rates of diffusion-limited reactions, we construct a model system consisting of a phospholipid vesicle encapsulating a small number of micro- or nanoparticles, the active motion of which can be induced by chemical or magnetic cues. We aim to determine a relation between active motion of particles and rates of enzymatic reactions in the confined volume. Our findings might illuminate how active motion influences cytoplasmic reaction dynamics, or may have played a role in protocell genetics.

  12. Process technology for multi-enzymatic reaction systems

    DEFF Research Database (Denmark)

    Xue, Rui; Woodley, John M.

    2012-01-01

    In recent years, biocatalysis has started to provide an important green tool in synthetic organic chemistry. Currently, the idea of using multi-enzymatic systems for industrial production of chemical compounds becomes increasingly attractive. Recent examples demonstrate the potential of enzymatic...... synthesis and fermentation as an alternative to chemical-catalysis for the production of pharmaceuticals and fine chemicals. In particular, the use of multiple enzymes is of special interest. However, many challenges remain in the scale-up of a multi-enzymatic system. This review summarizes and discusses...... the technology options and strategies that are available for the development of multi-enzymatic processes. Some engineering tools, including kinetic models and operating windows, for developing and evaluating such processes are also introduced....

  13. Stochastic dynamics and irreversibility

    CERN Document Server

    Tomé, Tânia

    2015-01-01

    This textbook presents an exposition of stochastic dynamics and irreversibility. It comprises the principles of probability theory and the stochastic dynamics in continuous spaces, described by Langevin and Fokker-Planck equations, and in discrete spaces, described by Markov chains and master equations. Special concern is given to the study of irreversibility, both in systems that evolve to equilibrium and in nonequilibrium stationary states. Attention is also given to the study of models displaying phase transitions and critical phenomema both in thermodynamic equilibrium and out of equilibrium. These models include the linear Glauber model, the Glauber-Ising model, lattice models with absorbing states such as the contact process and those used in population dynamic and spreading of epidemic, probabilistic cellular automata, reaction-diffusion processes, random sequential adsorption and dynamic percolation. A stochastic approach to chemical reaction is also presented.The textbook is intended for students of ...

  14. Bistability, electric potentials and sensor behaviour in an enzymatic reaction system

    International Nuclear Information System (INIS)

    Malchow, H.; Felber, F.

    1987-07-01

    A special ionic enzyme kinetics in a continuously stirred flow reactor which is membrane coupled to a reservoir is considered starting from a general expression for the substrate dependence of enzymatic reaction rates including pH effects. Both bistability of the reaction and electric potentials between the interior and exterior of the reactor can be observed having regard to mass and charge conservation as well as global electroneutrality. The sudden jumps at critical concentration values from one stable solution branch to the other on a hysteresis loop are supposed to be the basic action principle of a non-equilibrium concentration threshold sensor. (author). 38 refs, 3 figs

  15. Establishing MALDI-TOF as Versatile Drug Discovery Readout to Dissect the PTP1B Enzymatic Reaction.

    Science.gov (United States)

    Winter, Martin; Bretschneider, Tom; Kleiner, Carola; Ries, Robert; Hehn, Jörg P; Redemann, Norbert; Luippold, Andreas H; Bischoff, Daniel; Büttner, Frank H

    2018-07-01

    Label-free, mass spectrometric (MS) detection is an emerging technology in the field of drug discovery. Unbiased deciphering of enzymatic reactions is a proficient advantage over conventional label-based readouts suffering from compound interference and intricate generation of tailored signal mediators. Significant evolvements of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS, as well as associated liquid handling instrumentation, triggered extensive efforts in the drug discovery community to integrate the comprehensive MS readout into the high-throughput screening (HTS) portfolio. Providing speed, sensitivity, and accuracy comparable to those of conventional, label-based readouts, combined with merits of MS-based technologies, such as label-free parallelized measurement of multiple physiological components, emphasizes the advantages of MALDI-TOF for HTS approaches. Here we describe the assay development for the identification of protein tyrosine phosphatase 1B (PTP1B) inhibitors. In the context of this precious drug target, MALDI-TOF was integrated into the HTS environment and cross-compared with the well-established AlphaScreen technology. We demonstrate robust and accurate IC 50 determination with high accordance to data generated by AlphaScreen. Additionally, a tailored MALDI-TOF assay was developed to monitor compound-dependent, irreversible modification of the active cysteine of PTP1B. Overall, the presented data proves the promising perspective for the integration of MALDI-TOF into drug discovery campaigns.

  16. Preparation and Characterization of Enzyme Compartments in UV-Cured Polyurethane-Based Materials and Their Application in Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Diana Uhrich

    2017-11-01

    Full Text Available The preparation and characterization of UV-cured polyurethane-based materials for the mild inclusion immobilization of enzymes was investigated. Full curing of the polymer precursor/enzyme solution mixture was realized by a short irradiation with UV-light at ambient temperatures. The included aqueous enzyme solution remains highly dispersed in the polymer material with an even size distribution throughout the polymer material. The presented concept provides stable enzyme compartments which were applied for an alcohol dehydrogenase-catalyzed reduction reaction in organic solvents. Cofactor regeneration was achieved by a substrate-coupled approach via 2-propanol or an enzyme-coupled approach by a glucose dehydrogenase. This reaction concept can also be used for a simultaneous application of contrary biocatalytic reaction conditions within an enzymatic cascade reaction. Independent polymer-based reaction compartments were provided for two incompatible enzymatic reaction systems (alcohol dehydrogenase and hydroxynitrile lyase, while the relevant reactants diffuse between the applied compartments.

  17. Strong negative interference of ethamsylate (Dicynone®) in serum creatinine quantification via enzymatic assay using Trinder reaction.

    Science.gov (United States)

    Wiewiorka, Ondrej; Dastych, Milan; Čermáková, Zdenka

    2013-08-01

    With discrepancies encountered as early as the verification of enzymatic method for quantification of serum creatinine, our research pointed to a later confirmed interference caused by a compound called ethamsylate present in the commonly used antihemorrhagic drug Dicynone. We measured concentrations of creatinine of 10 patients with blood taken before and 15 minutes after the intravenous administration of a 500 mg dose of Dicynone. The creatinine concentration was determined using Jaffe method and enzymatic method that utilize Trinder reaction (Roche) in analyzer Cobas c 501 (Roche AG, Basel, Switzerland). We also monitored concentration of blood creatinine in three patients before and 15 minutes after application of Dicynone (500 mg i.v.) and in the following 6th, 12th, 18th, and 24th hours. We discovered a significant negative bias in creatinine results using enzymatic assay with Trinder reaction in blood taken 15 min after i.v. application of 500 mg Dicynone to patients compared to their pre-application values (average decrease of 47%). Unlike this, the results of compensated Jaffe method yielded steady results in all samples (average deviation 0.6% from original values). However, 12 h after the drug administration comparable results were seen as before the administration. Considering the strong negative interference of ethamsylate in enzymatic assay using Trinder reaction for creatinine quantification, blood from patients with prescribed Dicynone should be taken at least 12 h after the last application of the drug for obtaining the correct creatinine values.

  18. Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

    Science.gov (United States)

    Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

    2018-04-25

    This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

  19. Modeling networks of coupled enzymatic reactions using the total quasi-steady state approximation.

    Directory of Open Access Journals (Sweden)

    Andrea Ciliberto

    2007-03-01

    Full Text Available In metabolic networks, metabolites are usually present in great excess over the enzymes that catalyze their interconversion, and describing the rates of these reactions by using the Michaelis-Menten rate law is perfectly valid. This rate law assumes that the concentration of enzyme-substrate complex (C is much less than the free substrate concentration (S0. However, in protein interaction networks, the enzymes and substrates are all proteins in comparable concentrations, and neglecting C with respect to S0 is not valid. Borghans, DeBoer, and Segel developed an alternative description of enzyme kinetics that is valid when C is comparable to S0. We extend this description, which Borghans et al. call the total quasi-steady state approximation, to networks of coupled enzymatic reactions. First, we analyze an isolated Goldbeter-Koshland switch when enzymes and substrates are present in comparable concentrations. Then, on the basis of a real example of the molecular network governing cell cycle progression, we couple two and three Goldbeter-Koshland switches together to study the effects of feedback in networks of protein kinases and phosphatases. Our analysis shows that the total quasi-steady state approximation provides an excellent kinetic formalism for protein interaction networks, because (1 it unveils the modular structure of the enzymatic reactions, (2 it suggests a simple algorithm to formulate correct kinetic equations, and (3 contrary to classical Michaelis-Menten kinetics, it succeeds in faithfully reproducing the dynamics of the network both qualitatively and quantitatively.

  20. Optimization of reaction parameters for enzymatic glyceride synthesis from fish oil: Ethyl esters versus free fatty acids

    DEFF Research Database (Denmark)

    Ravn, Helle Christine; Damstrup, Marianne L.; Meyer, Anne S.

    2012-01-01

    Enzymatic conversion of fish oil free fatty acids (FFA) or fatty acid ethyl esters (FAE) into glycerides via esterification or transesterification was examined. The reactions catalyzed by Lipozyme™ 435, a Candida antarctica lipase, were optimized. Influence on conversion yields of fatty acid chain...... length, saturation degree, temperature, enzyme dosage, molar ratio glycerol:fatty acids, acyl source composition (w/w ratio FFA:FAE), and reaction time was evaluated collectively by multiple linear regression. All reaction variables influenced the conversion into glycerides. Transesterification of FAE...

  1. Design of an embedded inverse-feedforward biomolecular tracking controller for enzymatic reaction processes.

    Science.gov (United States)

    Foo, Mathias; Kim, Jongrae; Sawlekar, Rucha; Bates, Declan G

    2017-04-06

    Feedback control is widely used in chemical engineering to improve the performance and robustness of chemical processes. Feedback controllers require a 'subtractor' that is able to compute the error between the process output and the reference signal. In the case of embedded biomolecular control circuits, subtractors designed using standard chemical reaction network theory can only realise one-sided subtraction, rendering standard controller design approaches inadequate. Here, we show how a biomolecular controller that allows tracking of required changes in the outputs of enzymatic reaction processes can be designed and implemented within the framework of chemical reaction network theory. The controller architecture employs an inversion-based feedforward controller that compensates for the limitations of the one-sided subtractor that generates the error signals for a feedback controller. The proposed approach requires significantly fewer chemical reactions to implement than alternative designs, and should have wide applicability throughout the fields of synthetic biology and biological engineering.

  2. Using an enzymatic galactose assay to detect lactose glycation extents of two proteins caseinate and soybean protein isolate via the Maillard reaction.

    Science.gov (United States)

    Wang, Xiao-Peng; Zhao, Xin-Huai

    2017-06-01

    Glycation of food proteins via the Maillard reaction has been widely studied in the recent years; however, the amount of saccharide connected to proteins is usually not determined. An enzymatic galactose assay was proposed firstly in this study to detect lactose glycation extents of caseinate and soybean protein isolate (SPI) during the Maillard reaction at two temperatures and different times. The separated glycated proteins were hydrolysed to release galactose necessary for the enzymatic assay and glycation calculation. Caseinate and SPI both obtained the highest lactose glycation extents at 100 °C or 121 °C by a reaction time of 180 or 20 min. Short- and long-time reaction resulted in lower glycation extents. During the reaction, three chemical indices (absorbences at 294/490 nm and fluorescence intensities) of reaction mixtures increased continually, but another index reactable NH 2 of glycated proteins showed the opposite trend. In general, changing profiles of the four indices were inconsistent with those profiles of lactose glycation extents of glycated proteins, implying practical limitation of the four indices in studies. This proposed enzymatic assay could directly detect lactose glycation of the two proteins, and thus was more useful than the four chemical indices to monitor glycation of the two proteins. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  3. Absorption media for irreversibly gettering thionyl chloride

    Science.gov (United States)

    Buffleben, George; Goods, Steven H.; Shepodd, Timothy; Wheeler, David R.; Whinnery, Jr., LeRoy

    2002-01-01

    Thionyl chloride is a hazardous and reactive chemical used as the liquid cathode in commercial primary batteries. Contrary to previous thinking, ASZM-TEDA.RTM. carbon (Calgon Corporation) reversibly absorbs thionyl chloride. Thus, several candidate materials were examined as irreversible getters for thionyl chloride. The capacity, rate and effect of temperature were also explored. A wide variety of likely materials were investigated through screening experiments focusing on the degree of heat generated by the reaction as well as the material absorption capacity and irreversibility, in order to help narrow the group of possible getter choices. More thorough, quantitative measurements were performed on promising materials. The best performing getter was a mixture of ZnO and ASZM-TEDA.RTM. carbon. In this example, the ZnO reacts with thionyl chloride to form ZnCl.sub.2 and SO.sub.2. The SO.sub.2 is then irreversibly gettered by ASZM-TEDA.RTM. carbon. This combination of ZnO and carbon has a high capacity, is irreversible and functions effectively above -20.degree. C.

  4. Studies on thermal reactions and sintering behaviour of red clays by irreversible dilatometry

    Science.gov (United States)

    Anil, Asha; Misra, S. N.; Misra, N. M.

    2018-05-01

    Thermal behavior of clays strongly influences that of ceramic bodies made thereof and hence, its study is must for assessing its utility in ceramic products as well as to set the body composition. Irreversible dilatometry is an effective thermal analysis tool for evaluating thermal reactions as well as sintering behavior of clays or clay based ceramic bodies. In this study, irreversible dilatometry of four red clay samples (S, M, R and G) of Gujarat region, which vary in their chemical and mineralogical compositions was carried out using a Dilatometer and compared. Chemical analysis and XRD of red clays were carried out. XRD showed that major clay minerals in S, M and R clays are kaolinite. However, clay marked R and G showed presence of both kaolinite and illite and /muscovite. Presence of non-clay minerals such as hematite, quartz, anatase were also observed in all clays. XRD results were in agreement with chemical analyses results. Rational analyses showed variation in amount of clay and non-clay minerals in red clay samples. Evaluation of dilatometric curves showed that clay marked as S, M and R exhibit patterns typical for kaolinitic clays. Variation in linear expansion (up to 550°C) and shrinkage (above 550°C) between these three clays was found to be related to difference in amount of quartz and kaolinite respectively. However, dilatometric curve of G exhibit a pattern similar to that for an illitic clay. This study confirmed that sintering of investigated kaolinitic and illitic and / muscovitic red clays initiates at above 1060°C and 860°C respectively and this behaviour strongly depends upon type and amount of minerals and their chemical compositions.

  5. A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

    Science.gov (United States)

    Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

    2015-04-30

    Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

  6. Enzymatic processes in alternative reaction media: a mini review

    Directory of Open Access Journals (Sweden)

    Mansour Ghaffari-Moghaddam

    2015-08-01

    Full Text Available Biocatalysis is a growing field in the production of fine chemicals and will most probably increase its share in the future. Enzymatic reactions are carried out under mild conditions, i.e., non-toxic solvents, low temperature and pressure, which eliminates most environmental drawbacks associated with conventional production methods. The superiority of chemo-, regio- and enantioselectivity of enzymes exhibit significant advantages over conventional catalysts for production of fine chemicals, flavors, fragrances, agrochemicals and pharmaceuticals. Enzymes can function both in aqueous and non-aqueous solvents. As a result of the growing scientific and industrial interest towards green chemistry, green solvent systems, which are mainly water, supercritical fluids, ionic liquids, fluorinated solvents, and solvent-free systems have become more popular in biocatalysis. However, the activity and selectivity of an enzyme is heavily dependent on solvent properties. In this review, various green solvents were classified and some of their influential features on enzyme activity were discussed.

  7. Fish protein hydrolysate production from sardine solid waste by crude pepsin enzymatic hydrolysis in a bioreactor coupled to an ultrafiltration unit

    International Nuclear Information System (INIS)

    Benhabiles, M.S.; Abdi, N.; Drouiche, N.; Lounici, H.; Pauss, A.; Goosen, M.F.A.; Mameri, N.

    2012-01-01

    The aims of the study were to optimize the production a fish protein hydrolysate (FPH) by enzymatic hydrolysis of sardine solid waste using crude pepsin, and to scale up the process in a bioreactor coupled to an ultrafiltration unit for product recovery. Results showed that the crude pepsin prepared by autolysis of the mucous membranes of a sheep stomach at optimal conditions (i. e. pH = 1.5–2 and incubation time of 6 h) could be satisfactory used for the enzymatic hydrolysis of fish solid waste. The optimal conditions for enzymatic reaction were: temperature 48 °C, and pH 1.5. The scale up of the enzymatic hydrolysis and the coupling of the reactor an ultrafiltration unit to concentrate the hydrolysate gave good results with a rejection coefficient for the protein hydrolysate product in the range of 90%. The volumetric concentration factor was 2.5, with a permeate flux of 200 L m −2 bar −1 . However, the results also suggest that the ultrafiltration product concentration process may be operating beyond the critical flux at which point irreversible membrane fouling occurs. - Highlights: ► Evaluating to produce a (FPH) by enzymatic hydrolysis of sardine solid wastes was achieved. ► Investigation of key parameters for optimal conditions for enzymatic hydrolysis have been studied. ► Valorization of sardine waste was realized by enzymatic hydrolysis process. ► Performances of this enzyme gave comparable results to those obtained with commercial pepsin. ► The nutritional quality of the FPH produced appears to be satisfactory.

  8. Large-eddy simulation of pollutant dispersion from a ground-level area source over urban street canyons with irreversible chemical reactions

    Science.gov (United States)

    Du, T. Z.; Liu, C.-H.; Zhao, Y. B.

    2014-10-01

    In this study, the dispersion of chemically reactive pollutants is calculated by large-eddy simulation (LES) in a neutrally stratified urban canopy layer (UCL) over urban areas. As a pilot attempt, idealized street canyons of unity building-height-to-street-width (aspect) ratio are used. Nitric oxide (NO) is emitted from the ground surface of the first street canyon into the domain doped with ozone (O3). In the absence of ultraviolet radiation, this irreversible chemistry produces nitrogen dioxide (NO2), developing a reactive plume over the rough urban surface. A range of timescales of turbulence and chemistry are utilized to examine the mechanism of turbulent mixing and chemical reactions in the UCL. The Damköhler number (Da) and the reaction rate (r) are analyzed along the vertical direction on the plane normal to the prevailing flow at 10 m after the source. The maximum reaction rate peaks at an elevation where Damköhler number Da is equal or close to unity. Hence, comparable timescales of turbulence and reaction could enhance the chemical reactions in the plume.

  9. Reversible and Irreversible Binding of Nanoparticles to Polymeric Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang H. Binder

    2009-01-01

    Full Text Available Reversible and irreversible binding of CdSe-nanoparticles and nanorods to polymeric surfaces via a strong, multiple hydrogen bond (= Hamilton-receptor/barbituric acid is described. Based on ROMP-copolymers, the supramolecular interaction on a thin polymer film is controlled by living polymerization methods, attaching the Hamilton-receptor in various architectures, and concentrations. Strong binding is observed with CdSe-nanoparticles and CdSe-nanorods, whose surfaces are equipped with matching barbituric acid-moieties. Addition of polar solvents, able to break the hydrogen bonds leads to the detachment of the nanoparticles from the polymeric film. Irreversible binding is observed if an azide/alkine-“click”-reaction is conducted after supramolecular recognition of the nanoparticles on the polymeric surface. Thus reversible or irreversible attachment of the nanosized objects can be achieved.

  10. The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ju-Woon [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Oh, Sang-Hee [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Kim, Jae-Hun [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Byun, Eui-Hong [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Ree Kim, Mee [Department of Food and Nutrition, Chungnam National University, Gung-Dong 220, Yuseong, Daejeon 305-764 (Korea, Republic of); Baek, Min [Atomic Energy Policy Division, Ministry of Science and Technology, Government Complex-Gwacheon, Kyunggi 427-715 (Korea, Republic of); Byun, Myung-Woo [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of)]. E-mail: mwbyun@kaeri.re.kr

    2007-05-15

    The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring.

  11. The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

    International Nuclear Information System (INIS)

    Lee, Ju-Woon; Oh, Sang-Hee; Kim, Jae-Hun; Byun, Eui-Hong; Ree Kim, Mee; Baek, Min; Byun, Myung-Woo

    2007-01-01

    The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring

  12. Phosphorylated aminosugars: Synthesis, properties, and reactivity in enzymatic reactions

    International Nuclear Information System (INIS)

    Sem, D.S.; Cleland, W.W.

    1991-01-01

    A number of phosphorylated aminosugars have been prepared and tested as substrates for metabolic reactions. 6-Aminoglucose is a slow substrate for yeast hexokinase with a V max that is only 0.012% that of glucose. While V max is pH independent, V/K decreases below the pK of 9.0 of the amino group. 6-Aminoglucose is a competitive inhibitor vs glucose with a K i value increasing below the pK of 9 but leveling off at 33 mM below pH 7.16. Thus, protonation decreases binding affinity by 2.4 kcal/mol and only the neutral amine is catalytically competent. 6-Aminoglucose-6-P was synthesized enzymatically with hexokinase. Its pK's determined by 31 P NMR were 2.46 and 8.02 (α anomer) and 2.34 and 7.85 (β anomer), with a β:α ratio of 3.0. It is most stable at pH 12, while as a monoanion its half-life is 3 h. The 31 P NMR chemical shifts of the analogues are 8-8.5 ppm at pH 9.5. Their relative stability is 6-aminogluconate-6-P > 3-aminoglyceraldehyde-3-P > 6-aminoglucose-6-P > 6-aminofructose-1,6-bis-P≅6-aminofructose-6-P > 5-aminoribulose-5-P. These analogues were tested as substrates for their respective enzymes. Phosphorylated aminosugars are thus excellent isosteric analogues of normal metabolic intermediates, except for reactions catalyzed by kinases

  13. Irreversible social change

    NARCIS (Netherlands)

    Pols, A.J.K.; Romijn, H.A.; Collste, G.; Reuter, L.

    2014-01-01

    In this paper we evaluate how irreversible social change should be evaluated from an ethical perspective. First; we analyse the notion of irreversibility in general terms. We define a general notion of what makes a change irreversible; drawing on discussions in ecology and economics. This notion is

  14. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    Science.gov (United States)

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-04-26

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  15. PENGARUH SORPSI AIR DAN SUHU TRANSISI GELAS TERHADAP LAJU PENCOKLATAN NON-ENZIMATIS PADA PANGAN MODEL [The Effect of Water Sorption and Glass Transition Temperature on Non-Enzymatic Browning Reaction of Food Models

    Directory of Open Access Journals (Sweden)

    Dede R Adawiyah1

    2005-12-01

    Full Text Available This research was aimer/ to study the extend of non enzymatic browning reaction in food models containing the mixture of tapioca starch, casein, sucrose and oh at different moisture contents (2.55%, 5.26%, 7.54%, 15.20%. 15.93% and 23.99% and storage temperatures (30, 55 and 700C. The non-enzymatic browning reaction was detected from brown color intensity measured by spechtrophotometer and colorimetric methods. The non-enzymatic browning reaction or food model follow pseudo-zero order reaction, suggesting that browning reaction occurred at moisture content above monolayer zone. T-Tg (T storage - Tg prediction and reaction rate constant (k plots showed that browning reaction occurred at temperature around glass transition and increased significantly at 150 above Tg of casein. Tapioca starch in the food model was under glassy condition. The mobility of substrate increased and diffused at amorphous matrix.

  16. Comparison of the role that entropy has played in processes of non-enzymatic and enzymatic catalysis

    International Nuclear Information System (INIS)

    Dixon Pineda, Manuel Tomas

    2012-01-01

    The function that entropy has played is compared in processes of non-enzymatic and enzymatic catalysis. The processes followed are showed: the kinetics of the acid hydrolysis of 3-pentyl acetate and cyclopentyl acetate catalyzed by hydrochloric acid and enzymatic hydrolysis of ethyl acetate and γ-butyrolactone catalyzed by pig liver esterase. The activation parameters of Eyring were determined for each process and interpreted the contribution of the entropy of activation for catalysis in this type of model reactions. (author) [es

  17. Fish protein hydrolysate production from sardine solid waste by crude pepsin enzymatic hydrolysis in a bioreactor coupled to an ultrafiltration unit

    Energy Technology Data Exchange (ETDEWEB)

    Benhabiles, M.S.; Abdi, N. [National Polytechnic school of Algiers, B.P. 182-16200, El Harrach, Algiers (Algeria); Drouiche, N., E-mail: nadjibdrouiche@yahoo.fr [National Polytechnic school of Algiers, B.P. 182-16200, El Harrach, Algiers (Algeria); Silicon Technology Development Unit (UDTS) 2, Bd Frantz Fanon BP140, Alger-7 Merveilles, 16000 (Algeria); Lounici, H. [National Polytechnic school of Algiers, B.P. 182-16200, El Harrach, Algiers (Algeria); Pauss, A. [University of Technology of Compiegne, Departement Genie chimique,B.P. 20.509, 60205 Compiegne cedex (France); Goosen, M.F.A. [Alfaisal University, Riyadh (Saudi Arabia); Mameri, N. [University of Technology of Compiegne, Departement Genie chimique,B.P. 20.509, 60205 Compiegne cedex (France)

    2012-05-01

    The aims of the study were to optimize the production a fish protein hydrolysate (FPH) by enzymatic hydrolysis of sardine solid waste using crude pepsin, and to scale up the process in a bioreactor coupled to an ultrafiltration unit for product recovery. Results showed that the crude pepsin prepared by autolysis of the mucous membranes of a sheep stomach at optimal conditions (i. e. pH = 1.5-2 and incubation time of 6 h) could be satisfactory used for the enzymatic hydrolysis of fish solid waste. The optimal conditions for enzymatic reaction were: temperature 48 Degree-Sign C, and pH 1.5. The scale up of the enzymatic hydrolysis and the coupling of the reactor an ultrafiltration unit to concentrate the hydrolysate gave good results with a rejection coefficient for the protein hydrolysate product in the range of 90%. The volumetric concentration factor was 2.5, with a permeate flux of 200 L m{sup -2} bar{sup -1}. However, the results also suggest that the ultrafiltration product concentration process may be operating beyond the critical flux at which point irreversible membrane fouling occurs. - Highlights: Black-Right-Pointing-Pointer Evaluating to produce a (FPH) by enzymatic hydrolysis of sardine solid wastes was achieved. Black-Right-Pointing-Pointer Investigation of key parameters for optimal conditions for enzymatic hydrolysis have been studied. Black-Right-Pointing-Pointer Valorization of sardine waste was realized by enzymatic hydrolysis process. Black-Right-Pointing-Pointer Performances of this enzyme gave comparable results to those obtained with commercial pepsin. Black-Right-Pointing-Pointer The nutritional quality of the FPH produced appears to be satisfactory.

  18. A new approach to irreversibility in deep inelastic collisions

    International Nuclear Information System (INIS)

    Nemes, M.C.

    1982-01-01

    We use concepts of statistical mechanics to discuss the irreversible character of the experimental data in deep inelastic collisions. A definition of irreversibility proposed by Ruch permits a unified overview on current theories which describe these reactions. An information theoretical analysis of the data leads to a Fokker-Planck equation for the collective variables (excitation energy, charge and mass). The concept of mixing distance can serve as a quantitative measure to characterize the 'approach to equilibrium'. We apply it to the brownian motion as an illustration and also to the phenomenological analysis of deep inelastic scattering data with interesting results. (orig.)

  19. Quantum chemical modeling of enzymatic reactions: the case of histone lysine methyltransferase.

    Science.gov (United States)

    Georgieva, Polina; Himo, Fahmi

    2010-06-01

    Quantum chemical cluster models of enzyme active sites are today an important and powerful tool in the study of various aspects of enzymatic reactivity. This methodology has been applied to a wide spectrum of reactions and many important mechanistic problems have been solved. Herein, we report a systematic study of the reaction mechanism of the histone lysine methyltransferase (HKMT) SET7/9 enzyme, which catalyzes the methylation of the N-terminal histone tail of the chromatin structure. In this study, HKMT SET7/9 serves as a representative case to examine the modeling approach for the important class of methyl transfer enzymes. Active site models of different sizes are used to evaluate the methodology. In particular, the dependence of the calculated energies on the model size, the influence of the dielectric medium, and the particular choice of the dielectric constant are discussed. In addition, we examine the validity of some technical aspects, such as geometry optimization in solvent or with a large basis set, and the use of different density functional methods. Copyright 2010 Wiley Periodicals, Inc.

  20. Enzymatic Synthesis and Structural Characterization of Theanderose through Transfructosylation Reaction Catalyzed by Levansucrase from Bacillus subtilis CECT 39.

    Science.gov (United States)

    Ruiz-Aceituno, Laura; Sanz, Maria Luz; de Las Rivas, Blanca; Muñoz, Rosario; Kolida, Sofia; Jimeno, Maria Luisa; Moreno, F Javier

    2017-12-06

    This work addresses the high-yield and fast enzymatic production of theanderose, a naturally occurring carbohydrate, also known as isomaltosucrose, whose chemical structure determined by NMR is α-d-glucopyranosyl-(1 → 6)-α-d-glucopyranosyl-(1 → 2)-β-d-fructofuranose. The ability of isomaltose to act as an acceptor in the Bacillus subtilis CECT 39 levansucrase-catalyzed transfructosylation reaction to efficiently produce theanderose in the presence of sucrose as a donor is described by using four different sucrose:isomaltose concentration ratios. The maximum theanderose concentration ranged from 122.4 to 130.4 g L -1 , was obtained after only 1 h and at a moderate temperature (37 °C), leading to high productivity (109.7-130.4 g L -1 h -1 ) and yield (up to 37.3%) values. The enzymatic synthesis was highly regiospecific, since no other detectable acceptor reaction products were formed. The development of efficient and cost-effective procedures for the biosynthesis of unexplored but appealing oligosaccharides as potential sweeteners, such as theanderose, could help to expand its potential applications which are currently limited by their low availability.

  1. Modeling and simulation of enzymatic gluconic acid production using immobilized enzyme and CSTR-PFTR circulation reaction system.

    Science.gov (United States)

    Li, Can; Lin, Jianqun; Gao, Ling; Lin, Huibin; Lin, Jianqiang

    2018-04-01

    Production of gluconic acid by using immobilized enzyme and continuous stirred tank reactor-plug flow tubular reactor (CSTR-PFTR) circulation reaction system. A production system is constructed for gluconic acid production, which consists of a continuous stirred tank reactor (CSTR) for pH control and liquid storage and a plug flow tubular reactor (PFTR) filled with immobilized glucose oxidase (GOD) for gluconic acid production. Mathematical model is developed for this production system and simulation is made for the enzymatic reaction process. The pH inhibition effect on GOD is modeled by using a bell-type curve. Gluconic acid can be efficiently produced by using the reaction system and the mathematical model developed for this system can simulate and predict the process well.

  2. Irreversible adsorption of phenolic compounds by activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Grant, T.M.; King, C.J.

    1988-12-01

    Studies were undertaken to determine the reasons why phenolic sorbates can be difficult to remove and recover from activated carbons. The chemical properties of the sorbate and the adsorbent surface, and the influences of changes in the adsorption and desorption conditions were investigated. Comparison of isotherms established after different contact times or at different temperatures indicated that phenolic compounds react on carbon surfaces. The reaction rate is a strong function of temperature. Regeneration of carbons by leaching with acetone recovered at least as much phenol as did regeneration with other solvents or with displacers. The physiochemical properties of adsorbents influences irreversible uptakes. Sorbates differed markedly in their tendencies to undergo irreversible adsorption. 64 refs., 47 figs., 32 tabs.

  3. Irreversible adsorption of phenolic compounds by activated carbons

    International Nuclear Information System (INIS)

    Grant, T.M.; King, C.J.

    1988-12-01

    Studies were undertaken to determine the reasons why phenolic sorbates can be difficult to remove and recover from activated carbons. The chemical properties of the sorbate and the adsorbent surface, and the influences of changes in the adsorption and desorption conditions were investigated. Comparison of isotherms established after different contact times or at different temperatures indicated that phenolic compounds react on carbon surfaces. The reaction rate is a strong function of temperature. Regeneration of carbons by leaching with acetone recovered at least as much phenol as did regeneration with other solvents or with displacers. The physiochemical properties of adsorbents influences irreversible uptakes. Sorbates differed markedly in their tendencies to undergo irreversible adsorption. 64 refs., 47 figs., 32 tabs

  4. Automatic single- and multi-label enzymatic function prediction by machine learning

    Directory of Open Access Journals (Sweden)

    Shervine Amidi

    2017-03-01

    Full Text Available The number of protein structures in the PDB database has been increasing more than 15-fold since 1999. The creation of computational models predicting enzymatic function is of major importance since such models provide the means to better understand the behavior of newly discovered enzymes when catalyzing chemical reactions. Until now, single-label classification has been widely performed for predicting enzymatic function limiting the application to enzymes performing unique reactions and introducing errors when multi-functional enzymes are examined. Indeed, some enzymes may be performing different reactions and can hence be directly associated with multiple enzymatic functions. In the present work, we propose a multi-label enzymatic function classification scheme that combines structural and amino acid sequence information. We investigate two fusion approaches (in the feature level and decision level and assess the methodology for general enzymatic function prediction indicated by the first digit of the enzyme commission (EC code (six main classes on 40,034 enzymes from the PDB database. The proposed single-label and multi-label models predict correctly the actual functional activities in 97.8% and 95.5% (based on Hamming-loss of the cases, respectively. Also the multi-label model predicts all possible enzymatic reactions in 85.4% of the multi-labeled enzymes when the number of reactions is unknown. Code and datasets are available at https://figshare.com/s/a63e0bafa9b71fc7cbd7.

  5. A general framework for thermodynamically consistent parameterization and efficient sampling of enzymatic reactions.

    Directory of Open Access Journals (Sweden)

    Pedro Saa

    2015-04-01

    the kinetic behaviour of these enzymes, but it also provided insights about the particular features underpinning the observed kinetics. Overall, this framework will enable systematic parameterization and sampling of enzymatic reactions.

  6. Efficient one-pot enzymatic synthesis of alpha-(1 -> 4)-glucosidic disaccharides through a coupled reaction catalysed by Lactobacillus acidophilus NCFM maltose phosphorylase

    DEFF Research Database (Denmark)

    Nakai, Hiroyuki; Dilokpimol, Adiphol; Abou Hachem, Maher

    2010-01-01

    Lactobacillus acidophilus NCFM maltose phosphorylase (LaMalP) of glycoside hydrolase family 65 catalysed enzymatic synthesis of alpha-(1 -> 4)-glucostdic disacchandes from maltose and five monosacchandes in a coupled phosphorolysis/reverse phosphorolysis one-pot reaction Thus phosphorolysis...

  7. High-yield production of pure tagatose from fructose by a three-step enzymatic cascade reaction.

    Science.gov (United States)

    Lee, Seon-Hwa; Hong, Seung-Hye; Kim, Kyoung-Rok; Oh, Deok-Kun

    2017-08-01

    To produce tagatose from fructose with a high conversion rate and to establish a high-yield purification method of tagatose from the reaction mixture. Fructose at 1 M (180 g l -1 ) was converted to 0.8 M (144 g l -1 ) tagatose by a three-step enzymatic cascade reaction, involving hexokinase, plus ATP, fructose-1,6-biphosphate aldolase, phytase, over 16 h with a productivity of 9 g l -1 h -1 . No byproducts were detected. Tagatose was recrystallized from ethanol to a purity of 99.9% and a yield of 96.3%. Overall, tagatose at 99.9% purity was obtained from fructose with a yield of 77%. This is the first biotechnological production of tagatose from fructose and the first application of solvent recrystallization for the purification of rare sugars.

  8. On the impedance of galvanic cells XVIII. The potential dependence of the faradaic impedance in the case of an irreversible electrode reaction, and its application to A.C. polarography

    NARCIS (Netherlands)

    Timmer, B.; Sluyters-Rehbach, M.; Sluyters, J.H.

    A theoretical treatment for the potential dependence of the faradaic impedance, in the case that the electrode reaction behaves irreversibly with respect to the direct current, using the steady-state concept, is presented. An analysis of the expressions obtained in the complex impedance plane is

  9. Enzymatic conversion of sucrose to glucose and its anomerization by quantitative NMR spectroscopy: Application of a simple consecutive reaction rates approach

    Science.gov (United States)

    Singh, Jaideep; Her, Cheenou; Krishnan, V. V.

    2018-02-01

    The anomerization of carbohydrates is an essential process that determines the relative stabilization of stereoisomers in an aqueous solution. In a typical real-time enzyme kinetics experiment, the substrate (sucrose) is converted to glucose and fructose by the enzyme invertase. The product (α-D-glucose) starts to convert to β-D-glucose immediately by hydrolysis. Though the anomerization process is independent of the enzyme catalysis, the progress curve describing the production of β-D-glucose from α-D-glucose is directly affected by the kinetics of consecutive reactions. When α-D-glucose is continually converted to β-D-glucose, by the enzymatic action, the time course of both α- and β-D-glucose is influenced by the enzyme kinetics. Thus, a reversible first-order rate equation is not adequate to model the reaction mechanism, leading to erroneous results on the rates of formation of the glucose anomers. In this manuscript, we incorporate an approximate method to address consecutive general reactions involving enzyme kinetics and first-order reaction processes. The utility of the approach is demonstrated in the real-time NMR measurement of the anomerization process of α-D-glucose (enzymatically produced from sucrose) to β-D-glucose, as a function of invertase enzyme concentration. Variable temperature experiments were used to estimate the thermodynamic parameters of the anomerization process and are consistent with literature values.

  10. Peptide Drug Release Behavior from Biodegradable Temperature-Responsive Injectable Hydrogels Exhibiting Irreversible Gelation

    Directory of Open Access Journals (Sweden)

    Kazuyuki Takata

    2017-10-01

    Full Text Available We investigated the release behavior of glucagon-like peptide-1 (GLP-1 from a biodegradable injectable polymer (IP hydrogel. This hydrogel shows temperature-responsive irreversible gelation due to the covalent bond formation through a thiol-ene reaction. In vitro sustained release of GLP-1 from an irreversible IP formulation (F(P1/D+PA40 was observed compared with a reversible (physical gelation IP formulation (F(P1. Moreover, pharmaceutically active levels of GLP-1 were maintained in blood after subcutaneous injection of the irreversible IP formulation into rats. This system should be useful for the minimally invasive sustained drug release of peptide drugs and other water-soluble bioactive reagents.

  11. Enzymatic network for production of ether amines from alcohols

    NARCIS (Netherlands)

    Palacio, Cyntia M.; Crismaru, Gica Ciprian; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John; Baldenius, Kai-Uwe; Wu, Bian; Janssen, Dick

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the

  12. Kinetics of enzymatic high-solid hydrolysis of lignocellulosic biomass studied by calorimetry.

    Science.gov (United States)

    Olsen, Søren N; Lumby, Erik; McFarland, Kc; Borch, Kim; Westh, Peter

    2011-03-01

    Enzymatic hydrolysis of high-solid biomass (>10% w/w dry mass) has become increasingly important as a key step in the production of second-generation bioethanol. To this end, development of quantitative real-time assays is desirable both for empirical optimization and for detailed kinetic analysis. In the current work, we have investigated the application of isothermal calorimetry to study the kinetics of enzymatic hydrolysis of two substrates (pretreated corn stover and Avicel) at high-solid contents (up to 29% w/w). It was found that the calorimetric heat flow provided a true measure of the hydrolysis rate with a detection limit of about 500 pmol glucose s(-1). Hence, calorimetry is shown to be a highly sensitive real-time method, applicable for high solids, and independent on the complexity of the substrate. Dose-response experiments with a typical cellulase cocktail enabled a multidimensional analysis of the interrelationships of enzyme load and the rate, time, and extent of the reaction. The results suggest that the hydrolysis rate of pretreated corn stover is limited initially by available attack points on the substrate surface (conversion) but becomes proportional to enzyme dosage (excess of attack points) at later stages (>10% conversion). This kinetic profile is interpreted as an increase in polymer end concentration (substrate for CBH) as the hydrolysis progresses, probably due to EG activity in the enzyme cocktail. Finally, irreversible enzyme inactivation did not appear to be the source of reduced hydrolysis rate over time.

  13. Study on the Spectrophotometric Detection of Free Fatty Acids in Palm Oil Utilizing Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Nur Hidayah Azeman

    2015-07-01

    Full Text Available In this paper, a comprehensive study has been made on the detection of free fatty acids (FFAs in palm oil via an optical technique based on enzymatic aminolysis reactions. FFAs in crude palm oil (CPO were converted into fatty hydroxamic acids (FHAs in a biphasic lipid/aqueous medium in the presence of immobilized lipase. The colored compound formed after complexation between FHA and vanadium (V ion solution was proportional to the FFA content in the CPO samples and was analyzed using a spectrophotometric method. In order to develop a rapid detection system, the parameters involved in the aminolysis process were studied. The utilization of immobilized lipase as catalyst during the aminolysis process offers simplicity in the product isolation and the possibility of conducting the process under extreme reaction conditions. A good agreement was found between the developed method using immobilized Thermomyces lanuginose lipase as catalyst for the aminolysis process and the Malaysian Palm Oil Board (MPOB standard titration method (R2 = 0.9453.

  14. Glucose obtained from rice bran by ultrasound-assisted enzymatic hydrolysis

    Directory of Open Access Journals (Sweden)

    Raquel Cristine Kuhn

    2015-05-01

    Full Text Available In this work ultrasound-assisted solid-state enzymatic hydrolysis of rice bran to obtain fermentable sugars was investigated. For this purpose, process variables such as temperature, enzyme concentration and moisture content were evaluated during the enzymatic hydrolysis with and without ultrasound irradiation. The enzyme used is a blend of amylases derived from genetically modified strains of Trichoderma reesei. Kinetic of the enzymatic hydrolysis of rice bran at the constant-reaction rate period were measured. The best results for the ultrasound-assisted enzymatic hydrolysis was obtained using 3 wt% of enzyme, 60 oC and moisture content of 65 wt%, yielding 0.38 g sugar/g rice bran, whereas for the hydrolysis in the absence of ultrasound the highest yield was 0.20 g sugar/g rice bran using 3 wt% of enzyme, 60 oC and moisture content of 50 wt%. The use of ultrasound-assisted enzymatic hydrolysis of rice bran was intensified, obtaining around 74% more fermentable sugar than in the absence, showing that the use of ultrasound is a promising technology to be used in enzymatic reaction as an alternative of process intensification.

  15. Bovine glue (BioGlue) is catabolized by enzymatic reaction in the vascular dog model.

    Science.gov (United States)

    Van Belleghem, Yves; Forsyth, Ramses G; Narine, Kishan; Moerman, Annelies; Taeymans, Yves; Van Nooten, Guido J

    2004-06-01

    The aim of the study is to explore the feasibility, patency, and histologic changes of a sutureless vascular anastomotic technique using biological glue as sole fixation method. Eight mongrel dogs (+/-15 kg) underwent direct reanastomosis of their transsected iliac arteries. Both ends were placed on a 5-mm balloon and the anastomosis was secured with biological glue (BioGlue, Cryolife, Kennesaw, GA). No intravascular suture material was used. All survivors were angiographically controlled for patency after 6 weeks and 3 months. Then the animals were euthanized and tissues were obtained for histologic and pathologic examination by light and electron microscopy. All procedures were successful except for 1 animal that died of uncontrollable bleeding at the anastomotic site. All first-time angiographically controlled grafts except three were patent. One animal showed manifest signs of fungal infection. Histology detected early granulocyte infiltration with an important enzymatic reaction adjacent to the surface of glue. Later on, the glue gradually regressed to disappear completely. Fibroblastic neointimal lining was noticed in most of the anastomoses, with some marked differences in the endothelium compared with normal. Good permeability (57%) was observed in this new sutureless anastomotic technique in the canine model. In contrast to previous reported studies we noticed a clear enzymatic breakdown of the glue before total disappearance. It is not yet known to what extend use of the bovine glue was responsible for this phenomenon.

  16. Enzymatic approaches to rare sugar production.

    Science.gov (United States)

    Zhang, Wenli; Zhang, Tao; Jiang, Bo; Mu, Wanmeng

    Rare sugars have recently attracted much attention because of their potential applications in the food, nutraceutical, and pharmaceutical industries. A systematic strategy for enzymatic production of rare sugars, named Izumoring, was developed >10years ago. The strategy consists of aldose-ketose isomerization, ketose C-3 epimerization, and monosaccharide oxidation-reduction. Recent development of the Izumoring strategy is reviewed herein, especially the genetic approaches to the improvement of rare sugar-producing enzymes and the applications of target-oriented bioconversion. In addition, novel non-Izumoring enzymatic approaches are also summarized, including enzymatic condensation, phosphorylation-dephosphorylation cascade reaction, aldose epimerization, ulosonic acid decarboxylation, and biosynthesis of rare disaccharides. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Kinetic study of enzymatic hydrolysis of acid-pretreated coconut coir

    Science.gov (United States)

    Fatmawati, Akbarningrum; Agustriyanto, Rudy

    2015-12-01

    Biomass waste utilization for biofuel production such as bioethanol, has become more prominent currently. Coconut coir is one of lignocellulosic food wastes, which is abundant in Indonesia. Bioethanol production from such materials consists of more than one step. Pretreatment and enzymatic hydrolysis is crucial steps to produce sugar which can then be fermented into bioethanol. In this research, ground coconut coir was pretreated using dilute sulfuric acid at 121°C. This pretreatment had increased the cellulose content and decreased the lignin content of coconut coir. The pretreated coconut coir was hydrolyzed using a mix of two commercial cellulase enzymes at pH of 4.8 and temperature of 50°C. The enzymatic hydrolysis was conducted at several initial coconut coir slurry concentrations (0.1-2 g/100 mL) and reaction times (2-72 hours). The reducing sugar concentration profiles had been produced and can be used to obtain reaction rates. The highest reducing sugar concentration obtained was 1,152.567 mg/L, which was produced at initial slurry concentration of 2 g/100 mL and 72 hours reaction time. In this paper, the reducing sugar concentrations were empirically modeled as a function of reaction time using power equations. Michaelis-Menten kinetic model for enzymatic hydrolysis reaction is adopted. The kinetic parameters of that model for sulfuric acid-pretreated coconut coir enzymatic hydrolysis had been obtained which are Vm of 3.587×104 mg/L.h, and KM of 130.6 mg/L.

  18. High regioselective acetylation of vitamin A precursors using lipase ...

    African Journals Online (AJOL)

    Administrator

    2011-09-26

    Sep 26, 2011 ... acetates, vinyl acetate gave the best yield. A maximum monoester ... All other chemicals were supplied by Sigma Chemical Co. The solvents were all of analytical grade. Enzymatic reactions. Reactions were conducted in screw-cap vials. ... suitable acyl donor to make reaction process irreversible. Various ...

  19. Investigation of lipid oxidation and non-enzymatic browning reactions in marine PL emulsions

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

    Marine phospholipids (PL) have received much attention recently due to their numerous advantages. One of these advantages is their better resistance towards oxidation as compared to fish oil. In addition to the antioxidative properties of α-tocopherol and phospholipids, the better oxidative...... stability of marine PL might be attributed to antioxidative properties of pyrroles formed between oxidised lipids with amine groups from phosphatidylethanolamine (PE) or residues amino acids that are present in marine PL. The main objective of this study was to investigate if the presence of amine group...... of amino acids (leucine, methionine and lysine) from 2 authentic standards (PC and PE) and 2 purified marine PL (LC and MPL) through sonication method. Emulsions were incubated at 60 ºC for 0, 2, 4 and 6 days. Non-enzymatic browning reactions were investigated through measurement of i) Strecker aldehydes...

  20. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  1. 26kDa endochitinase from barley seeds: real-time monitoring of the enzymatic reaction and substrate binding experiments using electrospray ionization mass spectrometry

    DEFF Research Database (Denmark)

    Dennhart, Nicole; Weigang, Linda M M; Fujiwara, Maho

    2009-01-01

    A 26 kDa endochitinase from barley seeds was enzymatically characterized exclusively by electrospray ionization mass spectrometry (ESI-MS). At first, oligosaccharide hydrolysis catalyzed by the barley chitinase was monitored in real-time by ESI-MS. The reaction time-course obtained by ESI......-MS monitoring was found to be consistent with the data obtained earlier by HPLC, and the quantitative profile was successfully simulated by kinetic modeling of the enzymatic hydrolysis. It is obvious that the real-time monitoring method by ESI-MS allows a faster and cheaper determination of the chitinase...... of the enzymatic activity in E67Q is definitely caused by a point mutation of Glu67 but not due to partial unfolding of the mutated enzyme. Finally, association constants of enzyme-oligosaccharide complexes were calculated from Scatchard plots obtained by mass spectra. The binding free energy values obtained for E...

  2. Aza‐Michael addition reaction: Post‐polymerization modification and preparation of PEI/PEG‐based polyester hydrogels from enzymatically synthesized reactive polymers

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Stuparu, Mihaiela C.; Daugaard, Anders Egede

    2015-01-01

    The utility of aza‐Michael addition chemistry for post‐polymerization functionalization of enzymatically prepared polyesters is established. For this, itaconate ester and oligoethylene glycol are selected as monomers. A Candida Antarctica lipase B catalyzed polycondensation reaction between the two...... monomers provides the polyesters, which carry an activated carbon‐carbon double bond in the polymer backbone. These electron deficient alkenes represent suitable aza‐Michael acceptors and can be engaged in a nucleophilic addition reaction with small molecular mono‐amines (aza‐Michael donors) to yield...... functionalized linear polyesters. Employing a poly‐amine as the aza‐Michael donor, on the other hand, results in the formation of hydrophilic polymer networks....

  3. Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

    International Nuclear Information System (INIS)

    Hoang, Michelle V; Chung, Hyun-Joong; Elias, Anastasia L

    2016-01-01

    Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm −1 ) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ∼0.2 N mm −1 (method 1) and  >0.3 N mm −1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication. (paper)

  4. Enzymatic network for production of ether amines from alcohols

    DEFF Research Database (Denmark)

    Palacio, Cyntia M.; Crismaru, Ciprian G.; Bartsch, Sebastian

    2016-01-01

    We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production...... of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed...... for reactions containing 10mM alcohol and up to 280mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up....

  5. Non-Enzymatic-Browning-Reaction: A Versatile Route for Production of Nitrogen-Doped Carbon Dots with Tunable Multicolor Luminescent Display

    Science.gov (United States)

    Wei, Weili; Xu, Can; Wu, Li; Wang, Jiasi; Ren, Jinsong; Qu, Xiaogang

    2014-01-01

    The non-enzymatic browning, namely Maillard reaction is commonly invoked to account for abiotic chemical transformations of organic matter. Here we report a new reaction pathway via the Maillard reaction to systematically synthesize a series of nitrogen-doped carbon dots (C-dots) with superhigh quantum yield (QY) and tunable multicolor luminescent displayment. The starting materials are glucose and the serial amino acid analogues which allow systemically controlling luminescent and physicochemical properties of C-dots at will. Unexpectedly, the as-prepared C-dots possess bright photoluminescence with QY up to 69.1% which is almost the highest ever reported, favorable biocompatibility, excellent aqueous and nonaqueous dispersibility, ultrahigh photostability, and readily functionalization. We have demonstrated that they are particularly suitable for multicolor luminescent display and long-term and real-time cellular imaging. Furthermore, the methodology is readily scalable to large yield, and can provide sufficient amount of C-dots for practical demands.

  6. Green enzymatic production of glyceryl monoundecylenate using immobilized Candida antarctica lipase B.

    Science.gov (United States)

    Yadav, Manish G; Kavadia, Monali R; Vadgama, Rajeshkumar N; Odaneth, Annamma A; Lali, Arvind M

    2017-11-26

    Enzymatic synthesis of glyceryl monoundecylenate (GMU) was performed using indigenously immobilized Candida anatarctica lipase B preparation (named as PyCal) using glycerol and undecylenic acid as substrates. The effect of molar ratio, enzyme load, reaction time, and organic solvent on the reaction conversion was determined. Both batch and continuous processes for GMU synthesis with shortened reaction time were developed. Under optimized batch reaction conditions such as 1:5 molar ratio of undecylenic acid and glycerol, 2 h of reaction time at 30% substrate concentration in tert-butyl alcohol, conversion of 82% in the absence of molecular sieve, and conversion of 93% in the presence of molecular sieve were achieved. Packed bed reactor studies resulted in high conversion of 86% in 10-min residence time. Characterization of formed GMU was performed by FTIR, MS/MS. Enzymatic process resulted in GMU as a predominant product in high yield and shorter reaction time periods with GMU content of 92% and DAG content of 8%. Optimized GMU synthesis in the present study can be used as a useful reference for industrial synthesis of fatty acid esters of glycerol by the enzymatic route.

  7. Advances in quantum and molecular mechanical (QM/MM) simulations for organic and enzymatic reactions.

    Science.gov (United States)

    Acevedo, Orlando; Jorgensen, William L

    2010-01-19

    Application of combined quantum and molecular mechanical (QM/MM) methods focuses on predicting activation barriers and the structures of stationary points for organic and enzymatic reactions. Characterization of the factors that stabilize transition structures in solution and in enzyme active sites provides a basis for design and optimization of catalysts. Continued technological advances allowed for expansion from prototypical cases to mechanistic studies featuring detailed enzyme and condensed-phase environments with full integration of the QM calculations and configurational sampling. This required improved algorithms featuring fast QM methods, advances in computing changes in free energies including free-energy perturbation (FEP) calculations, and enhanced configurational sampling. In particular, the present Account highlights development of the PDDG/PM3 semi-empirical QM method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo (MC) simulations, and a polynomial quadrature method for efficient modeling of proton-transfer reactions. The utility of this QM/MM/MC/FEP methodology is illustrated for a variety of organic reactions including substitution, decarboxylation, elimination, and pericyclic reactions. A comparison to experimental kinetic results on medium effects has verified the accuracy of the QM/MM approach in the full range of solvents from hydrocarbons to water to ionic liquids. Corresponding results from ab initio and density functional theory (DFT) methods with continuum-based treatments of solvation reveal deficiencies, particularly for protic solvents. Also summarized in this Account are three specific QM/MM applications to biomolecular systems: (1) a recent study that clarified the mechanism for the reaction of 2-pyrone derivatives catalyzed by macrophomate synthase as a tandem Michael-aldol sequence rather than a Diels-Alder reaction, (2) elucidation of the mechanism of action of fatty

  8. Rational design of functional and tunable oscillating enzymatic networks

    Science.gov (United States)

    Semenov, Sergey N.; Wong, Albert S. Y.; van der Made, R. Martijn; Postma, Sjoerd G. J.; Groen, Joost; van Roekel, Hendrik W. H.; de Greef, Tom F. A.; Huck, Wilhelm T. S.

    2015-02-01

    Life is sustained by complex systems operating far from equilibrium and consisting of a multitude of enzymatic reaction networks. The operating principles of biology's regulatory networks are known, but the in vitro assembly of out-of-equilibrium enzymatic reaction networks has proved challenging, limiting the development of synthetic systems showing autonomous behaviour. Here, we present a strategy for the rational design of programmable functional reaction networks that exhibit dynamic behaviour. We demonstrate that a network built around autoactivation and delayed negative feedback of the enzyme trypsin is capable of producing sustained oscillating concentrations of active trypsin for over 65 h. Other functions, such as amplification, analog-to-digital conversion and periodic control over equilibrium systems, are obtained by linking multiple network modules in microfluidic flow reactors. The methodology developed here provides a general framework to construct dissipative, tunable and robust (bio)chemical reaction networks.

  9. Irreversibility and self-organization in spin glasses. 1. Origin of irreversibility in spin glasses

    International Nuclear Information System (INIS)

    Kovrov, V.P.; Kurbatov, A.M.

    1989-05-01

    The origin of irreversibility in spin glasses is found out on the basis of the analytical study of the well-known TAP equations. Connection between irreversible jumpwise transitions and a positive feedback in spin glasses is discussed. (author). 7 refs, 4 figs

  10. An Immunosensing System Using Stilbene Glycoside as a Fluorogenic Substrate for an Enzymatic Reaction Model

    Directory of Open Access Journals (Sweden)

    Ya-Fei Tan

    2008-09-01

    Full Text Available A natural product, stilbene glycoside (2,3,5,4’-tetrahydroxydiphenylethylene-2-O-glucoside, TBG, has been evaluated for the first time as a potential substrate for horseradish peroxidase (HRP-catalyzed fluorogenic reactions. The properties of TBG as a fluorogenic substrate for HRP and its application in a fluorometric enzyme-linked immunosensing system were compared with commercially available substrates such as p-hydroxyphenylpropionic acid (pHPPA, chavicol and Amplex red using Brucella melitensis antibody (BrAb as a model analyte. The immunosensing body based on HRP-BrAb was constructed by dispersing graphite, BrAg and paraffin wax at room temperature. In a competitive immunoassay procedure, the BrAb competed with HRP-BrAb to react with the immobilized BrAg. In the enzymatic reaction, the binding HRP-BrAb on the sensing body surface can catalyze the polymerization reaction of TBG by H2O2 forming fluorescent dimers and causing an increase in fluorescence intensity. TBG showed comparable ability for HRP detection and its enzyme-linked immunosensing reaction system, in a linear detection ranging of 3.5´10-8~7.6´10-6g/L and with a detection limit of 1.7´10-9 g/L. The immobilized biocomposite surface could be regenerated with excellent reproducibility (RSD=3.8% by simply polishing with an alumina paper. The proposed immunosensing system has been used to determine the BrAb in rabbit serum samples with satisfactory results.

  11. Enzymatic Inverse Opal Hydrogel Particles for Biocatalyst.

    Science.gov (United States)

    Wang, Huan; Gu, Hongcheng; Chen, Zhuoyue; Shang, Luoran; Zhao, Ze; Gu, Zhongze; Zhao, Yuanjin

    2017-04-19

    Enzymatic carriers have a demonstrated value for chemical reactions and industrial applications. Here, we present a novel kind of inverse opal hydrogel particles as the enzymatic carriers. The particles were negatively replicated from spherical colloidal crystal templates by using magnetic nanoparticles tagged acrylamide hydrogel. Thus, they were endowed with the features of monodispersity, small volume, complete penetrating structure, and controllable motion, which are all beneficial for improving the efficiency of biocatalysis. In addition, due to the ordered porous nanostructure, the inverse opal hydrogel particles were imparted with unique photonic band gaps (PBGs) and vivid structural colors for encoding varieties of immobilized enzymes and for constructing a multienzymes biocatalysis system. These features of the inverse opal hydrogel particles indicate that they are ideal enzymatic carriers for biocatalysis.

  12. Enzymatic oxidation of rutin by horseradish peroxidase: kinetic mechanism and identification of a dimeric product by LC-Orbitrap mass spectrometry.

    Science.gov (United States)

    Savic, Sasa; Vojinovic, Katarina; Milenkovic, Sanja; Smelcerovic, Andrija; Lamshoeft, Marc; Petronijevic, Zivomir

    2013-12-15

    Flavonoid oxidation is important issue in food processing and quality. The kinetic mechanism of enzymatic oxidation of rutin by horseradish peroxidase (HRP) was studied. Rutin oxidation reaction was followed by recording of spectral changes over the time at 360 nm. The studied oxidation is mostly enzymatic and less part non-enzymatic. The reaction with HRP has a higher rate compared with the reaction without of HRP, whereby is part of non-enzymatic reaction about 10% of the total reaction. Kinetic parameters were determined from graphics of linear Michaelis-Menten equation, and it was found that investigated reactions of rutin oxidation by HRP take place in a ping-pong kinetic mechanism. High resolution HPLC-MS analysis of the mixture of oxidized products of rutin revealed the presence of rutin dimer. Because of widely distribution of rutin as well as presence of peroxidases and hydrogen peroxide in fresh foods identification of this enzymatic modification product can be beneficial for foods quality and safety. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Use of hydrostatic pressure for modulation of protein chemical modification and enzymatic selectivity.

    Science.gov (United States)

    Makarov, Alexey A; Helmy, Roy; Joyce, Leo; Reibarkh, Mikhail; Maust, Mathew; Ren, Sumei; Mergelsberg, Ingrid; Welch, Christopher J

    2016-05-11

    Using hydrostatic pressure to induce protein conformational changes can be a powerful tool for altering the availability of protein reactive sites and for changing the selectivity of enzymatic reactions. Using a pressure apparatus, it has been demonstrated that hydrostatic pressure can be used to modulate the reactivity of lysine residues of the protein ubiquitin with a water-soluble amine-specific homobifunctional coupling agent. Fewer reactive lysine residues were observed when the reaction was carried out under elevated pressure of 3 kbar, consistent with a pressure-induced conformational change of ubiquitin that results in fewer exposed lysine residues. Additionally, modulation of the stereoselectivity of an enzymatic transamination reaction was observed at elevated hydrostatic pressure. In one case, the minor diasteromeric product formed at atmospheric pressure became the major product at elevated pressure. Such pressure-induced alterations of protein reactivity may provide an important new tool for enzymatic reactions and the chemical modification of proteins.

  14. Enzymatic epoxidation of biodiesel optimized by response surface ...

    African Journals Online (AJOL)

    During the enzymatic epoxidation of biodiesel, stearic acid was selected as oxygen carrier. Enzyme screening and the load of stearic acid were investigated. The effects of four main reaction conditions including reaction time, temperature, enzyme load, and mole ratio of H2O2/C=C-bonds on the epoxy oxygen group content ...

  15. Impact of the fouling mechanism on enzymatic depolymerization of xylan in different configurations of membrane reactors

    DEFF Research Database (Denmark)

    Mohd Sueb, Mohd Shafiq Bin; Luo, Jianquan; Meyer, Anne S.

    2017-01-01

    In order to maximize enzymatic xylan depolymerization while simultaneously purifying the resulting monosaccharide (xylose), different ultrafiltration (UF) membrane reactor configurations were evaluated. Initial results showed that the two hydrolytic enzymes required for complete depolymerization...... which hindered enzymatic attack in addition to fouling. Reaction with both enzymes followed by UF was found to be the optimal configuration, providing at least 40% higher xylan hydrolysis than the cascade configuration (involving sequential reaction with each of the enzymes separately......) and the simultaneous reaction-filtration with both enzymes, respectively. This study thus confirmed that the reactor configuration has a crucial impact on the performance of both the reaction and the separation process of xylose during enzymatic xylan degradation, and that the type of fouling mechanism varies...

  16. Perspectives for the industrial enzymatic production of glycosides.

    Science.gov (United States)

    de Roode, B Mattheus; Franssen, Maurice C R; van der Padt, Albert; Boom, Remko M

    2003-01-01

    Glycosides are of commercial interest for industry in general and specifically for the pharmaceutical and food industry. Currently chemical preparation of glycosides will not meet EC food regulations, and therefore chemical preparation of glycosides is not applicable in the food industry. Thus, enzyme-catalyzed reactions are a good alternative. However, until now the low yields obtained by enzymatic methods prevent the production of glycosides on a commercial scale. Therefore, high yields should be established by a combination of optimum reaction conditions and continuous removal of the product. Unfortunately, a bioreactor for the commercial scale production of glycosides is not available. The aim of this article is to discuss the literature with respect to enzymatic production of glycosides and the design of an industrially viable bioreactor system.

  17. Examination of various postulates of irreversibility

    Energy Technology Data Exchange (ETDEWEB)

    Salmon, J [Conservatoire National des Arts et Metiers (CNAM), 75 - Paris (France)

    1977-01-01

    Firstly, it is shown that it is necessary to break the reversible character of the B.B.G.K.Y. system of equations by means of a postulate of irreversibility to obtain a kinetic equation compatible with the second principle of thermodynamics. Next, three postulates of irreversibility are examined: that of molecular chaos, that of linear relaxation and, finally, that of superposition. Then the corresponding kinetic equations and the expressions for the viscosity coefficient to which they lead are determined. Comparison with experiment is made each time. Lastly, an attempt to obtain an irreversible kinetic equation without introducing a postulate of irreversibility in the B.B.G.K.Y. system is realized. This consists in adding a complementary irreversible term to the fundamental equation of the dynamics of a particle. The suggested term is of quantum origin and leads to a kinetic equation of the Fokker-Planck type.

  18. Enzymatic Transesterification of Ethyl Ferulate with Fish Oil and Reaction Optimization by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Zhiyong Yang

    2012-01-01

    Full Text Available The enzymatic transesterification of ethyl ferulate (EF with fish oil from cod liver was investigated with Novozym® 435 as catalyst under solvent-free conditions. The purpose of the study is to evaluate the synthesis system for the production of feruloyl fish oil in industry. The modified HPLC method was first set up to characterise the reaction products together with liquid chromatography electrospray time-of-flight mass spectrometry (HPLC-ESI-TOF-MS. The influence of the addition of glycerol to the system on the feruloyl acylglycerol profile was investigated in terms of transesterification performance. The bioconversion rate of EF can be significantly increased with the increased formation of feruloyl fish oil products when appropriate amount of glycerol is present in the reaction. Therefore, an equivalent molar amount of glycerol was added to EF for the practical optimization of the system. The mutual effects of temperature (40 to 70 °C, reaction time (1 to 5 days, enzyme load (2 to 20 % and molar ratio of fish oil and EF in the substrate (1 to 5 were thus studied with the assistance of response surface methodology (RSM for the purpose of maximizing the formation of feruloyl fish oil. The models were well fitted and verified. The optimized conditions were found to be: temperature 70 °C, enzyme load 4.3 %, substrate ratio 4.7, and reaction time 5 days. Under these conditions, the maximum conversion of EF reached 92.4 %, and the formation of feruloyl fish oil reached 80.4 %, but the formation of by-product was minimized to 11.4 % only.

  19. Increased release of fermentable sugars from elephant grass by enzymatic hydrolysis in the presence of surfactants

    International Nuclear Information System (INIS)

    Menegol, Daiane; Scholl, Angélica Luisi; Fontana, Roselei Claudete; Dillon, Aldo José Pinheiro; Camassola, Marli

    2014-01-01

    Highlights: • Milling is an attractive method to enhance the enzymatic hydrolysis of biomass. • Surfactants improve the efficiency of lignocellulose enzymatic hydrolysis. • Pretreatment with NaOH, smaller particle size and Tween 80® were more efficient. - Abstract: In the search for renewable energy sources, elephant grass is an alternative substrate for ethanol production, but this substrate must be hydrolyzed by cellulases and xylanases to liberate fermentable sugars. During enzymatic hydrolysis, cellulase activity is reduced by the irreversible adsorption of cellulase onto cellulose, decreasing the rate of hydrolysis. Adding surfactants during hydrolysis can improve the process. The effects of Tween® and Triton® surfactants on the enzymatic hydrolysis of elephant grass were evaluated in this context. The data indicate that pretreatment with sodium hydroxide, along with a smaller particle size (0.075–0.152 mm) and the use of Tween 80®, increased the efficiency of releasing reducing sugars from pretreated elephant grass biomass. Thus, it is possible to reduce grinding costs in second-generation ethanol production through the use of surfactants, as they allow efficient hydrolysis of larger biomass particles

  20. Enzymatic Synthesis of Psilocybin.

    Science.gov (United States)

    Fricke, Janis; Blei, Felix; Hoffmeister, Dirk

    2017-09-25

    Psilocybin is the psychotropic tryptamine-derived natural product of Psilocybe carpophores, the so-called "magic mushrooms". Although its structure has been known for 60 years, the enzymatic basis of its biosynthesis has remained obscure. We characterized four psilocybin biosynthesis enzymes, namely i) PsiD, which represents a new class of fungal l-tryptophan decarboxylases, ii) PsiK, which catalyzes the phosphotransfer step, iii) the methyltransferase PsiM, catalyzing iterative N-methyl transfer as the terminal biosynthetic step, and iv) PsiH, a monooxygenase. In a combined PsiD/PsiK/PsiM reaction, psilocybin was synthesized enzymatically in a step-economic route from 4-hydroxy-l-tryptophan. Given the renewed pharmaceutical interest in psilocybin, our results may lay the foundation for its biotechnological production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John

    2015-01-01

    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

  2. Quantitation of Na+, K+-atpase Enzymatic Activity in Tissues of the Mammalian Vestibular System

    Science.gov (United States)

    Kerr, T. P.

    1985-01-01

    In order to quantify vestibular Na(+), K(+)-ATPase, a microassay technique was developed which is sufficiently sensitive to measure the enzymatic activity in tissue from a single animal. The assay was used to characterize ATPase in he vestibular apparatus of the Mongolian gerbil. The quantitative procedure employs NPP (5 mM) as synthetic enzyme substrate. The assay relies upon spectrophotometric measurement (410 nm) of nitrophenol (NP) released by enzymatic hydrolysis of the substrate. Product formation in the absence of ouabain reflects both specific (Na(+), K(+)-ATPase) and non-specific (Mg(++)-ATPase) enzymatic activity. By measuring the accumulation of reaction product (NP) at three-minute intervals during the course of incubation, it is found that the overall enzymatic reaction proceeds linearly for at least 45 minutes. It is therefore possible to determine two separate reaction rates from a single set of tissues. Initial results indicate that total activity amounts to 53.3 + or - 11.2 (S.E.M.) nmol/hr/mg dry tissue, of which approximately 20% is ouabain-sensitive.

  3. Aqueous two-phase systems for extractive enzymatic hydrolysis of biomass

    DEFF Research Database (Denmark)

    Bussamra, Bianca Consorti; Azzoni, Sindelia Freitas; Mussatto, Solange I.

    and enzymes, phase diagrams and volumetric ratios. The results of this project will make possible to design a process that enables high sugar concentration during the hydrolysis reaction, overcoming one of the biggest drawbacks regarding the production of second-generation ethanol: the enzymatic inhibition...... optimal aqueous two-phase systems for the separation of sugars and enzymes, which allow the development of an improved second-generation ethanol process.......Sugars derived from lignocellulosic materials are the main carbon sources in bio-based processes aiming to produce renewable fuels and chemicals. One of the major drawbacks during enzymatic hydrolysis of lignocellulosic materials to obtainsugars is the inhibition of enzymes by reaction products...

  4. Ecological optimization for generalized irreversible Carnot refrigerators

    International Nuclear Information System (INIS)

    Chen Lingen; Zhu Xiaoqin; Sun Fengrui; Wu Chih

    2005-01-01

    The optimal ecological performance of a Newton's law generalized irreversible Carnot refrigerator with the losses of heat resistance, heat leakage and internal irreversibility is derived by taking an ecological optimization criterion as the objective, which consists of maximizing a function representing the best compromise between the exergy output rate and exergy loss rate (entropy production rate) of the refrigerator. Numerical examples are given to show the effects of heat leakage and internal irreversibility on the optimal performance of generalized irreversible refrigerators

  5. Chemo‐enzymatic epoxidation–process options for improving biocatalytic productivity

    DEFF Research Database (Denmark)

    Hagström, Anna E. V.; Törnvall, Ulrika; Nordblad, Mathias

    2011-01-01

    The reactor choice is crucial when designing a process where inactivation of the biocatalyst is a problem. The main bottleneck for the chemo‐enzymatic epoxidation has been found to be enzyme inactivation by the hydrogen peroxide, H2O2, substrate. In the work reported here, the effect of reaction...... parameters on the reaction performance have been investigated and used to establish suitable operating strategies to minimize the inactivation of the enzyme, using rapeseed methyl ester (RME) as a substrate in a solvent‐free system. The use of a controlled fed‐batch reactor for maintaining H2O2 concentration...... at 1.5 M resulted in increased productivity, up to 76 grams of product per gram of biocatalyst with higher retention of enzyme activity. Further investigation included a multistage design that separated the enzymatic reaction and the saturation of the RME substrate with H2O2 into different vessels...

  6. New eutectic ionic liquids for lipase activation and enzymatic preparation of biodiesel†

    Science.gov (United States)

    Zhao, Hua; Baker, Gary A.; Holmes, Shaletha

    2012-01-01

    The enzymatic preparation of biodiesel has been hampered by the lack of suitable solvents with desirable properties such as high lipase compatibility, low cost, low viscosity, high biodegradability, and ease of product separation. Recent interest in using ionic liquids (ILs) as advanced reaction media has led to fast reaction rates and high yields in the enzymatic synthesis of biodiesel. However, conventional (i.e., cation–anion paired) ILs based on imidazolium and other quaternary ammonium salts remain too expensive for wide application at industrial scales. In this study, we report on newly-synthesized eutectic ILs derived from choline acetate or choline chloride coupled with biocompatible hydrogen-bond donors, such as glycerol. These eutectic solvents have favorable properties including low viscosity, high biodegradability, and excellent compatibility with Novozym® 435, a commercial immobilized Candida antarctica lipase B. Furthermore, in a model biodiesel synthesis system, we demonstrate high reaction rates for the enzymatic transesterification of Miglyol® oil 812 with methanol, catalyzed by Novozym® 435 in choline acetate/glycerol (1 : 1.5 molar ratio). The high conversion (97%) of the triglyceride obtained within 3 h, under optimal conditions, suggests that these novel eutectic solvents warrant further exploration as potential media in the enzymatic production of biodiesel. PMID:21283901

  7. Immobilization of alcohol dehydrogenase on ceramic silicon carbide membranes for enzymatic CH3 OH production

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Ma, Nicolaj; Berendt, Kasper

    2018-01-01

    BACKGROUND Alcohol dehydrogenase (ADH; EC 1.1.1.1) catalyzes oxidation of CH3OH to CHOH during NAD+ reduction to NADH. ADH can also accelerate the reverse reaction, which is studied as part of cascadic enzymatic conversion of CO2 to CH3OH. In the present study, immobilization of ADH onto macropor......BACKGROUND Alcohol dehydrogenase (ADH; EC 1.1.1.1) catalyzes oxidation of CH3OH to CHOH during NAD+ reduction to NADH. ADH can also accelerate the reverse reaction, which is studied as part of cascadic enzymatic conversion of CO2 to CH3OH. In the present study, immobilization of ADH onto......‐of‐concept for the use of NaOH‐treated SiC membranes for covalent enzyme immobilization and biocatalytic efficiency improvement of ADH during multiple reaction cycles. These data have implications for the development of robust extended enzymatic reactions....

  8. Quantifying the limits of transition state theory in enzymatic catalysis.

    Science.gov (United States)

    Zinovjev, Kirill; Tuñón, Iñaki

    2017-11-21

    While being one of the most popular reaction rate theories, the applicability of transition state theory to the study of enzymatic reactions has been often challenged. The complex dynamic nature of the protein environment raised the question about the validity of the nonrecrossing hypothesis, a cornerstone in this theory. We present a computational strategy to quantify the error associated to transition state theory from the number of recrossings observed at the equicommittor, which is the best possible dividing surface. Application of a direct multidimensional transition state optimization to the hydride transfer step in human dihydrofolate reductase shows that both the participation of the protein degrees of freedom in the reaction coordinate and the error associated to the nonrecrossing hypothesis are small. Thus, the use of transition state theory, even with simplified reaction coordinates, provides a good theoretical framework for the study of enzymatic catalysis. Copyright © 2017 the Author(s). Published by PNAS.

  9. Advanced Caries Microbiota in Teeth with Irreversible Pulpitis.

    Science.gov (United States)

    Rôças, Isabela N; Lima, Kenio C; Assunção, Isauremi V; Gomes, Patrícia N; Bracks, Igor V; Siqueira, José F

    2015-09-01

    Bacterial taxa in the forefront of caries biofilms are candidate pathogens for irreversible pulpitis and are possibly the first ones to invade the pulp and initiate endodontic infection. This study examined the microbiota of the most advanced layers of dentinal caries in teeth with irreversible pulpitis. DNA extracted from samples taken from deep dentinal caries associated with pulp exposures was analyzed for the presence and relative levels of 33 oral bacterial taxa by using reverse-capture checkerboard hybridization assay. Quantification of total bacteria, streptococci, and lactobacilli was also performed by using real-time quantitative polymerase chain reaction. Associations between the target bacterial taxa and clinical signs/symptoms were also evaluated. The most frequently detected taxa in the checkerboard assay were Atopobium genomospecies C1 (53%), Pseudoramibacter alactolyticus (37%), Streptococcus species (33%), Streptococcus mutans (33%), Parvimonas micra (13%), Fusobacterium nucleatum (13%), and Veillonella species (13%). Streptococcus species, Dialister invisus, and P. micra were significantly associated with throbbing pain, S. mutans with pain to percussion, and Lactobacillus with continuous pain (P pulpitis is suspected. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  10. In search of principles for a Theory of Organisms

    Indian Academy of Sciences (India)

    2015-12-01

    Dec 1, 2015 ... 6 For example, irreversibility means that we can tell when a movie is ..... cells, and estrogen cancels the action of this constraint ... cycle is a representation of enzymatic reactions and physical ..... man breast cells in real time.

  11. Operation variables in transesterification of vegetable oil: an enzymatic catalysis review

    Directory of Open Access Journals (Sweden)

    Andrés Felipe Rojas González

    2010-01-01

    Full Text Available This paper presents the results of a literature review regarding how operating conditions influence vegetable oil enzymatic transesterification yield. The following parameters were studied: temperature and time reaction, alcohol: oil molar ratio, alcohol type, biocatalyst type and concentration, solvent, mixed intensity, reagent purity and free fatty acid and moisture concentration. Yields greater than 90% can be achieved in the enzymatic catalyst of vegetable oil using 35-50°C temperatures, long time reactions (7- 90h and a 3:1alcohol: vegetable oil molar ratio; however, such values would intrinsically depend on the type of lipase and oil u- sed. It was also found that free fatty acid and moisture concentration were parameters which did not require rigorous control due to high enzyme specificity. Lipases immobilised from Pseudomona cepacia bacteria and Rhizopus orizae fungi were most used in vegetable oil enzymatic transesterification.

  12. Production of MAG via enzymatic glycerolysis

    Science.gov (United States)

    Jamlus, Norul Naziraa Ahmad; Derawi, Darfizzi; Salimon, Jumat

    2015-09-01

    Enzymatic glycerolysis of a medium chain methyl ester, methyl laurate was performed using lipase Candida antarctica (Novozyme 435) for 6 hours at 55°C. The percentage of components mixture of product were determined by using gas chromatography technique. The enzymatic reaction was successfully produced monolaurin (45.9 %), dilaurin (47.1 %) and trilaurin (7.0 %) respectively. Thin layer chromatography (TLC) plate also showed a good separation of component spots. Fourier transformation infra-red (FTIR) spectrum showed the presence of ester carbonyl at wavenumber 1739.99 cm-1 and hydrogen bonded O-H at 3512.03 cm-1. The product is potentially to be used as emulsifier and additive in food industry, pharmaceutical, as well as antibacterial.

  13. Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

    KAUST Repository

    Shi, Junfeng; Yuan, Dan; Haburcak, Richard; Zhang, Qiang; Zhao, Chao; Zhang, Xixiang; Xu, Bing

    2015-01-01

    Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

  14. Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

    KAUST Repository

    Shi, Junfeng

    2015-10-14

    Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

  15. Real-time ESI-MS of enzymatic conversion: impact of organic solvents and multiplexing.

    Science.gov (United States)

    Scheerle, Romy K; Grassmann, Johanna; Letzel, Thomas

    2012-01-01

    Different enzymatic assays were characterized systematically by real-time electrospray ionization mass spectrometry (ESI-MS) in the presence of organic solvents as well as in multiplex approaches and in a combination of both. Typically, biological enzymatic reactions are studied in aqueous solutions, since most enzymes show their full activity solely in aqueous solutions. However, in recent years, the use of organic solvents in combination with enzymatic reactions has gained increasing interest due to biotechnological advantages in chemical synthesis, development of online coupled setups screening for enzyme regulatory compounds, advantages regarding mass spectrometric detection and others. In the current study, the influence of several common organic solvents (methanol, ethanol, isopropanol, acetone, acetonitrile) on enzymatic activity (hen egg white lysozyme, chitinase, α-chymotrypsin, elastase from human neutrophils and porcine pancreas, acetylcholinesterase) was tested. Moreover, multiplexing is a promising approach enabling fast and cost-efficient screening methods, e.g. for determination of inhibitors in complex mixtures or in the field of biomedical research. Although in multiplexed setups the enzymatic activity may be affected by the presence of other substrates and/or enzymes, the expected advantages possibly will predominate. To investigate those effects, we measured multiple enzymatic assays simultaneously. For all conducted measurements, the conversion rate of the substrate(s) was calculated, which reflects the enzymatic activity. The results provide an overview about the susceptibility of the selected enzymes towards diverse factors and a reference point for many applications in analytical chemistry and biotechnology.

  16. Entropy, Extropy and the Physical Driver of Irreversibility

    Directory of Open Access Journals (Sweden)

    Attila Grandpierre

    2012-06-01

    Full Text Available We point out that the fundamental irreversibility of Nature requires the introduction of a suitable measure for the distance from equilibrium. We show that entropy, which is widely held to be such a measure, suffers from the problem that it does not have a physical meaning, since it is introduced on the basis of mathematical arguments. As a consequence, the basic physics beyond irreversibility has remained obscure. We present here a simple but transparent physical approach for solving the problem of irreversibility. This approach shows that extropy, the fundamental thermodynamic variable introduced by Katalin Martinás, is the suitable measure for the distance from equilibrium, since it corresponds to the actual driver of irreversible processes. Since extropy explicitly contains in its definition all the general thermodynamic forces that drive irreversible processes, extropy is the suitable physical measure of irreversibility.

  17. Modeling of the Reaction Mechanism of Enzymatic Radical C–C Coupling by Benzylsuccinate Synthase

    Directory of Open Access Journals (Sweden)

    Maciej Szaleniec

    2016-04-01

    Full Text Available Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C–C coupling catalyzed by benzylsuccinate synthase (BSS. BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i What mechanistic details of the BSS reaction yield the most probable molecular model? (ii What is the molecular basis of enantiospecificity of BSS? (iii Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R-benzylsuccinate as a product and a kinetic isotope effect (KIE ranging between 2 and 4? The quantum mechanics (QM modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C–H activation and not C–C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R orientation and reverse preference of benzyl radical attack on fumarate in pro(S pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5 is still higher than the experimentally observed values (4.0 which suggests that both C–H activation and radical quenching may jointly be involved in the kinetic control of the reaction.

  18. Does acetaminophen/hydrocodone affect cold pulpal testing in patients with symptomatic irreversible pulpitis? A prospective, randomized, double-blind, placebo-controlled study.

    Science.gov (United States)

    Fowler, Sara; Fullmer, Spencer; Drum, Melissa; Reader, Al

    2014-12-01

    The purpose of this prospective randomized, double-blind, placebo-controlled study was to determine the effects of a combination dose of 1000 mg acetaminophen/10 mg hydrocodone on cold pulpal testing in patients experiencing symptomatic irreversible pulpitis. One hundred emergency patients in moderate to severe pain diagnosed with symptomatic irreversible pulpitis of a mandibular posterior tooth randomly received, in a double-blind manner, identical capsules of either a combination of 1000 mg acetaminophen/10 hydrocodone or placebo. Cold testing with Endo-Ice (1,1,1,2 tetrafluoroethane; Hygenic Corp, Akron, OH) was performed at baseline and every 10 minutes for 60 minutes. Pain to cold testing was recorded by the patient using a Heft-Parker visual analog scale. Patients' reaction to the cold application was also rated. Cold testing at baseline and at 10 minutes resulted in severe pain for both the acetaminophen/hydrocodone and placebo groups. Although pain ratings decreased from 20-60 minutes, the ratings still resulted in moderate pain. Patient reaction to cold testing showed that 56%-62% had a severe reaction. Although the reactions decreased in severity over the 60 minutes, 20%-34% still had severe reactions at 60 minutes. Regarding pain and patients' reactions to cold testing, there were no significant differences between the combination acetaminophen/hydrocodone and placebo groups at any time period. A combination dose of 1000 mg of acetaminophen/10 mg of hydrocodone did not statistically affect cold pulpal testing in patients presenting with symptomatic irreversible pulpitis. Patients experienced moderate to severe pain and reactions to cold testing. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  19. Multicompartment Artificial Organelles Conducting Enzymatic Cascade Reactions inside Cells

    DEFF Research Database (Denmark)

    Gallardo, Maria Godoy; Labay, Cédric Pierre; Trikalitis, Vasileios

    2017-01-01

    Cell organelles are subcellular structures entrapping a set of enzymes to achieve a specific functionality. The incorporation of artificial organelles into cells is a novel medical paradigm which might contribute to the treatment of various cell disorders by replacing malfunctioning organelles....... In particular, artificial organelles are expected to be a powerful solution in the context of enzyme replacement therapy since enzymatic malfunction is the primary cause of organelle dysfunction. Although several attempts have been made to encapsulate enzymes within a carrier vehicle, only few intracellularly...

  20. Self-powered gustation electronic skin for mimicking taste buds based on piezoelectric-enzymatic reaction coupling process

    Science.gov (United States)

    Zhao, Tianming; Fu, Yongming; He, Haoxuan; Dong, Chuanyi; Zhang, Linlin; Zeng, Hui; Xing, Lili; Xue, Xinyu

    2018-02-01

    A new self-powered wearable gustation electronic skin for mimicking taste buds has been realized based on enzyme-modified/ZnO nanowire arrays on patterned-electrode flexible substrate. The e-skin can actively taste beverages or fruits without any external electric power. Through the piezoelectric-enzymatic reaction coupling effect, the nanowires can harvest the mechanical energy of body movement and output piezoelectric signal. The piezoelectric output is significantly dependent on the concentration of target analyte. The response for detecting 2 × 10-2 M ascorbic acid (ascorbate acid oxidase@ZnO) is up to 171.747, and the selectivity is high. The response for detecting 50% alcohol (alcohol oxidase@ZnO) is up to 45.867. Our results provide a new research direction for the development of multifunctional e-skin and expand the study scope for self-powered bionic systems.

  1. Isothermal calorimetry on enzymatic biodiesel production

    DEFF Research Database (Denmark)

    Fjerbæk, Lene

    2008-01-01

    information about effects taking place when using lipases immobilized on an inert carrier for transesterification of a triglyceride and an alcohol as for biodiesel production. The biodiesel is produced by rapeseed oil and methanol as well as ethanol and a commercial biocatalyst Novozym 435 from Novozymes...... containing a Candida Antarctica B lipase immobilized on an acrylic resin. The reaction investigated is characterized by immiscible liquids (oil, methanol, glycerol and biodiesel) and enzymes imm. on an inert carrier during reaction, which allows several effects to take place that during normal reaction...... conditions can not be elucidated. These effects have been observed with isothermal calorimetry bringing forth new information about the reaction of enzymes catalyzing transesterification. Enzymatic biodiesel production has until now not been investigated with isothermal microcalorimetry, but the results...

  2. Production of Fish Hydrolysates Protein From Waste of Fish Carp (Cyprinus Carpio) by Enzymatic Hydrolysis

    OpenAIRE

    Saputra, Dede; Nurhayati, Tati

    2016-01-01

    Fish Protein Hydrolysates (FPH) is the mixed products of polypeptide, dipeptides, and amino acid. It can be produced from materials that contained of protein by acid reaction, base reaction or enzymatic hydrolysis. The objectives of this study were to study the production of FPH from fish carp meat at post rigor phase and viscera by enzymatic hydrolysis, to determine the specific activity of papain enzyme, and to determine the solubility of FPH. Capacity of fish hydrolyzing can be identified ...

  3. Irreversible dynamics, Onsager-Casimir symmetry, and an application to turbulence.

    Science.gov (United States)

    Ottinger, Hans Christian

    2014-10-01

    Irreversible contributions to the dynamics of nonequilibrium systems can be formulated in terms of dissipative, or irreversible, brackets. We discuss the structure of such irreversible brackets in view of a degeneracy implied by energy conservation, where we consider different types of symmetries of the bracket corresponding to the Onsager and Casimir symmetries of linear irreversible thermodynamics. Slip and turbulence provide important examples of antisymmetric irreversible brackets and offer guidance for the more general modeling of irreversible dynamics without entropy production. Conversely, turbulence modeling could benefit from elucidating thermodynamic structure. The examples suggest constructing antisymmetric irreversible brackets in terms of completely antisymmetric functions of three indices. Irreversible brackets without well-defined symmetry properties can arise for rare events, causing big configurational changes.

  4. Metal-free bioconjugation reactions.

    Science.gov (United States)

    van Berkel, Sander S; van Delft, Floris L

    2013-01-01

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

  5. Hydraulically irreversible fouling on ceramic MF/UF membranes: comparison of fouling indices, foulant composition and irreversible pore narrowing

    KAUST Repository

    Shang, Ran; Vuong, Francois; Hu, Jingyi; Li, Sheng; Kemperman, Antoine J.B.; Nijmeijer, Kitty; Cornelissen, Emile R.; Heijman, Sebastiaan G.J.; Rietveld, Luuk C.

    2015-01-01

    The application of ceramic membranes in water treatment is becoming increasing attractive because of their long life time and excellent chemical, mechanical and thermal stability. However, fouling of ceramic membranes, especially hydraulically irreversible fouling, is still a critical aspect affecting the operational cost and energy consumption in water treatment plants. In this study, four ceramic membranes with pore sizes or molecular weight cut-off (MWCO) of 0.20 μm, 0.14 μm, 300 kDa and 50 kDa were compared during natural surface water filtration with respect to hydraulically irreversible fouling index (HIFI), foulant composition and narrowing of pore size due to the irreversible fouling. Our results showed that the hydraulically irreversible fouling index (HIFI) was proportional to the membrane pore size (r2=0.89) when the same feed water was filtrated. The UF membranes showed lower HIFI values than the MF membranes. Pore narrowing (internal fouling) was found to be a main fouling pattern of the hydraulically irreversible fouling. The internal fouling was caused by monolayer adsorption of foulants with different sizes that is dependent on the size of the membrane pore.

  6. Hydraulically irreversible fouling on ceramic MF/UF membranes: comparison of fouling indices, foulant composition and irreversible pore narrowing

    KAUST Repository

    Shang, Ran

    2015-05-06

    The application of ceramic membranes in water treatment is becoming increasing attractive because of their long life time and excellent chemical, mechanical and thermal stability. However, fouling of ceramic membranes, especially hydraulically irreversible fouling, is still a critical aspect affecting the operational cost and energy consumption in water treatment plants. In this study, four ceramic membranes with pore sizes or molecular weight cut-off (MWCO) of 0.20 μm, 0.14 μm, 300 kDa and 50 kDa were compared during natural surface water filtration with respect to hydraulically irreversible fouling index (HIFI), foulant composition and narrowing of pore size due to the irreversible fouling. Our results showed that the hydraulically irreversible fouling index (HIFI) was proportional to the membrane pore size (r2=0.89) when the same feed water was filtrated. The UF membranes showed lower HIFI values than the MF membranes. Pore narrowing (internal fouling) was found to be a main fouling pattern of the hydraulically irreversible fouling. The internal fouling was caused by monolayer adsorption of foulants with different sizes that is dependent on the size of the membrane pore.

  7. Evaluation of wet oxidation pretreatment for enzymatic hydrolysis of softwood

    DEFF Research Database (Denmark)

    Palonen, H.; Thomsen, A.B.; Tenkanen, M.

    2004-01-01

    The wet oxidation pretreatment (water, oxygen, elevated temperature, and pressure) of softwood (Picea abies) was investigated for enhancing enzymatic hydrolysis. The pretreatment was preliminarily optimized. Six different combinations of reaction time, temperature, and pH were applied......, and the compositions of solid and liquid fractions were analyzed. The solid fraction after wet oxidation contained 58-64% cellulose, 2-16% hemicellulose, and 24-30% lignin. The pretreatment series gave information about the roles of lignin and hemicellulose in the enzymatic hydrolysis. The temperature...

  8. Dynamic modeling and validation of a lignocellulosic enzymatic hydrolysis process

    DEFF Research Database (Denmark)

    Prunescu, Remus Mihail; Sin, Gürkan

    2013-01-01

    The enzymatic hydrolysis process is one of the key steps in second generation biofuel production. After being thermally pretreated, the lignocellulosic material is liquefied by enzymes prior to fermentation. The scope of this paper is to evaluate a dynamic model of the hydrolysis process...... on a demonstration scale reactor. The following novel features are included: the application of the Convection–Diffusion–Reaction equation to a hydrolysis reactor to assess transport and mixing effects; the extension of a competitive kinetic model with enzymatic pH dependency and hemicellulose hydrolysis......; a comprehensive pH model; and viscosity estimations during the course of reaction. The model is evaluated against real data extracted from a demonstration scale biorefinery throughout several days of operation. All measurements are within predictions uncertainty and, therefore, the model constitutes a valuable...

  9. Enzymatic Modification of Sphingomyelin

    DEFF Research Database (Denmark)

    Due to its major role in maintaining the water-retaining properties of the epidermis, ceramide is of great commercial potential in cosmetic and pharmaceuticals such as hair and skin care products. Currently, chemical synthesis of ceramide is a costly process, and developments of alternative cost......-efficient, high yield production methods are of great interest. In the present study, the potential of producing ceramide through the enzymatic hydrolysis of sphingomyelin have been studied. sphingomyelin is a ubiquitous membrane-lipid and rich in dairy products or by-products. It has been verified...... that sphingomyelin modification gives a feasible approach to the potential production of ceramide. The reaction system has been improved through system evaluation and the optimization of several important factors, and phospholipase C from Clostridium perfringens shows higher activity towards the hydrolysis reaction...

  10. Enzymatic modification of starch

    DEFF Research Database (Denmark)

    Jensen, Susanne Langgård

    In the food industry approaches for using bioengineering are investigated as alternatives to conventional chemical and physical starch modification techniques in development of starches with specific properties. Enzyme-assisted post-harvest modification is an interesting approach to this, since...... it is considered a clean and energy saving technology. This thesis aimed to investigate the effect of using reaction conditions, simulating an industrial process, for enzymatic treatment of starch with branching enzyme (BE) from Rhodothermus obamensis. Thus treatements were conducted at 70°C using very high...... substrate concentration (30-40% dry matter (DM)) and high enzyme activity (750-2250 BE units (BEU)/g sample). Starches from various botanical sources, representing a broad range of properties, were used as substrates. The effects of the used conditions on the BE-reaction were evaluated by characterization...

  11. Chemical boundary layers in CVD II. Reversible reactions

    NARCIS (Netherlands)

    Croon, de M.H.J.M.; Giling, L.J.

    1990-01-01

    In addition to irreversible reactions, which were treated in part I, reversible reactions in the gas phase have beenstudied using the concept of the chemical boundary layer. The analysis is given for the situations in which either the forwardor the back reaction is dominant. Two conceptual models

  12. A compartmentalized out-of-equilibrium enzymatic reaction network for sustained autonomous movement

    NARCIS (Netherlands)

    Nijemeisland, M.; Abdelmohsen, L.K.E.A.; Huck, W.T.S.; Wilson, D.A.; van Hest, J.C.M.

    2016-01-01

    Every living cell is a compartmentalized out-ofequilibrium system exquisitely able to convert chemical energy into function. In order to maintain homeostasis, the flux of metabolites is tightly controlled by regulatory enzymatic networks. A crucial prerequisite for the development of lifelike

  13. Pyridoxine Supplementation Improves the Activity of Recombinant Glutamate Decarboxylase and the Enzymatic Production of Gama-Aminobutyric Acid.

    Directory of Open Access Journals (Sweden)

    Yan Huang

    Full Text Available Glutamate decarboxylase (GAD catalyzes the irreversible decarboxylation of L-glutamate to the valuable food supplement γ-aminobutyric acid (GABA. In this study, GAD from Escherichia coli K12, a pyridoxal phosphate (PLP-dependent enzyme, was overexpressed in E. coli. The GAD produced in media supplemented with 0.05 mM soluble vitamin B6 analog pyridoxine hydrochloride (GAD-V activity was 154.8 U mL-1, 1.8-fold higher than that of GAD obtained without supplementation (GAD-C. Purified GAD-V exhibited increased activity (193.4 U mg-1, 1.5-fold higher than that of GAD-C, superior thermostability (2.8-fold greater than that of GAD-C, and higher kcat/Km (1.6-fold higher than that of GAD-C. Under optimal conditions in reactions mixtures lacking added PLP, crude GAD-V converted 500 g L-1 monosodium glutamate (MSG to GABA with a yield of 100%, and 750 g L-1 MSG with a yield of 88.7%. These results establish the utility of pyridoxine supplementation and lay the foundation for large-scale enzymatic production of GABA.

  14. Irreversibility and dissipation in finite-state automata

    International Nuclear Information System (INIS)

    Ganesh, Natesh; Anderson, Neal G.

    2013-01-01

    Irreversibility and dissipation in finite-state automata (FSA) are considered from a physical-information-theoretic perspective. A quantitative measure for the computational irreversibility of finite automata is introduced, and a fundamental lower bound on the average energy dissipated per state transition is obtained and expressed in terms of FSA irreversibility. The irreversibility measure and energy bound are germane to any realization of a deterministic automaton that faithfully registers abstract FSA states in distinguishable states of a physical system coupled to a thermal environment, and that evolves via a sequence of interactions with an external system holding a physical instantiation of a random input string. The central result, which is shown to follow from quantum dynamics and entropic inequalities alone, can be regarded as a generalization of Landauer's Principle applicable to FSAs and tailorable to specified automata. Application to a simple FSA is illustrated.

  15. Development of an enzymatic microreactor based on microencapsulated laccase with off-line capillary electrophoresis for measurement of oxidation reactions.

    Science.gov (United States)

    Roman-Gusetu, Georgiana; Waldron, Karen C; Rochefort, Dominic

    2009-11-20

    Microencapsulation is used here as a new technique to immobilize enzymes in a microreactor coupled off-line to capillary electrophoresis (CE), allowing the determination of enzymatic reaction products. The redox enzyme laccase was encapsulated using the method of interfacial cross-linking of poly(ethyleneimine) (PEI). The 50 microm diameter capsules were slurry packed from a suspension into a capillary-sized reactor made easily and quickly from a short length of 530 microm diameter fused-silica tubing. The volume of the bed of laccase microcapsules in the microreactor was in the order of 1.1 microL through which 50 microL of the substrate o-phenylenediamine (OPD) was flowed. The oxidation product 2,3-diaminophenazine (DAP) and the remaining OPD were quantified by CE in a pH 2.5 phosphate buffer. Peak migration time reproducibility was in the order of 0.4% RSD and peak area reproducibility was less than 1.7% RSD within the same day. Using the OPD peak area calibration curve, a conversion efficiency of 48% was achieved for a 2-min oxidation reaction in the microreactor.

  16. Combined subcritical water and enzymatic hydrolysis for reducing sugar production from coconut husk

    Science.gov (United States)

    Muharja, Maktum; Junianti, Fitri; Nurtono, Tantular; Widjaja, Arief

    2017-05-01

    Coconut husk wastes are abundantly available in Indonesia. It has a potential to be used into alternative renewable energy sources such as hydrogen using enzymatic hydrolysis followed by a fermentation process. Unfortunately, enzymatic hydrolysis is hampered by the complex structure of lignocellulose, so the cellulose component is hard to degrade. In this study, Combined Subcritical Water (SCW) and enzymatic hydrolysis are applied to enhance fermentable, thereby reducing production of sugar from coconut husk. There were two steps in this study, the first step was coconut husk pretreated by SCW in batch reactor at 80 bar and 150-200°C for 60 minutes reaction time. Secondly, solid fraction from the results of SCW was hydrolyzed using the mixture of pure cellulose and xylanase enzymes. Analysis was conducted on untreated and SCW-treated by gravimetric assay, liquid fraction after SCW and solid fraction after enzymatic hydrolysis using DNS assay. The maximum yield of reducing sugar (including xylose, arabinose glucose, galactose, mannose) was 1.254 gr per 6 gr raw material, representing 53.95% of total sugar in coconut husk biomass which was obtained at 150°C 80 bar for 60 minutes reaction time of SCW-treated and 6 hour of enzymatic hydrolysis using mixture of pure cellulose and xylanase enzymes (18.6 U /gram of coconut husk).

  17. Include dispersion in quantum chemical modeling of enzymatic reactions: the case of isoaspartyl dipeptidase.

    Science.gov (United States)

    Zhang, Hai-Mei; Chen, Shi-Lu

    2015-06-09

    The lack of dispersion in the B3LYP functional has been proposed to be the main origin of big errors in quantum chemical modeling of a few enzymes and transition metal complexes. In this work, the essential dispersion effects that affect quantum chemical modeling are investigated. With binuclear zinc isoaspartyl dipeptidase (IAD) as an example, dispersion is included in the modeling of enzymatic reactions by two different procedures, i.e., (i) geometry optimizations followed by single-point calculations of dispersion (approach I) and (ii) the inclusion of dispersion throughout geometry optimization and energy evaluation (approach II). Based on a 169-atom chemical model, the calculations show a qualitative consistency between approaches I and II in energetics and most key geometries, demonstrating that both approaches are available with the latter preferential since both geometry and energy are dispersion-corrected in approach II. When a smaller model without Arg233 (147 atoms) was used, an inconsistency was observed, indicating that the missing dispersion interactions are essentially responsible for determining equilibrium geometries. Other technical issues and mechanistic characteristics of IAD are also discussed, in particular with respect to the effects of Arg233.

  18. Thermal mechanisms responsible for the irreversible degradation of superconductivity in commercial superconductors

    Science.gov (United States)

    Romanovskii, V. R.

    2017-08-01

    Conditions for the irreversible propagation of thermal instabilities in commercial superconductors subjected to intense and soft cooling have been formulated. An analysis has been conducted using two types of the superconductor's I-V characteristics, i.e., an ideal I-V characteristic, which assumes a step superconducting-to-normal transition, and a continuous I-V characteristic, which is described by a power law. The propagation rate of thermal instabilities along the superconducting composite has been determined. Calculations have been made for both subcritical and supercritical values of the current. It has been shown that they propagate along a commercial superconductor in the form of a switching wave. In rapidly cooled commercial superconductors, the steady-state rate of thermal instability propagation in the longitudinal direction can only be positive because there is no region of steady stabilization. It has been proved that, in the case of thermal instability irreversible propagation, the rise in the commercial superconductor temperature is similar to diffusion processes that occur in explosive chain reactions.

  19. Extended Irreversible Thermodynamics

    CERN Document Server

    Jou, David

    2010-01-01

    This is the 4th edition of the highly acclaimed monograph on Extended Irreversible Thermodynamics, a theory that goes beyond the classical theory of irreversible processes. In contrast to the classical approach, the basic variables describing the system are complemented by non-equilibrium quantities. The claims made for extended thermodynamics are confirmed by the kinetic theory of gases and statistical mechanics. The book covers a wide spectrum of applications, and also contains a thorough discussion of the foundations and the scope of the current theories on non-equilibrium thermodynamics. For this new edition, the authors critically revised existing material while taking into account the most recent developments in fast moving fields such as heat transport in micro- and nanosystems or fast solidification fronts in materials sciences. Several fundamental chapters have been revisited emphasizing physics and applications over mathematical derivations. Also, fundamental questions on the definition of non-equil...

  20. Methylation reactions, the redox balance and atherothrombosis: the search for a link with hydrogen sulfide.

    Science.gov (United States)

    Lupoli, Roberta; Di Minno, Alessandro; Spadarella, Gaia; Franchini, Massimo; Sorrentino, Raffaella; Cirino, Giuseppe; Di Minno, Giovanni

    2015-06-01

    It is now clear that homocysteine (Hcy) is irreversibly degraded to hydrogen sulfide (H(2)S), an endogenous gasotransmitter that causes in vivo platelet activation via upregulation of phospholipase A2 and downstream boost of the arachidonate cascade. This mechanism involves a transsulfuration pathway. Based on these new data, clinical and experimental models on the relationships between Hcy and folate pathways in vascular disease and information on the Hcy controversy have been reanalyzed in the present review. Most interventional trials focused on Hcy lowering by folate administration did not exclude patients routinely taking the arachidonate inhibitor aspirin. This may have influenced the results of some of these trials. It is also clear that nutritional intake of folate affects several enzymatic reactions of the methionine-Hcy cycle and associated one-carbon metabolism and, thereby, both methylation reactions and redox balance. Hence, it is conceivable that the abnormally high Hcy levels seen in pathologic states reflect a poorly elucidated perturbation of such reactions and of such balance. While it is unknown whether there is an interplay between H2S, methylation reactions, and redox balance, measuring the sole reduction of blood Hcy that follows folate administration may well be an oversimplified approach to a complex biologic perturbation. The need to investigate this complex framework is thoroughly discussed in this article. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

  1. Laboratory-scale method for enzymatic saccharification of lignocellulosic biomass at high-solids loadings

    Directory of Open Access Journals (Sweden)

    Dibble Clare J

    2009-11-01

    Full Text Available Abstract Background Screening new lignocellulosic biomass pretreatments and advanced enzyme systems at process relevant conditions is a key factor in the development of economically viable lignocellulosic ethanol. Shake flasks, the reaction vessel commonly used for screening enzymatic saccharifications of cellulosic biomass, do not provide adequate mixing at high-solids concentrations when shaking is not supplemented with hand mixing. Results We identified roller bottle reactors (RBRs as laboratory-scale reaction vessels that can provide adequate mixing for enzymatic saccharifications at high-solids biomass loadings without any additional hand mixing. Using the RBRs, we developed a method for screening both pretreated biomass and enzyme systems at process-relevant conditions. RBRs were shown to be scalable between 125 mL and 2 L. Results from enzymatic saccharifications of five biomass pretreatments of different severities and two enzyme preparations suggest that this system will work well for a variety of biomass substrates and enzyme systems. A study of intermittent mixing regimes suggests that mass transfer limitations of enzymatic saccharifications at high-solids loadings are significant but can be mitigated with a relatively low amount of mixing input. Conclusion Effective initial mixing to promote good enzyme distribution and continued, but not necessarily continuous, mixing is necessary in order to facilitate high biomass conversion rates. The simplicity and robustness of the bench-scale RBR system, combined with its ability to accommodate numerous reaction vessels, will be useful in screening new biomass pretreatments and advanced enzyme systems at high-solids loadings.

  2. Thermodynamically based solvent design for enzymatic saccharide acylation with hydroxycinnamic acids in non-conventional media

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Kontogeorgis, Georgios; Riisager, Anders

    2012-01-01

    as well as other enzymatic hydroxycinnamate acylations in ionic liquid systems. The choice of solvent system is highly decisive for enzyme stability, selectivity, and reaction yields in these synthesis reactions. To increase the understanding of the reaction environment and to facilitate solvent screening......-free microemulsions of a hydrocarbon, a polar alcohol, and water are interesting solvent systems because they accommodate different substrate and product solubilities and maintain enzyme stability. Ionic liquids may provide advantages as solvents in terms of increased substrate and product solubility, higher...... of their amphiphilicity and antioxidative potential. Synthetic reactions using mono- or disaccharides as one of the substrates may moreover direct new routes for biomass upgrading in the biorefinery. The paper reviews the available data for enzymatic hydroxycinnamate saccharide ester synthesis in organic solvent systems...

  3. Attribution of irreversible loss to anthropogenic climate change

    Science.gov (United States)

    Huggel, Christian; Bresch, David; Hansen, Gerrit; James, Rachel; Mechler, Reinhard; Stone, Dáithí; Wallimann-Helmer, Ivo

    2016-04-01

    The Paris Agreement (2015) under the UNFCCC has anchored loss and damage in a separate article which specifies that understanding and support should be enhanced in areas addressing loss and damage such as early warning, preparedness, insurance and resilience. Irreversible loss is a special category under loss and damage but there is still missing clarity over what irreversible loss actually includes. Many negative impacts of climate change may be handled or mitigated by existing risk management, reduction and absorption approaches. Irreversible loss, however, is thought to be insufficiently addressed by risk management. Therefore, countries potentially or actually affected by irreversible loss are calling for other measures such as compensation, which however is highly contested in international climate policy. In Paris (2015) a decision was adopted that loss and damage as defined in the respective article of the agreement does not involve compensation and liability. Nevertheless, it is likely that some sort of mechanism will eventually need to come into play for irreversible loss due to anthropogenic climate change, which might involve compensation, other forms of non-monetary reparation, or transformation. Furthermore, climate litigation has increasingly been attempted to address negative effects of climate change. In this context, attribution is important to understand the drivers of change, what counts as irreversible loss due to climate change, and, possibly, who or what is responsible. Here we approach this issue by applying a detection and attribution perspective on irreversible loss. We first analyze detected climate change impacts as assessed in the IPCC Fifth Assessment Report. We distinguish between irreversible loss in physical, biological and human systems, and accordingly identify the following candidates of irreversible loss in these systems: loss of glaciers and ice sheets, loss of subsurface ice (permafrost) and related loss of lake systems; loss

  4. Modelling the Effects of Ageing Time of Starch on the Enzymatic Activity of Three Amylolytic Enzymes

    Science.gov (United States)

    Guerra, Nelson P.; Pastrana Castro, Lorenzo

    2012-01-01

    The effect of increasing ageing time (t) of starch on the activity of three amylolytic enzymes (Termamyl, San Super, and BAN) was investigated. Although all the enzymatic reactions follow michaelian kinetics, v max decreased significantly (P enzymes and the release of the reaction products to the medium. A similar effect was observed when the enzymatic reactions were carried out with unaged starches supplemented with different concentrations of gelatine [G]. The inhibition in the amylolytic activities was best mathematically described by using three modified forms of the Michaelis-Menten model, which included a term to consider, respectively, the linear, exponential, and hyperbolic inhibitory effects of t and [G]. PMID:22666116

  5. Enzymatic labelling of. gamma. -globulin and insulin with iodine-125

    Energy Technology Data Exchange (ETDEWEB)

    Lucka, B; Russin, K [Institute of Nuclear Physics, Krakow (Poland)

    1979-01-01

    The parameters of enzymatic labelling of proteins with iodine 125 were examined. The manner and sequence of reagent addition, the effects of reagent concentration, reaction time and total Na/sup 125/I activity on the labelling yield were determined.

  6. Effect and Modeling of Glucose Inhibition and In Situ Glucose Removal During Enzymatic Hydrolysis of Pretreated Wheat Straw

    DEFF Research Database (Denmark)

    Andric, Pavle; Meyer, Anne S.; Jensen, Peter Arendt

    2010-01-01

    The enzymatic hydrolysis of lignocellulosic biomass is known to be product-inhibited by glucose. In this study, the effects on cellulolytic glucose yields of glucose inhibition and in situ glucose removal were examined and modeled during extended treatment of heat-pretreated wheat straw......, during 96 h of reaction. When glucose was removed by dialysis during the enzymatic hydrolysis, the cellulose conversion rates and glucose yields increased. In fact, with dialytic in situ glucose removal, the rate of enzyme-catalyzed glucose release during 48-72 h of reaction recovered from 20......-40% to become approximate to 70% of the rate recorded during 6-24 h of reaction. Although Michaelis-Menten kinetics do not suffice to model the kinetics of the complex multi-enzymatic degradation of cellulose, the data for the glucose inhibition were surprisingly well described by simple Michaelis...

  7. Irreversibility Curve on Y1–xLuxBa2Cu3O7–δ (x=0.4, 0.5 and 0.6) superconducting

    International Nuclear Information System (INIS)

    Grimaldos, J F Cepeda; Supelano G, I; Santos, A Sarmiento; Chiquillo, M V; Martínez B, D; Vargas, C A Parra

    2014-01-01

    The irreversibility line in the H–T plane divides the irreversible and reversible behaviour of the magnetization which is of importance for the characterization of high T c superconductors. In this work, we report the production of Y 1–X Lu X Ba 2 Cu 3 O 7–δ (X=0.4, 0.5 and 0.6) superconducting system using the usual solid state reaction method. The irreversibility line H–T plane for the Y 1–X Lu X Ba 2 Cu 3 O 7–δ polycrystalline sample was investigated. The curves of magnetization ZFC (cero field cooled)- FC (field cooled) were measured in magnetic fields between 100 Oe and 4000 Oe, and allowed to obtain the values for irreversibility and critical temperatures

  8. Kinetic Modelling and Experimental Studies for the Effects of Fe2+ Ions on Xylan Hydrolysis with Dilute-Acid Pretreatment and Subsequent Enzymatic Hydrolysis

    Directory of Open Access Journals (Sweden)

    Hui Wei

    2018-01-01

    Full Text Available High-temperature (150–170 °C pretreatment of lignocellulosic biomass with mineral acids is well established for xylan breakdown. Fe2+ is known to be a cocatalyst of this process although kinetics of its action remains unknown. The present work addresses the effect of ferrous ion concentration on sugar yield and degradation product formation from corn stover for the entire two-step treatment, including the subsequent enzymatic cellulose hydrolysis. The feedstock was impregnated with 0.5% acid and 0.75 mM iron cocatalyst, which was found to be optimal in preliminary experiments. The detailed kinetic data of acid pretreatment, with and without iron, was satisfactorily modelled with a four-step linear sequence of first-order irreversible reactions accounting for the formation of xylooligomers, xylose and furfural as intermediates to provide the values of Arrhenius activation energy. Based on this kinetic modelling, Fe2+ turned out to accelerate all four reactions, with a significant alteration of the last two steps, that is, xylose degradation. Consistent with this model, the greatest xylan conversion occurred at the highest severity tested under 170 °C/30 min with 0.75 mM Fe2+, with a total of 8% xylan remaining in the pretreated solids, whereas the operational conditions leading to the highest xylose monomer yield, 63%, were milder, 150 °C with 0.75 mM Fe2+ for 20 min. Furthermore, the subsequent enzymatic hydrolysis with the prior addition of 0.75 mM of iron(II increased the glucose production to 56.3% from 46.3% in the control (iron-free acid. The detailed analysis indicated that conducting the process at lower temperatures yet long residence times benefits the yield of sugars. The above kinetic modelling results of Fe2+ accelerating all four reactions are in line with our previous mechanistic research showing that the pretreatment likely targets multiple chemistries in plant cell wall polymer networks, including those represented by the C

  9. Thermo effect of chemical reaction in irreversible electrochemical systems

    International Nuclear Information System (INIS)

    Tran Vinh Quy; Nguyen Tang

    1989-01-01

    From first law of thermodynamics the expressions of statistical calculation of 'Fundamental' and 'Thermo-chemical' thermal effects are obtained. Besides, method of calculation of thermal effect of chemical reactions in non-equilibrium electro-chemical systems is accurately discussed. (author). 7 refs

  10. Behavior of the irreversibility line in the new superconductor La1.5+xBa1.5+x-yCayCu3Oz

    International Nuclear Information System (INIS)

    Parra Vargas, C.A.; Pimentel, J.L.; Pureur, P.; Landínez Téllez, D.A.; Roa-Rojas, J.

    2012-01-01

    The irreversibility properties of high-T c superconductors are of major importance for technological applications. For example, a high irreversibility magnetic field is a more desirable quality for a superconductor . The irreversibility line in the H-T plane is constituted by experimental points, which divides the irreversible and reversible behavior of the magnetization. The irreversibility lines for series of La 1.5+x Ba 1.5+x-y Ca y Cu 3 O z polycrystalline samples with different doping were investigated. The samples were synthesized using the usual solid estate reaction method. Rietveld-type refinement of x-ray diffraction patterns permitted to determine the crystallization of material in a tetragonal structure. Curves of magnetization ZFC-FC for the system La 1.5+x Ba 1.5+x-y Ca y Cu 3 O z , were measured in magnetic fields of the 10-20,000 Oe, and allowed to obtain the values for the irreversibility and critical temperatures. The data of irreversibility temperature allowed demarcating the irreversibility line, T irr (H). Two main lines are used for the interpretation of the irreversibility line: one of those which suppose that the vortexes are activated thermally and the other proposes that associated to T irr a phase transition occurs. The irreversibility line is described by a power law. The obtained results allow concluding that in the system La 1.5+x Ba 1.5+x-y Ca y Cu 3 O z a characteristic bend of the Almeida-Thouless (AT) tendency is dominant for low fields and a bend Gabay-Toulouse (GT) behavior for high magnetic fields. This feature of the irreversibility line has been reported as a characteristic of granular superconductors and it corroborates the topological effects of vortexes mentioned by several authors .

  11. Site-Specific Bioconjugation of an Organometallic Electron Mediator to an Enzyme with Retained Photocatalytic Cofactor Regenerating Capacity and Enzymatic Activity

    Directory of Open Access Journals (Sweden)

    Sung In Lim

    2015-04-01

    Full Text Available Photosynthesis consists of a series of reactions catalyzed by redox enzymes to synthesize carbohydrates using solar energy. In order to take the advantage of solar energy, many researchers have investigated artificial photosynthesis systems mimicking the natural photosynthetic enzymatic redox reactions. These redox reactions usually require cofactors, which due to their high cost become a key issue when constructing an artificial photosynthesis system. Combining a photosensitizer and an Rh-based electron mediator (RhM has been shown to photocatalytically regenerate cofactors. However, maintaining the high concentration of cofactors available for efficient enzymatic reactions requires a high concentration of the expensive RhM; making this process cost prohibitive. We hypothesized that conjugation of an electron mediator to a redox enzyme will reduce the amount of electron mediators necessary for efficient enzymatic reactions. This is due to photocatalytically regenerated NAD(PH being readily available to a redox enzyme, when the local NAD(PH concentration near the enzyme becomes higher. However, conventional random conjugation of RhM to a redox enzyme will likely lead to a substantial loss of cofactor regenerating capacity and enzymatic activity. In order to avoid this issue, we investigated whether bioconjugation of RhM to a permissive site of a redox enzyme retains cofactor regenerating capacity and enzymatic activity. As a model system, a RhM was conjugated to a redox enzyme, formate dehydrogenase obtained from Thiobacillus sp. KNK65MA (TsFDH. A RhM-containing azide group was site-specifically conjugated to p-azidophenylalanine introduced to a permissive site of TsFDH via a bioorthogonal strain-promoted azide-alkyne cycloaddition and an appropriate linker. The TsFDH-RhM conjugate exhibited retained cofactor regenerating capacity and enzymatic activity.

  12. Enhanced enzymatic cellulose degradation by cellobiohydrolases via product removal

    DEFF Research Database (Denmark)

    Ahmadi Gavlighi, Hassan; Meyer, Anne S.; Mikkelsen, Jørn Dalgaard

    2013-01-01

    Product inhibition by cellobiose decreases the rate of enzymatic cellulose degradation. The optimal reaction conditions for two Emericella (Aspergillus) nidulans-derived cellobiohydrolases I and II produced in Pichia pastoris were identified as CBHI: 52 °C, pH 4.5–6.5, and CBHII: 46 °C, pH 4.......8. The optimum in a mixture of the two was 50 °C, pH 4.9. An almost fourfold increase in enzymatic hydrolysis yield was achieved with intermittent product removal of cellobiose with membrane filtration (2 kDa cut-off): The conversion of cotton cellulose after 72 h was ~19 % by weight, whereas the conversion...

  13. Enzymatic determination of cadmium, zinc, and lead in plant materials

    International Nuclear Information System (INIS)

    Muginova, S.V.; Veselova, I.A.; Parova, L.M.; Shekhovtseva, T.N.

    2008-01-01

    Prospects are outlined for using the following enzymes (native and immobilized on polyurethane foam) in the rapid and highly sensitive determination of cadmium, zinc, and lead ions in plant materials (wild grass, fresh pea, and grape): horseradish peroxidase and alkaline phosphatases isolated from chicken intestine and Greenland seal small intestine. The analytical ranges of the above metals are 1x10 -3 -25; 7x10 -3 -250, and 3x10 -2 -67 mg/kg dry matter, respectively. The enzymatic determination procedures developed are based on the inhibiting effect of metal ions on the catalytic activity of peroxidase in the oxidation of o-dianisidine with hydrogen peroxide and alkaline phosphatases in the hydrolysis of p-nitrophenyl phosphate. The rates of enzymatic reactions were monitored spectrophotometrically or visually. In the analysis of plant extracts, their high acidity was diminished by choosing optimum dilution factors and pH values for test samples and the nature and concentration of a buffer solution. The interference of iron(III) was removed by introducing a 0.1 M tartaric acid solution into the indicator reaction. The accuracy of the results of the enzymatic determination of cadmium, zinc, and lead in plant materials was supported by atomic absorption spectrometry and anodic stripping voltammetry [ru

  14. Bimolecular interaction of argpyrimidine (a Maillard reaction product) in in vitro non-enzymatic protein glycation model and its potential role as an antiglycating agent.

    Science.gov (United States)

    Bhattacherjee, Abhishek; Dhara, Kaliprasanna; Chakraborti, Abhay Sankar

    2017-09-01

    Non- enzymatic glycation, also known as Maillard reaction, is one of the most important and investigated reactions in biochemistry. Maillard reaction products (MRPs) like protein-derived advanced glycation end products (AGEs) are often referred to cause pathophysiological complications in human systems. On contrary, several MRPs are exogenously used as antioxidant, antimicrobial and flavouring agents. In the preset study, we have shown that argpyrimidine, a well-established AGE, interacts with bovine serum albumin (BSA) and glucose individually in standard BSA-glucose model system and successfully inhibits glycation of the protein. Bimolecular interaction of argpyrimidine with glucose or BSA has been studied independently. Chromatographic purification, different spectroscopic studies and molecular modeling have been used to evaluate the nature and pattern of interactions. Binding of argpyrimidine with BSA prevents incorporation of glucose inside the native protein. Argpyrimidine can also directly entrap glucose. Both these interactions may be associated with the antiglycation potential of argpyrimidine, indicating a beneficial function of an AGE. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Generalized irreversible heat-engine experiencing a complex heat-transfer law

    International Nuclear Information System (INIS)

    Chen Lingen; Li Jun; Sun Fengrui

    2008-01-01

    The fundamental optimal relation between optimal power-output and efficiency of a generalized irreversible Carnot heat-engine is derived based on a generalized heat-transfer law, including a generalized convective heat-transfer law and a generalized radiative heat-transfer law, q ∝ (ΔT n ) m . The generalized irreversible Carnot-engine model incorporates several internal and external irreversibilities, such as heat resistance, bypass heat-leak, friction, turbulence and other undesirable irreversibility factors. The added irreversibilities, besides heat resistance, are characterized by a constant parameter and a constant coefficient. The effects of heat-transfer laws and various loss terms are analyzed. The results obtained corroborate those in the literature

  16. Enzymatic Hydrolysis of Pretreated Fibre Pressed Oil Palm Frond by using Sacchariseb C6

    Science.gov (United States)

    Hashim, F. S.; Yussof, H. W.; Zahari, M. A. K. M.; Rahman, R. A.; Illias, R. M.

    2017-06-01

    Enzymatic hydrolysis becomes a prominent technology for conversion of cellulosic biomass to its glucose monomers that requires an action of cellulolytic enzymes in a sequential and synergistic manner. In this study, the effect of agitation speed, glucan loading, enzyme loading, temperature and reaction time on the production of glucose from fibre pressed oil palm frond (FPOPF) during enzymatic hydrolysis was screened by a half factorial design 25-1 using Response Surface Methodology (RSM). The FPOPF sample was first delignified by alkaline pretreatment at 4.42 (w/v) sodium hydroxide for an hour prior to enzymatic hydrolysis using commercial cellulase enzyme, Sacchariseb C6. The effect of enzymatic hydrolysis on the structural of FPOPF has been evaluated by Scanning Electron Microscopy (SEM) analysis. Characterization of raw FPOPF comprised of 4.5 extractives, 40.7 glucan, 26.1 xylan, 26.2 lignin and 1.8 ash, whereas for pretreated FPOPF gave 0.3 extractives, 61.4 glucan, 20.4 xylan, 13.3 lignin and 1.3 ash. From this study, it was found that the best enzymatic hydrolysis condition yielded 33.01 ± 0.73 g/L of glucose when performed at 200 rpm of agitation speed, 60 FPU/mL of enzyme loading, 4 (w/w) of glucan loading, temperature at 55 □ and 72 hours of reaction time. The model obtained was significant with p-value enzymatic hydrolysis from pretreated FPOPF produce high amount of glucose that enhances it potential for industrial application. This glucose can be further used to produce high-value products.

  17. The Value of Fighting Irreversible Demise by Softening the Irreversible Cost

    NARCIS (Netherlands)

    Magis, P.; Sbuelz, A.

    2005-01-01

    We study a novel issue in the real-options-based technology innovation literature by means of double barrier contingent claims analysis.We show how much a ¯rm with the monopoly over a project is willing to spend in investment technology innovation that softens the irreversible cost of accessing the

  18. Irreversible work in a thermal medium with colored noise

    International Nuclear Information System (INIS)

    Ohkuma, Takahiro

    2009-01-01

    Irreversible work and its fluctuations in a classical system governed by non-Markovian stochastic dynamics are investigated. The production of irreversible work depends not only on the protocol of an operation but also on the details of the non-Markovian memory. We consider a generalized Langevin equation with a memory kernel and derive an expression for the irreversible work in the case of slow operations by carrying out an expansion of this memory kernel in the parameter representing the length of the memory. We apply our formulation to a harmonically trapped system and demonstrate the efficiency of a cycle by evaluating the irreversible work. It is found that a decrease in the irreversible work due to the memory effect can occur for an operation through which the trap is squeezed. The results for this harmonic system are verified exactly in the case that the memory kernel has exponential decay

  19. Irreversible work in a thermal medium with colored noise

    Science.gov (United States)

    Ohkuma, Takahiro

    2009-10-01

    Irreversible work and its fluctuations in a classical system governed by non-Markovian stochastic dynamics are investigated. The production of irreversible work depends not only on the protocol of an operation but also on the details of the non-Markovian memory. We consider a generalized Langevin equation with a memory kernel and derive an expression for the irreversible work in the case of slow operations by carrying out an expansion of this memory kernel in the parameter representing the length of the memory. We apply our formulation to a harmonically trapped system and demonstrate the efficiency of a cycle by evaluating the irreversible work. It is found that a decrease in the irreversible work due to the memory effect can occur for an operation through which the trap is squeezed. The results for this harmonic system are verified exactly in the case that the memory kernel has exponential decay.

  20. Irreversible thermodynamic analysis and application for molecular heat engines

    Science.gov (United States)

    Lucia, Umberto; Açıkkalp, Emin

    2017-09-01

    Is there a link between the macroscopic approach to irreversibility and microscopic behaviour of the systems? Consumption of free energy keeps the system away from a stable equilibrium. Entropy generation results from the redistribution of energy, momentum, mass and charge. This concept represents the essence of the thermodynamic approach to irreversibility. Irreversibility is the result of the interaction between systems and their environment. The aim of this paper is to determine lost works in a molecular engine and compare results with macro (classical) heat engines. Firstly, irreversible thermodynamics are reviewed for macro and molecular cycles. Secondly, irreversible thermodynamics approaches are applied for a quantum heat engine with -1/2 spin system. Finally, lost works are determined for considered system and results show that macro and molecular heat engines obey same limitations. Moreover, a quantum thermodynamic approach is suggested in order to explain the results previously obtained from an atomic viewpoint.

  1. Exergetic efficiency optimization for an irreversible heat pump ...

    Indian Academy of Sciences (India)

    side ... For irreversible cycle, the internal irreversibility, i.e., non-isentropic losses in the ... constant thermal capacitance rate (the product of mass flow rate and specific heat), .... reversed Brayton cycle is dependent on the external heat transfer ...

  2. Effect of disinfection on irreversible hydrocolloid and alternative impression materials and the resultant gypsum casts.

    Science.gov (United States)

    Suprono, Montry S; Kattadiyil, Mathew T; Goodacre, Charles J; Winer, Myron S

    2012-10-01

    Many new products have been introduced and marketed as alternatives to traditional irreversible hydrocolloid materials. These alternative materials have the same structural formula as addition reaction silicone, also known as vinyl polysiloxane (VPS), impression materials. Currently, there is limited in vitro and in vivo research on these products, including on the effects of chemical disinfectants on the materials. The purpose of this study was to compare the effects of a spray disinfecting technique on a traditional irreversible hydrocolloid and 3 new alternative impression materials in vitro. The tests were performed in accordance with the American National Standards Institute/American Dental Association (ANSI/ADA) Specification Nos. 18 and 19. Under standardized conditions, 100 impressions were made of a ruled test block with an irreversible hydrocolloid and 3 alternative impression materials. Nondisinfected irreversible hydrocolloid was used as the control. The impressions were examined for surface detail reproduction before and after disinfection with a chloramine-T product. Type III and Type V dental stone casts were evaluated for linear dimensional change and gypsum compatibility. Comparisons of linear dimensional change were analyzed with 2-way ANOVA of mean ranks with the Scheffé post hoc comparisons (α=.05). Data for surface detail reproduction were analyzed with the Wilcoxon Signed-Rank procedure and gypsum compatibility with the Kruskal-Wallis Rank procedure (α=.05). The alternative impression materials demonstrated significantly better outcomes with all 3 parameters tested. Disinfection with chloroamine-T did not have any effect on the 3 alternative impression materials. The irreversible hydrocolloid groups produced the most variability in the measurements of linear dimensional change. All of the tested materials were within the ADA's acceptable limit of 1.0% for linear dimensional change, except for the disinfected irreversible hydrocolloid

  3. The detection of local irreversibility in time series based on segmentation

    Science.gov (United States)

    Teng, Yue; Shang, Pengjian

    2018-06-01

    We propose a strategy for the detection of local irreversibility in stationary time series based on multiple scale. The detection is beneficial to evaluate the displacement of irreversibility toward local skewness. By means of this method, we can availably discuss the local irreversible fluctuations of time series as the scale changes. The method was applied to simulated nonlinear signals generated by the ARFIMA process and logistic map to show how the irreversibility functions react to the increasing of the multiple scale. The method was applied also to series of financial markets i.e., American, Chinese and European markets. The local irreversibility for different markets demonstrate distinct characteristics. Simulations and real data support the need of exploring local irreversibility.

  4. ENCAPSULATION OF HORSERADISH PEROXIDASE-GLUCOSE OXIDASE (HRP-GOx IN SILICA AQUAGEL SYNTHESIZED FROM RICE HULL ASH FOR ENZYMATIC REACTION OF GLUCOSE

    Directory of Open Access Journals (Sweden)

    Nuryono Nuryono

    2010-06-01

    Full Text Available In recent years, the sol-gel technique has attracted increasing interest as a unique approach to immobilize biomolecules for bioanalytical applications as well as biochemical and biophysical studies. In this research, encapsulation of Horseradish peroxidase-Glucose oxidase (HRP-GOx enzymes in silica aquagel from rice hull ash by sol-gel process has been carried out. In addition, the effect of several parameters (weight ratio of HRP to GOx, pH, temperature, sodium ion concentration on enzyme activity was studied, as well. Rice hull ash, which was produced by ashing at 700 °C, was extracted it's silika by NaOH solution 1 M at 100 °C for two hours to produce sodium silikate (Na2SiO3 solution. The Na2SiO3 solution with pH of 13 was added with a strong cation exchanger resin, to produce sol solution with the pH of 4. Encapsulation was emphasized by mixing sol solution and phosphate buffer pH 7 containing HRP-GOx solution at volume ratio of buffer to sol solution 1:5. The mixture was transferred into 96-microwell plate and was aged for 24 hours. Enzymatic reaction was carried out by adding chromogenic solution of phenol and 4-aminoantipyrine (4-AAP and b-D-glucose solution (as substrate into the microwell. Enzymatic activity was examined by measuring absorbance of product solution at 490 nm with ELISA reader. Result of enzymatic activity for encapsulated enzymes (SGE was compared to that for free enzymes (EB. Results showed that at the investigated condition, HRP-GOx enzymes gave high activity at weight ratio of HRP to GOx 10:1 and pH 7 for both SGE and EB. Encapsulation caused the enzymes activity decrease to 53.0±0.2 %. However, SGE was observed to be more stable on pH and temperature changes than EB. Study on the effect of sodium concentration showed that the increase of sodium concentration from 0.10 to 0.37 M decreased the enzymatic activity to 56±0.2%. Reusability test showed that the synthesized SGE was reusable with activity decrease of 60

  5. Degradations and Rearrangement Reactions

    Science.gov (United States)

    Zhang, Jianbo

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

  6. State of the art and prospective of lipase-catalyzed transesterification reaction for biodiesel production

    International Nuclear Information System (INIS)

    Amini, Zeynab; Ilham, Zul; Ong, Hwai Chyuan; Mazaheri, Hoora; Chen, Wei-Hsin

    2017-01-01

    Highlights: • Enzymatic transesterification process is less energy intensive and robust. • Nano-materials are promising immobilization supports for lipase. • Packed-bed reactors are appropriate for scale-up use. • Potential recombinant, whole cell and recombinant whole cell lipases were enlisted. • Genetic engineering is a promising prospect in biodiesel area. - Abstract: The world demand for fuel as energy sources have arisen the need for generating alternatives such as biofuel. Biodiesel is a renewable fuel used particularly in diesel engines. Currently, biodiesel is mainly produced through transesterification reactions catalyzed by chemical catalysts, which produces higher fatty acid alkyl esters in shorter reaction time. Although extensive investigations on enzymatic transesterification by downstream processing were carried out, enzymatic transesterification has yet to be used in scale-up since commercial lipases are chiefly limited to the cost as well as long reaction time. While numerous lipases were studied and proven to have the high catalytic capacity, still enzymatic reaction requires more investigation. To fill this gap, finding optimal conditions for the reaction such as alcohol and oil choice, water content, reaction time and temperature through proper reaction modelling and simulations as well as the appropriate design and use of reactors for large scale production are crucial issues that need to be accurately addressed. Furthermore, lipase concentration, alternative lipase resources through whole cell technology and genetic engineering, recent immobilizing materials including nanoparticles, and the capacity of enzyme to be reused are important criteria to be neatly investigated. The present work reviews the current biodiesel feedstock, catalysis, general and novel immobilizing materials, bioreactors for enzymatic transesterification, potential lipase resources, intensification technics, and process modelling for enzymatic

  7. Reaction Decoder Tool (RDT): extracting features from chemical reactions.

    Science.gov (United States)

    Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

    2016-07-01

    Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

  8. Method for the enzymatic production of hydrogen

    Science.gov (United States)

    Woodward, J.; Mattingly, S.M.

    1999-08-24

    The present invention is an enzymatic method for producing hydrogen comprising the steps of: (a) forming a reaction mixture within a reaction vessel comprising a substrate capable of undergoing oxidation within a catabolic reaction, such as glucose, galactose, xylose, mannose, sucrose, lactose, cellulose, xylan and starch; the reaction mixture also comprising an amount of glucose dehydrogenase in an amount sufficient to catalyze the oxidation of the substrate, an amount of hydrogenase sufficient to catalyze an electron-requiring reaction wherein a stoichiometric yield of hydrogen is produced, an amount of pH buffer in an amount sufficient to provide an environment that allows the hydrogenase and the glucose dehydrogenase to retain sufficient activity for the production of hydrogen to occur and also comprising an amount of nicotinamide adenine dinucleotide phosphate sufficient to transfer electrons from the catabolic reaction to the electron-requiring reaction; (b) heating the reaction mixture at a temperature sufficient for glucose dehydrogenase and the hydrogenase to retain sufficient activity and sufficient for the production of hydrogen to occur, and heating for a period of time that continues until the hydrogen is no longer produced by the reaction mixture, wherein the catabolic reaction and the electron-requiring reactions have rates of reaction dependent upon the temperature; and (c) detecting the hydrogen produced from the reaction mixture. 8 figs.

  9. The construction, fouling and enzymatic cleaning of a textile dye surface.

    Science.gov (United States)

    Onaizi, Sagheer A; He, Lizhong; Middelberg, Anton P J

    2010-11-01

    The enzymatic cleaning of a rubisco protein stain bound onto Surface Plasmon Resonance (SPR) biosensor chips having a dye-bound upper layer is investigated. This novel method allowed, for the first time, a detailed kinetic study of rubisco cleanability (defined as fraction of adsorbed protein removed from a surface) from dyed surfaces (mimicking fabrics) at different enzyme concentrations. Analysis of kinetic data using an established mathematical model able to decouple enzyme transfer and reaction processes [Onaizi, He, Middelberg, Chem. Eng. Sci. 64 (2008) 3868] revealed a striking effect of dyeing on enzymatic cleaning performance. Specifically, the absolute rate constants for enzyme transfer to and from a dye-bound rubisco stain were significantly higher than reported previously for un-dyed surfaces. These increased transfer rates resulted in higher surface cleanability. Higher enzyme mobility (i.e., higher enzyme adsorption and desorption rates) at the liquid-dye interface was observed, consistent with previous suggestions that enzyme surface mobility is likely correlated with overall enzyme cleaning performance. Our results show that reaction engineering models of enzymatic action at surfaces may provide insight able to guide the design of better stain-resistant surfaces, and may also guide efforts to improve cleaning formulations. Copyright 2010 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Chase A. Klingaman

    2017-02-01

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

  11. General thermodynamic performance of irreversible absorption heat pump

    International Nuclear Information System (INIS)

    Zhao Xiling; Fu Lin; Zhang Shigang

    2011-01-01

    The absorption heat pump (AHP) was studied with thermodynamics. A four reservoirs model of absorption heat pump was established considering the heat resistance, heat leak and the internal irreversibility. The reasonable working regions, the performance effects of irreversibility, heat leak and the correlation of four components were studied. When studying the effects of internal irreversibility, two internal irreversibility parameters (I he for generator-absorber assembly and I re for evaporator-condenser assembly) were introduced to distinguish the different effects. When studying the heat transfer relations of four components, a universal relationship between the main parameters were deduced. The results which have more realized meaning show that, the reduction of the friction, heat loss, and internal dissipations of the evaporator-condenser assembly are more important than its reduction of generator-absorber assembly, and lessening the heat leak of generator are more important than its reduction of other components to improve the AHP performance.

  12. Nanosilver: A Catalyst in Enzymatic Hydrolysis of Starch

    Directory of Open Access Journals (Sweden)

    Falkowska Marta

    2014-09-01

    Full Text Available Silver nanoparticles are widely used, because of their antimicrobial properties. In this paper, the rate of starch digestion in the presence of nanocatalyst was compared with the rate of reaction without nanosilver. The rate of enzymatic degradation of starch was found to be increased in the presence of silver nanoparticles. It is considered that α-amylase was immobilized onto the surface of nanoparticles.

  13. Irreversible stochastic processes on lattices

    International Nuclear Information System (INIS)

    Nord, R.S.

    1986-01-01

    Models for irreversible random or cooperative filling of lattices are required to describe many processes in chemistry and physics. Since the filling is assumed to be irreversible, even the stationary, saturation state is not in equilibrium. The kinetics and statistics of these processes are described by recasting the master equations in infinite hierarchical form. Solutions can be obtained by implementing various techniques: refinements in these solution techniques are presented. Programs considered include random dimer, trimer, and tetramer filling of 2D lattices, random dimer filling of a cubic lattice, competitive filling of two or more species, and the effect of a random distribution of inactive sites on the filling. Also considered is monomer filling of a linear lattice with nearest neighbor cooperative effects and solve for the exact cluster-size distribution for cluster sizes up to the asymptotic regime. Additionally, a technique is developed to directly determine the asymptotic properties of the cluster size distribution. Finally cluster growth is considered via irreversible aggregation involving random walkers. In particular, explicit results are provided for the large-lattice-size asymptotic behavior of trapping probabilities and average walk lengths for a single walker on a lattice with multiple traps. Procedures for exact calculation of these quantities on finite lattices are also developed

  14. Multi-Scale Computational Enzymology: Enhancing Our Understanding of Enzymatic Catalysis

    Science.gov (United States)

    Gherib, Rami; Dokainish, Hisham M.; Gauld, James W.

    2014-01-01

    Elucidating the origin of enzymatic catalysis stands as one the great challenges of contemporary biochemistry and biophysics. The recent emergence of computational enzymology has enhanced our atomistic-level description of biocatalysis as well the kinetic and thermodynamic properties of their mechanisms. There exists a diversity of computational methods allowing the investigation of specific enzymatic properties. Small or large density functional theory models allow the comparison of a plethora of mechanistic reactive species and divergent catalytic pathways. Molecular docking can model different substrate conformations embedded within enzyme active sites and determine those with optimal binding affinities. Molecular dynamics simulations provide insights into the dynamics and roles of active site components as well as the interactions between substrate and enzymes. Hybrid quantum mechanical/molecular mechanical (QM/MM) can model reactions in active sites while considering steric and electrostatic contributions provided by the surrounding environment. Using previous studies done within our group, on OvoA, EgtB, ThrRS, LuxS and MsrA enzymatic systems, we will review how these methods can be used either independently or cooperatively to get insights into enzymatic catalysis. PMID:24384841

  15. Multi-Scale Computational Enzymology: Enhancing Our Understanding of Enzymatic Catalysis

    Directory of Open Access Journals (Sweden)

    Rami Gherib

    2013-12-01

    Full Text Available Elucidating the origin of enzymatic catalysis stands as one the great challenges of contemporary biochemistry and biophysics. The recent emergence of computational enzymology has enhanced our atomistic-level description of biocatalysis as well the kinetic and thermodynamic properties of their mechanisms. There exists a diversity of computational methods allowing the investigation of specific enzymatic properties. Small or large density functional theory models allow the comparison of a plethora of mechanistic reactive species and divergent catalytic pathways. Molecular docking can model different substrate conformations embedded within enzyme active sites and determine those with optimal binding affinities. Molecular dynamics simulations provide insights into the dynamics and roles of active site components as well as the interactions between substrate and enzymes. Hybrid quantum mechanical/molecular mechanical (QM/MM can model reactions in active sites while considering steric and electrostatic contributions provided by the surrounding environment. Using previous studies done within our group, on OvoA, EgtB, ThrRS, LuxS and MsrA enzymatic systems, we will review how these methods can be used either independently or cooperatively to get insights into enzymatic catalysis.

  16. Chain length distribution and kinetic characteristics of an enzymatically produced polymer

    NARCIS (Netherlands)

    Mulders, K.J.M.; Beeftink, H.H.

    2013-01-01

    Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model

  17. Enzymatic halogenation and oxidation using an alcohol oxidase-vanadium chloroperoxidase cascade

    NARCIS (Netherlands)

    But, Andrada; Noord, Van Aster; Poletto, Francesca; Sanders, Johan P.M.; Franssen, Maurice C.R.; Scott, Elinor L.

    2017-01-01

    The chemo-enzymatic cascade which combines alcohol oxidase from Hansenula polymorpha (AOXHp) with vanadium chloroperoxidase (VCPO), for the production of biobased nitriles from amino acids was investigated. In the first reaction H2O2 (and acetaldehyde) are generated from ethanol and oxygen by AOXHp.

  18. Shape and topology optimization of enzymatic microreactors

    DEFF Research Database (Denmark)

    Pereira Rosinha, Ines

    for effective and cost efficient reactors for pharmaceutical processes forces the industry to search for better technologies. In biochemical engineering, the used reactor design in a given process is usually limited to a range of well-established configurations and layouts. Usually the implemented reactors...... in a chemical process do not always yield in the best reaction conditions.This thesis develops an innovative application of topology and shape optimization methods to achemical engineering problem. The main goal is to design a reactor according to the limitations of the reaction system by modifying the reactor...... configuration. In this thesis structural optimization methods were exclusively applied to enzymatic microreactors. The case studies were chosen such that they can be experimentally tested afterwards. In this way, the design of the reactor is customized to the reaction system and itcontributes to the reduction...

  19. EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user's guide, and related documentation (Version 7.0)

    International Nuclear Information System (INIS)

    Wolery, T.J.; Daveler, S.A.

    1992-01-01

    EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ''single-point'' thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics

  20. Thermodynamic Analysis of an Irreversible Maisotsenko Reciprocating Brayton Cycle

    Directory of Open Access Journals (Sweden)

    Fuli Zhu

    2018-03-01

    Full Text Available An irreversible Maisotsenko reciprocating Brayton cycle (MRBC model is established using the finite time thermodynamic (FTT theory and taking the heat transfer loss (HTL, piston friction loss (PFL, and internal irreversible losses (IILs into consideration in this paper. A calculation flowchart of the power output (P and efficiency (η of the cycle is provided, and the effects of the mass flow rate (MFR of the injection of water to the cycle and some other design parameters on the performance of cycle are analyzed by detailed numerical examples. Furthermore, the superiority of irreversible MRBC is verified as the cycle and is compared with the traditional irreversible reciprocating Brayton cycle (RBC. The results can provide certain theoretical guiding significance for the optimal design of practical Maisotsenko reciprocating gas turbine plants.

  1. Antibiotic use for irreversible pulpitis.

    Science.gov (United States)

    Agnihotry, Anirudha; Fedorowicz, Zbys; van Zuuren, Esther J; Farman, Allan G; Al-Langawi, Jassim Hasan

    2016-02-17

    Irreversible pulpitis, which is characterised by acute and intense pain, is one of the most frequent reasons that patients attend for emergency dental care. Apart from removal of the tooth, the customary way of relieving the pain of irreversible pulpitis is by drilling into the tooth, removing the inflamed pulp (nerve) and cleaning the root canal. However, a significant number of dentists continue to prescribe antibiotics to stop the pain of irreversible pulpitis.This review updates the previous version published in 2013. To assess the effects of systemic antibiotics for irreversible pulpitis. We searched the Cochrane Oral Health Group's Trials Register (to 27 January 2016); the Cochrane Central Register of Controlled Trials (CENTRAL) (The Cochrane Library 2015, Issue 12); MEDLINE via Ovid (1946 to 27 January 2016); EMBASE via Ovid (1980 to 27 January 2016), ClinicalTrials.gov (to 27 January 2016) and the WHO International Clinical Trials Registry Platform (to 27 January 2016). There were no language restrictions in the searches of the electronic databases. Randomised controlled trials which compared pain relief with systemic antibiotics and analgesics, against placebo and analgesics in the acute preoperative phase of irreversible pulpitis. Two review authors screened studies and extracted data independently. We assessed the quality of the evidence of included studies using GRADEpro software. Pooling of data was not possible and a descriptive summary is presented. One trial assessed at low risk of bias, involving 40 participants was included in this update of the review. The quality of the body of evidence was rated low for the different outcomes. There was a close parallel distribution of the pain ratings in both the intervention and placebo groups over the seven-day study period. There was insufficient evidence to claim or refute a benefit for penicillin for pain intensity. There was no significant difference in the mean total number of ibuprofen tablets over the

  2. Enzymatic production of biodiesel from microalgal oil using ethyl acetate as an acyl acceptor.

    Science.gov (United States)

    Alavijeh, Razieh Shafiee; Tabandeh, Fatemeh; Tavakoli, Omid; Karkhane, Aliasghar; Shariati, Parvin

    2015-01-01

    Microalgae have become an important source of biomass for biodiesel production. In enzymatic transesterification reaction, the enzyme activity is decreased in presence of alcohols. The use of different acyl acceptors such as methyl/ethyl acetate is suggested as an alternative and effective way to overcome this problem. In this study, ethyl acetate was used for the first time in the enzymatic production of biodiesel by using microalga, Chlorella vulgaris, as a triglyceride source. Enzymatic conversion of such fatty acids to biodiesel was catalyzed by Novozym 435 as an efficient immobilized lipase which is extensively used in biodiesel production. The best conversion yield of 66.71% was obtained at the ethyl acetate to oil molar ratio of 13:1 and Novozym 435 concentration of 40%, based on the amount of oil, and a time period of 72 h at 40℃. The results showed that ethyl acetate have no adverse effect on lipase activity and the biodiesel amount was not decreased even after seven transesterification cycles, so ethyl acetate has a great potential to be substituted for short-chain alcohols in transesterification reaction.

  3. Modeling enzymatic hydrolysis of lignocellulosic substrates using confocal fluorescence microscopy I: filter paper cellulose.

    Science.gov (United States)

    Luterbacher, Jeremy S; Moran-Mirabal, Jose M; Burkholder, Eric W; Walker, Larry P

    2015-01-01

    Enzymatic hydrolysis is one of the critical steps in depolymerizing lignocellulosic biomass into fermentable sugars for further upgrading into fuels and/or chemicals. However, many studies still rely on empirical trends to optimize enzymatic reactions. An improved understanding of enzymatic hydrolysis could allow research efforts to follow a rational design guided by an appropriate theoretical framework. In this study, we present a method to image cellulosic substrates with complex three-dimensional structure, such as filter paper, undergoing hydrolysis under conditions relevant to industrial saccharification processes (i.e., temperature of 50°C, using commercial cellulolytic cocktails). Fluorescence intensities resulting from confocal images were used to estimate parameters for a diffusion and reaction model. Furthermore, the observation of a relatively constant bound enzyme fluorescence signal throughout hydrolysis supported our modeling assumption regarding the structure of biomass during hydrolysis. The observed behavior suggests that pore evolution can be modeled as widening of infinitely long slits. The resulting model accurately predicts the concentrations of soluble carbohydrates obtained from independent saccharification experiments conducted in bulk, demonstrating its relevance to biomass conversion work. © 2014 Wiley Periodicals, Inc.

  4. A Factorial Analysis Study on Enzymatic Hydrolysis of Fiber Pressed Oil Palm Frond for Bioethanol Production

    Science.gov (United States)

    Hashim, F. S.; Yussof, H. W.; Zahari, M. A. K. M.; Illias, R. M.; Rahman, R. A.

    2016-03-01

    Different technologies have been developed to for the conversion of lignocellulosic biomass to suitable fermentation substrates for bioethanol production. The enzymatic conversion of cellulose seems to be the most promising technology as it is highly specific and does not produce substantial amounts of unwanted byproducts. The effects of agitation speed, enzyme loading, temperature, pH and reaction time on the conversion of glucose from fiber pressed oil palm frond (FPOPF) for bioethanol production were screened by statistical analysis using response surface methodology (RSM). A half fraction two-level factorial analysis with five factors was selected for the experimental design to determine the best enzymatic conditions that produce maximum amount of glucose. FPOPF was pre-treated with alkaline prior to enzymatic hydrolysis. The enzymatic hydrolysis was performed using a commercial enzyme Cellic CTec2. From this study, the highest yield of glucose concentration was 9.736 g/L at 72 hours reaction time at 35 °C, pH 5.6, and 1.5% (w/v) of enzyme loading. The model obtained was significant with p-value model had a maximum point which is likely to be the optimum point and possible for the optimization process.

  5. Unravelling the origin of irreversible capacity loss in NaNiO 2 for high voltage sodium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Liguang; Wang, Jiajun; Zhang, Xiaoyi; Ren, Yang; Zuo, Pengjian; Yin, Geping; Wang, Jun

    2017-04-01

    Layered transition metal compounds have attracted much attention due to their high theoretical capacity and energy density for sodium ion batteries. However, this kind of material suffers from serious irreversible capacity decay during the charge and discharge process. Here, using synchrotron-based operando transmission X-ray microscopy and high-energy X-ray diffraction combined with electrochemical measurements, the visualization of the dissymmetric phase transformation and structure evolution mechanism of layered NaNiO2 material during initial charge and discharge cycles are clarified. Phase transformation and deformation of NaNiO2 during the voltage range of below 3.0 V and over 4.0 V are responsible for the irreversible capacity loss during the first cycling, which is also confirmed by the evolution of reaction kinetics behavior obtained by the galvanostatic intermittent titration technique. These findings reveal the origin of the irreversibility of NaNiO2 and offer valuable insight into the phase transformation mechanism, which will provide underlying guidance for further development of high-performance sodium ion batteries.

  6. Conducts of disinfection, pouring and storage of irreversible hydrocolloid impressions by undergraduate students

    Directory of Open Access Journals (Sweden)

    Thalisson Saymo de Oliveira SILVA

    Full Text Available Abstract Introduction Obtaining dental models that accurately represent the molded oral tissue requires professional attention, especially when using irreversible hydrocolloid as a molding material. Objective To evaluate the conducts of undergraduate dental students at different internships for the disinfecting procedures, pouring, and storage of irreversible hydrocolloid impressions. Material and method This is an observational, cross-sectional and descriptive study with a census sample of 89 students enrolled in the supervised internships I, II, III and IV. Data collection was performed using a structured questionnaire containing eight questions. Data were analyzed at the 5% significance level. Result Most of the students (88.8% performed the disinfection procedure, for which the most widely used method (64.6% was the application of sodium hypochlorite 1% spray stored in a sealed container. The most common disinfection time was 10 minutes (86.1%. Students in the early internships performed better in regard to the proportion of water/plaster to be used compared with students in the final internships. At all internships, pouring and storage of the ensemble of mold and model were neglected during the setting reaction. There was a statistically significant association between the stage and the disinfection method, the ratio of water/powder and pouring of the model (p<0.05. Conclusion Students exhibited appropriate conduct of disinfection; however, they should be encouraged to use evidence-based clinical practices in order to improve the procedures of pouring and storage of irreversible hydrocolloid molds.

  7. Applications of a single-molecule detection in early disease diagnosis and enzymatic reaction study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jiangwei [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    Various single-molecule techniques were utilized for ultra-sensitive early diagnosis of viral DNA and antigen and basic mechanism study of enzymatic reactions. DNA of human papilloma virus (HPV) served as the screening target in a flow system. Alexa Fluor 532 (AF532) labeled single-stranded DNA probes were hybridized to the target HPV-16 DNA in solution. The individual hybridized molecules were imaged with an intensified charge-coupled device (ICCD) in two ways. In the single-color mode, target molecules were detected via fluorescence from hybridized probes only. This system could detect HPV-16 DNA in the presence of human genomic DNA down to 0.7 copy/cell and had a linear dynamic range of over 6 orders of magnitude. In the dual-color mode, fluorescence resonance energy transfer (FRET) was employed to achieve zero false-positive count. We also showed that DNA extracts from Pap test specimens did not interfere with the system. A surface-based method was used to improve the throughput of the flow system. HPV-16 DNA was hybridized to probes on a glass surface and detected with a total internal reflection fluorescence (TIRF) microscope. In the single-probe mode, the whole genome and target DNA were fluorescently labeled before hybridization, and the detection limit is similar to the flow system. In the dual-probe mode, a second probe was introduced. The linear dynamic range covers 1.44-7000 copies/cell, which is typical of early infection to near-cancer stages. The dual-probe method was tested with a crudely prepared sample. Even with reduced hybridization efficiency caused by the interference of cellular materials, we were still able to differentiate infected cells from healthy cells. Detection and quantification of viral antigen with a novel single-molecule immunosorbent assay (SMISA) was achieved. Antigen from human immunodeficiency virus type 1(HIV-1) was chosen to be the target in this study. The target was sandwiched between a monoclonal capture antibody and a

  8. Irreversible Change of the Pore Structure of ZIF-8 in Carbon Dioxide Capture with Water Coexistence

    DEFF Research Database (Denmark)

    Liu, Huang; Guo, Ping; Regueira Muñiz, Teresa

    2016-01-01

    The performance of zeolitic imidazolate framework 8 (ZIF-8) for CO2 capture under three different conditions (wetted ZIF-8, ZIF-8/water slurry, and ZIF-8/water-glycol slurry) was systemically investigated. This investigation included the study of the pore structure stability of ZIF-8 by using X......-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman detection technologies. Our results show that the CO2 adsorption ability of ZIF-8 could be substantially increased under the existence of liquid water. However, the structure characterization of the recovered ZIF-8...... showed an irreversible change of its framework, which occurs during the CO2 capture process. It was found that there is an irreversible chemical reaction among ZIF-8, water, and CO2, which creates both zinc carbonate (or zinc carbonate hydroxides) and single 2-methylimidazole crystals, and therefore...

  9. Optimization of an irreversible Stirling regenerative cycle

    International Nuclear Information System (INIS)

    Aragón-González, G; Cano-Bianco, M; León-Galicia, A; Rivera-Camacho, J M

    2015-01-01

    In this work a Stirling regenerative cycle with some irreversibilities is analyzed. The analyzed irreversibilities are located at the heat exchangers. They receive a finite amount of heat and heat leakage occurs between both reservoirs. Using this model, power and the efficiency at maximum power are obtained. Some optimal design parameters for the exchanger heat areas and thermal conductances are presented. The relation between the power, efficiency and the results obtained are shown graphically

  10. Reversible and irreversible heat engine and refrigerator cycles

    Science.gov (United States)

    Leff, Harvey S.

    2018-05-01

    Although no reversible thermodynamic cycles exist in nature, nearly all cycles covered in textbooks are reversible. This is a review, clarification, and extension of results and concepts for quasistatic, reversible and irreversible processes and cycles, intended primarily for teachers and students. Distinctions between the latter process types are explained, with emphasis on clockwise (CW) and counterclockwise (CCW) cycles. Specific examples of each are examined, including Carnot, Kelvin and Stirling cycles. For the Stirling cycle, potentially useful task-specific efficiency measures are proposed and illustrated. Whether a cycle behaves as a traditional refrigerator or heat engine can depend on whether it is reversible or irreversible. Reversible and irreversible-quasistatic CW cycles both satisfy Carnot's inequality for thermal efficiency, η ≤ η C a r n o t . Irreversible CCW cycles with two reservoirs satisfy the coefficient of performance inequality K ≤ K C a r n o t . However, an arbitrary reversible cycle satisfies K ≥ K C a r n o t when compared with a reversible Carnot cycle operating between its maximum and minimum temperatures, a potentially counterintuitive result.

  11. Correlating enzymatic browning inhibition and antioxidant ability of Maillard reaction products derived from different amino acids.

    Science.gov (United States)

    Xu, Haining; Zhang, Xiaoming; Karangwa, Eric; Xia, Shuqin

    2017-09-01

    Up to now, only limited research on enzymatic browning inhibition capacity (BIC) of Maillard reaction products (MRPs) has been reported and there are still no overall and systematic researches on MRPs derived from different amino acids. In the present study, BIC and antioxidant capacity, including 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity and Fe 2+ reducing power activity, of the MRPs derived from 12 different amino acids and three reducing sugars were investigated. The MRPs of cysteine (Cys), cystine, arginine (Arg) and histidine (His) showed higher BIC compared to other amino acids. Lysine (Lys)-MRPs showed the highest absorbance value at 420 nm (A 420 ) but very limited BIC, whereas Cys-MRPs, showed the highest BIC and the lowest A 420 . The A 420 can roughly reflect the trend of BIC of MRPs from different amino acids, except Cys and Lys. MRPs from tyrosine (Tyr) showed the most potent antioxidant capacity but very limited BIC, whereas Cys-MRPs showed both higher antioxidant capacity and BIC compared to other amino acids. Partial least squares regression analysis showed positive and significant correlation between BIC and Fe 2+ reducing power of MRPs from 12 amino acids with glucose or fructose, except Lys, Cys and Tyr. The suitable pH for generating efficient browning inhibition compounds varies depending on different amino acids: acidic pH was favorable for Cys, whereas neutral and alkaline pH were suitable for His and Arg, respectively. Increasing both heating temperature and time over a certain range could improve the BIC of MRPs of Cys, His and Arg, whereas any further increase deteriorates their browning inhibition efficiencies. The types of amino acid, initial pH, temperature and time of the Maillard reaction were found to greatly influence the BIC and antioxidant capacity of the resulting MRPs. There is no clear relationship between BIC and the antioxidant capacity of MRPs when reactant type and processing parameters of the Maillard

  12. Photoelectrochemical enzymatic biosensors.

    Science.gov (United States)

    Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

    2017-06-15

    Enzymatic biosensors have been valuable bioanalytical devices for analysis of diverse targets in disease diagnosis, biological and biomedical research, etc. Photoelectrochemical (PEC) bioanalysis is a recently emerged method that promptly becoming a subject of new research interests due to its attractive potential for future bioanalysis with high sensitivity and specificity. PEC enzymatic biosensors integrate the inherent sensitivities of PEC bioanalysis and the selectivity of enzymes and thus share their both advantages. Currently, PEC enzymatic biosensors have become a hot topic of significant research and the recent impetus has grown rapidly as demonstrated by increased research papers. Given the pace of advances in this area, this review will make a thorough discussion and survey on the fundamentals, sensing strategies, applications and the state of the art in PEC enzymatic biosensors, followed by future prospects based on our own opinions. We hope this work could provide an accessible introduction to PEC enzymatic biosensors for any scientist. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Process Evaluation Tools for Enzymatic Cascades Welcome Message

    DEFF Research Database (Denmark)

    Abu, Rohana

    improvement and implementation. Hence, the goal of this thesis is to evaluate the process concepts in enzymatic cascades in a systematic manner, using tools such as thermodynamic and kinetic analysis. Three relevant case studies have been used to exemplify the approach. In the first case study, thermodynamic......Biocatalysis is attracting significant attention from both academic and industrial scientists due to the excellent capability of enzyme to catalyse selective reactions. Recently, much interest has been shown in the application of enzymatic cascades as a useful tool in organic synthesis......, the kinetics can be controlled in a highly efficient way to achieve a sufficiently favourable conversion to a given target product. This is exemplified in the second case study, in the kinetic modelling of the formation of 2-ketoglutarate from glucoronate, the second case study. This cascade consists of 4...

  14. Irreversible climate change due to carbon dioxide emissions

    Science.gov (United States)

    Solomon, Susan; Plattner, Gian-Kasper; Knutti, Reto; Friedlingstein, Pierre

    2009-01-01

    The severity of damaging human-induced climate change depends not only on the magnitude of the change but also on the potential for irreversibility. This paper shows that the climate change that takes place due to increases in carbon dioxide concentration is largely irreversible for 1,000 years after emissions stop. Following cessation of emissions, removal of atmospheric carbon dioxide decreases radiative forcing, but is largely compensated by slower loss of heat to the ocean, so that atmospheric temperatures do not drop significantly for at least 1,000 years. Among illustrative irreversible impacts that should be expected if atmospheric carbon dioxide concentrations increase from current levels near 385 parts per million by volume (ppmv) to a peak of 450–600 ppmv over the coming century are irreversible dry-season rainfall reductions in several regions comparable to those of the “dust bowl” era and inexorable sea level rise. Thermal expansion of the warming ocean provides a conservative lower limit to irreversible global average sea level rise of at least 0.4–1.0 m if 21st century CO2 concentrations exceed 600 ppmv and 0.6–1.9 m for peak CO2 concentrations exceeding ≈1,000 ppmv. Additional contributions from glaciers and ice sheet contributions to future sea level rise are uncertain but may equal or exceed several meters over the next millennium or longer. PMID:19179281

  15. Intrinsic irreversibility in quantum theory

    International Nuclear Information System (INIS)

    Prigogine, I.; Petrosky, T.Y.

    1987-01-01

    Quantum theory has a dual structure: while solutions of the Schroedinger equation evolve in a deterministic and time reversible way, measurement introduces irreversibility and stochasticity. This presents a contrast to Bohr-Sommerfeld-Einstein theory, in which transitions between quantum states are associated with spontaneous and induced transitions, defined in terms of stochastic processes. A new form of quantum theory is presented here, which contains an intrinsic form of irreversibility, independent of observation. This new form applies to situations corresponding to a continuous spectrum and to quantum states with finite life time. The usual non-commutative algebra associated to quantum theory is replaced by more general algebra, in which operators are also non-distributive. Our approach leads to a number of predictions, which hopefully may be verified or refuted in the next years. (orig.)

  16. Irreversibility and self-organization in spin glasses. 2. Irreversibility and the problem of configuration averaging

    International Nuclear Information System (INIS)

    Kovrov, V.P.; Kurbatov, A.M.

    1989-05-01

    The generalization of a configuration averaging to a system displaying irreversible effects is suggested. The properties of the ''pathological'' equilibrium state at low temperatures are determined and discussed. (author). 16 refs, 3 figs

  17. Enzymatic Activity Detection via Electrochemistry for Enceladus

    Science.gov (United States)

    Studemeister, Lucy; Koehne, Jessica; Quinn, Richard

    2017-01-01

    Electrochemical detection of biological molecules is a pertinent topic and application in many fields such as medicine, environmental spills, and life detection in space. Proteases, a class of molecules of interest in the search for life, catalyze the hydrolysis of peptides. Trypsin, a specific protease, was chosen to investigate an optimized enzyme detection system using electrochemistry. This study aims at providing the ideal functionalization of an electrode that can reliably detect a signal indicative of an enzymatic reaction from an Enceladus sample.

  18. Enzymatic browning and after-cooking darkening of Jerusalem artichoke tubers (Helianthus tuberosus L.)

    DEFF Research Database (Denmark)

    Bach, Vibe; Bennedbæk-Jensen, Sidsel; Clausen, Morten Rahr

    2013-01-01

    Jerusalem artichoke tubers (Helianthus tuberosus L.) undergo enzymatic browning when peeled or cut, and turn grey after boiling, due to after-cooking darkening reactions between iron and phenolic acids. In an attempt to reveal the components responsible for these discolouration reactions, sensory...... evaluation and instrumental colour measurements were related to contents of total phenolics, phenolic acids, organic acids and iron in three varieties of raw and boiled Jerusalem artichoke tubers harvested in the autumn and the spring. No differences were found between varieties in sensory evaluated...... enzymatic browning, but Rema and Draga had higher scores than Mari in after-cooking darkening. Jerusalem artichoke tubers had higher contents of total phenolics, phenolic acids and citric acid in the autumn and low contents in the spring, while it was the opposite for malic acid. None of the chemical...

  19. [Optimization of enzymatic extraction of polysaccharide from Dendrobium officinale by box-Behnken design and response surface methodology].

    Science.gov (United States)

    Hu, Jian-mei; Li, Jing-ling; Feng, Peng; Zhang, Xiang-dong; Zhong, Ming

    2014-01-01

    To optimize the processing of enzymatic extraction of polysaccharide from Dendrobium officinale. With phenol-sulfuric acid method and the DNS determination polysaccharide, Box-Behnken response surface methodology was used to optimize different enzyme dosage, reaction temperature and reaction time by using Design-Expert 8.05 software for data analysis and processing. According to Box-Behnken response, the best extraction conditions for the polysaccharide from Dendrobium officinale were as follows: the amount of enzyme complex was 3.5 mg/mL, hydrolysis temperature was 53 degrees C, and reaction time was 70 min. In accordance with the above process, the polysaccharide yield was 16.11%. Box-Behnken response surface methodology is used to optimize the enzymatic extraction process for the polysaccharide in this study, which is effective, stable and feasible.

  20. Optimization at different loads by minimization of irreversibilities

    International Nuclear Information System (INIS)

    Wong, K.F.V.; Niu, Z.

    1991-01-01

    This paper reports that the irreversibility of the power cycle was chosen as the objective function as this function can successfully measure both the quality and quantity of energy flow in the cycle. Minimization of the irreversibility ensures that the power cycle will operate more efficiently. One feature of the present work is that the boiler, turbine, condenser and heaters are treated as one system for the purpose of optimization. In the optimization model, nine regression formulae are used, which are obtained from the measured test data. From the results of the present work, it can be seen that the optimization model developed can represent the effect of operational parameters on the power plant first and second law efficiency. Some of the results can be used to provide guidance for the optimal operation of the power plant. When the power cycle works at full load, the main steam temperature and pressure should be at the upper limit for minimal irreversibility of the system. If the load is less than 65% of its design capacity, the steam temperature and pressure should be decreased for a lower irreversibility of the system

  1. EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4

    Energy Technology Data Exchange (ETDEWEB)

    Wolery, T.J.; Daveler, S.A.

    1992-10-09

    EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.

  2. Pretreatment of corn stover using wet oxidation to enhance enzymatic digestibility

    DEFF Research Database (Denmark)

    Varga, E.; Schmidt, A.S.; Reczey, K.

    2003-01-01

    was about 85%. Decreasing the hydrolysis temperature to 40degreesC increased hydrolysis time from 24 to 72 h. Decreasing the enzyme loading to 5 FPU/g of DM biomass slightly decreased the enzymatic conversion from 83.4 to 71%. Thus, enzyme loading can be reduced without significantly affecting......) was investigated to enhance the enzymatic digestibility of corn stover. Six different combinations of reaction temperature, time, and pH were applied. The best conditions (60 g/L of corn stover, 195degreesC, 15 min, 12 bar O-2, 2 g/L of Na2CO) increased the enzymatic conversion of corn stover four times, compared...... to untreated material. Under these conditions 60% of hemicellulose and 30% of lignin were solubilized, whereas 90% of cellulose remained in the solid fraction. After 24-h hydrolysis at 50degreesC using 25 filter paper units (FPU)/g of drymatter (DM) biomass, the achieved conversion of cellulose to glucose...

  3. Kinetics of enzymatic trans-esterification of glycerides for biodiesel production.

    Science.gov (United States)

    Calabrò, Vincenza; Ricca, Emanuele; De Paola, Maria Gabriela; Curcio, Stefano; Iorio, Gabriele

    2010-08-01

    In this paper, the reaction of enzymatic trans-esterification of glycerides with ethanol in a reaction medium containing hexane at a temperature of 37 degrees C has been studied. The enzyme was Lipase from Mucor miehei, immobilized on ionic exchange resin, aimed at achieving high catalytic specific surface and recovering, regenerating and reusing the biocatalyst. A kinetic analysis has been carried out to identify the reaction path; the rate equation and kinetic parameters have been also calculated. The kinetic model has been validated by comparison between predicted and experimental results. Mass transport resistances estimation was undertaken in order to verify that the kinetics found was intrinsic. Model potentialities in terms of reactors design and optimization are also shown.

  4. Enzymatic synthesis of C-11 formaldehyde: concise communication

    International Nuclear Information System (INIS)

    Slegers, G.; Lambrecht, R.H.D.; Vandewalle, T.; Meulewaeter, L.; Vandecasteele, C.

    1984-01-01

    An enzymatic synthesis of C-11 formaldehyde from C-11 methanol is presented, with immobilized alcohol oxidase and catalase: a rapid, simple procedure, with a high and reproducible yield. Carbon-11 methanol is oxidized to C-11 formaldehyde by passage over a column on which the enzymes alcohol oxidase and catalase are immobilized. The catalase increases reaction velocity by recycling the oxygen, and prevents destruction of the alcohol oxidase by eliminating the excess of hydrogen peroxide. The yield of the enzyme-catalyzed oxidation was 80-95%. A specific activity of 400-450 mCi/μmole was obtained at EOB + 20 min. Various immobilization techniques and the optimal reaction conditions of the immobilized enzymes are investigated

  5. AST1306, a novel irreversible inhibitor of the epidermal growth factor receptor 1 and 2, exhibits antitumor activity both in vitro and in vivo.

    Directory of Open Access Journals (Sweden)

    Hua Xie

    Full Text Available Despite the initial response to the reversible, ATP-competitive quinazoline inhibitors that target ErbB-family, such a subset of cancer patients almost invariably develop resistance. Recent studies have provided compelling evidence that irreversible ErbB inhibitors have the potential to override this resistance. Here, we found that AST1306, a novel anilino-quinazoline compound, inhibited the enzymatic activities of wild-type epidermal growth factor receptor (EGFR and ErbB2 as well as EGFR resistant mutant in both cell-free and cell-based systems. Importantly, AST1306 functions as an irreversible inhibitor, most likely through covalent interaction with Cys797 and Cys805 in the catalytic domains of EGFR and ErbB2, respectively. Further studies showed that AST1306 inactivated pathways downstream of these receptors and thereby inhibited the proliferation of a panel of cancer cell lines. Although the activities of EGFR and ErbB2 were similarly sensitive to AST1306, ErbB2-overexpressing cell lines consistently exhibited more sensitivity to AST1306 antiproliferative effects. Consistent with this, knockdown of ErbB2, but not EGFR, decreased the sensitivity of SK-OV-3 cells to AST1306. In vivo, AST1306 potently suppressed tumor growth in ErbB2-overexpressing adenocarcinoma xenograft and FVB-2/N(neu transgenic breast cancer mouse models, but weakly inhibited the growth of EGFR-overexpressing tumor xenografts. Tumor growth inhibition induced by a single dose of AST1306 in the SK-OV-3 xenograft model was accompanied by a rapid (within 2 h and sustained (≥24 h inhibition of both EGFR and ErbB2, consistent with an irreversible inhibition mechanism. Taken together, these results establish AST1306 as a selective, irreversible ErbB2 and EGFR inhibitor whose growth-inhibitory effects are more potent in ErbB2-overexpressing cells.

  6. Methods for determining enzymatic activity comprising heating and agitation of closed volumes

    Science.gov (United States)

    Thompson, David Neil; Henriksen, Emily DeCrescenzo; Reed, David William; Jensen, Jill Renee

    2016-03-15

    Methods for determining thermophilic enzymatic activity include heating a substrate solution in a plurality of closed volumes to a predetermined reaction temperature. Without opening the closed volumes, at least one enzyme is added, substantially simultaneously, to the closed volumes. At the predetermined reaction temperature, the closed volumes are agitated and then the activity of the at least one enzyme is determined. The methods are conducive for characterizing enzymes of high-temperature reactions, with insoluble substrates, with substrates and enzymes that do not readily intermix, and with low volumes of substrate and enzyme. Systems for characterizing the enzymes are also disclosed.

  7. Process development for gelatinisation and enzymatic hydrolysis of starch at high concentrations

    NARCIS (Netherlands)

    Baks, T.

    2007-01-01

    cum laude graduation (with distinction) Enzymatic hydrolysis of starch is encountered in day-to-day life for instance in the dishwasher during removal of stains with detergents or in our mouth during chewing of starch-based foods in the presence of saliva. The reaction is also important for the

  8. Effect of Thermal Processing towards Lipid Oxidation and Non-enzymatic Browning Reactions of Antartic Krill (Euphausia superba) Meal.

    Science.gov (United States)

    Liu, Yanzi; Cong, Peixu; Li, Beijia; Song, Yu; Liu, Yanjun; Xu, Jie; Xue, Changhu

    2018-04-13

    Antarctic krill is a huge source of biomass and prospective high-quality lipid source. Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), nutritionally important lipid components with poor oxidative stability, were used as markers of oxidation during thermal processing of Antarctic krill (Euphausia superba) meal by evaluating the lipolysis, lipid oxidation, and non-enzymatic browning reactions. Liquid chromatography-mass spectrometry of the phospholipids (PLs) and the main oxidation products of free fatty acids (FFAs) and phosphatidylcholine (PC) was effective for evaluating the oxidation of EPA and DHA. During boiling, oxidation of EPA and DHA in the FFA and PC fractions and hydrolysis of the fatty acids at the sn-2 position of the PLs were predominant. The changes in PC during drying were mainly attributed to the oxidation of EPA and DHA. Heat treatment increased the oxidation products and concentration of hydrophobic pyrrole owing to pyrrolization between phosphatidylethanolamine (PE) and the lipid oxidation products. The lipid oxidation level of Antarctic krill increased after drying, owing to prolonged heating under the severe conditions. This article is protected by copyright. All rights reserved.

  9. A Simple Method To Demonstrate the Enzymatic Production of Hydrogen from Sugar

    Science.gov (United States)

    Hershlag, Natalie; Hurley, Ian; Woodward, Jonathan

    1998-10-01

    There is current interest in and concern for the development of environmentally friendly bioprocesses whereby biomass and the biodegradable content of municipal wastes can be converted to useful forms of energy. For example, cellulose, a glucose polymer that is the principal component of biomass and paper waste, can be enzymatically degraded to glucose, which can subsequently be converted by fermentation or further enzymatic reaction to fuels such as ethanol or hydrogen. These products represent alternative energy sources to fossil fuels such as oil. Demonstration of the relevant reactions in high-school and undergraduate college laboratories would have value not only in illustrating environmentally friendly biotechnology for the utilization of renewable energy sources, such as cellulosic wastes, but could also be used to teach the principles of enzyme-catalyzed reactions. In the experimental protocol described here, it has been demonstrated that the common sugar glucose can be used to produce hydrogen using two enzymes, glucose dehydrogenase and hydrogenase. No sophisticated or expensive hydrogen detection equipment is required-only a redox dye, benzyl viologen, which turns purple when it is reduced. The color can be detected by a simple colorimeter. Furthermore, it is shown that the renewable resource cellulose, in its soluble derivative from carboxymethylcellulose, as well as aspen-wood waste, is also a source of hydrogen if the enzyme cellulase is included in the reaction mixture.

  10. Isolation and Characterization of Human Dental Pulp Stem Cells from Cryopreserved Pulp Tissues Obtained from Teeth with Irreversible Pulpitis.

    Science.gov (United States)

    Malekfar, Azin; Valli, Kusum S; Kanafi, Mohammad Mahboob; Bhonde, Ramesh R

    2016-01-01

    Human dental pulp stem cells (DPSCs) are becoming an attractive target for therapeutic purposes because of their neural crest origin and propensity. Although DPSCs can be successfully cryopreserved, there are hardly any reports on cryopreservation of dental pulp tissues obtained from teeth diagnosed with symptomatic irreversible pulpitis during endodontic treatment and isolation and characterization of DPSCs from such cryopreserved pulp. The aim of this study was to cryopreserve the said pulp tissues to propagate and characterize isolated DPSCs. A medium consisting of 90% fetal bovine serum and 10% dimethyl sulfoxide was used for cryopreservation of pulp tissues. DPSCs were isolated from fresh and cryopreserved pulp tissues using an enzymatic method. Cell viability and proliferation were determined using the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay. DPSC migration and interaction were analyzed with the wound healing assay. Mesenchymal characteristics of DPSCs were verified by flow cytometric analysis of cell surface CD markers. The osteogenic and adipogenic potential of DPSCs was shown by von Kossa and oil red O staining methods, respectively, and the polymerase chain reaction method. We found no significant difference in CD marker expression and osteogenic and adipogenic differentiation potential of DPSCs obtained from fresh and cryopreserved dental pulp tissue. Our study shows that dental pulp can be successfully cryopreserved without losing normal characteristics and differentiation potential of their DPSCs, thus making them suitable for dental banking and future therapeutic purposes. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  11. Reactor design for minimizing product inhibition during enzymatic lignocellulose hydrolysis: I. Significance and mechanism of cellobiose and glucose inhibition on cellulolytic enzymes

    DEFF Research Database (Denmark)

    Andric, Pavle; Meyer, Anne S.; Jensen, Peter Arendt

    2010-01-01

    Achievement of efficient enzymatic degradation of cellulose to glucose is one of the main prerequisites and one of the main challenges in the biological conversion of lignocellulosic biomass to liquid fuels and other valuable products. The specific inhibitory interferences by cellobiose and glucose...... on enzyme-catalyzed cellulose hydrolysis reactions impose significant limitations on the efficiency of lignocellulose conversion especially at high-biomass dry matter conditions. To provide the base for selecting the optimal reactor conditions, this paper reviews the reaction kinetics, mechanisms......, and significance of this product inhibition, notably the cellobiose and glucose inhibition, on enzymatic cellulose hydrolysis. Particular emphasis is put on the distinct complexity of cellulose as a substrate, the multi-enzymatic nature of the cellulolytic degradation, and the particular features of cellulase...

  12. Substance P and CGRP expression in dental pulps with irreversible pulpitis.

    Science.gov (United States)

    Sattari, Mandana; Mozayeni, Mohammad Ali; Matloob, Arash; Mozayeni, Maryam; Javaheri, Homan H

    2010-08-01

    The purpose of this study was to compare substance P (SP) and calcitonin gene-related peptide (CGRP) expression in pulp tissue with clinically diagnosed symptomatic and asymptomatic irreversible pulpitis. Healthy pulps acted as controls. Five normal pulps and 40 with irreversible pulpitis (20 symptomatic and 20 asymptomatic) were obtained from 45 different patients. SP and CGRP expression was determined by competition binding assays using enzyme immunoassay. anova and Mann-Whitney tests were used to ascertain if there were statistically significant differences between the groups. The results showed that neuropeptides were found in all pulp samples. The highest and the lowest expressions for SP and CGRP were found in symptomatic irreversible pulpitis and healthy pulps groups, respectively. The differences between healthy pulps and the groups of pulps having irreversible pulpitis were significant (P pulpitis groups (P pulpitis groups were not significant. This study demonstrated that the expression of CGRP and SP is significantly higher in pulps with irreversible pulpitis compared with healthy pulps.

  13. Analytical Validation of a New Enzymatic and Automatable Method for d-Xylose Measurement in Human Urine Samples

    Directory of Open Access Journals (Sweden)

    Israel Sánchez-Moreno

    2017-01-01

    Full Text Available Hypolactasia, or intestinal lactase deficiency, affects more than half of the world population. Currently, xylose quantification in urine after gaxilose oral administration for the noninvasive diagnosis of hypolactasia is performed with the hand-operated nonautomatable phloroglucinol reaction. This work demonstrates that a new enzymatic xylose quantification method, based on the activity of xylose dehydrogenase from Caulobacter crescentus, represents an excellent alternative to the manual phloroglucinol reaction. The new method is automatable and facilitates the use of the gaxilose test for hypolactasia diagnosis in the clinical practice. The analytical validation of the new technique was performed in three different autoanalyzers, using buffer or urine samples spiked with different xylose concentrations. For the comparison between the phloroglucinol and the enzymatic assays, 224 urine samples of patients to whom the gaxilose test had been prescribed were assayed by both methods. A mean bias of −16.08 mg of xylose was observed when comparing the results obtained by both techniques. After adjusting the cut-off of the enzymatic method to 19.18 mg of xylose, the Kappa coefficient was found to be 0.9531, indicating an excellent level of agreement between both analytical procedures. This new assay represents the first automatable enzymatic technique validated for xylose quantification in urine.

  14. Guinea pig ductus arteriosus. II - Irreversible closure after birth.

    Science.gov (United States)

    Fay, F. S.; Cooke, P. H.

    1972-01-01

    To investigate the mechanism underlying irreversibility of ductal closure after birth, studies were undertaken to determine the exact time course for the onset of irreversible closure of the guinea pig ductus arteriosus. Parallel studies of the reactivity of ductal smooth muscle to oxygen and studies of the postpartum cellular changes within the vessel were also carried out.

  15. Pretreatment of corn stover using wet oxidation to enhance enzymatic digestibility.

    Science.gov (United States)

    Varga, Eniko; Schmidt, Anette S; Réczey, Kati; Thomsen, Anne Belinda

    2003-01-01

    Corn stover is an abundant, promising raw material for fuel ethanol production. Although it has a high cellulose content, without pretreatment it resists enzymatic hydrolysis, like most lignocellulosic materials. Wet oxidation (water, oxygen, mild alkali or acid, elevated temperature and pressure) was investigated to enhance the enzymatic digestibility of corn stover. Six different combinations of reaction temperature, time, and pH were applied. The best conditions (60 g/L of corn stover, 195 degrees C, 15 min, 12 bar O2, 2 g/L of Na2CO3) increased the enzymatic conversion of corn stover four times, compared to untreated material. Under these conditions 60% of hemicellulose and 30% of lignin were solubilized, whereas 90% of cellulose remained in the solid fraction. After 24-h hydrolysis at 50 degrees C using 25 filter paper units (FPU)/g of drymatter (DM) biomass, the achieved conversion of cellulose to glucose was about 85%. Decreasing the hydrolysis temperature to 40 degrees C increased hydrolysis time from 24 to 72 h. Decreasing the enzyme loading to 5 FPU/g of DM biomass slightly decreased the enzymatic conversion from 83.4 to 71%. Thus, enzyme loading can be reduced without significantly affecting the efficiency of hydrolysis, an important economical aspect.

  16. Lignin from hydrothermally pretreated grass biomass retards enzymatic cellulose degradation by acting as a physical barrier rather than by inducing nonproductive adsorption of enzymes

    DEFF Research Database (Denmark)

    Djajadi, Demi T.; Jensen, Mads M.; Oliveira, Marlene

    2018-01-01

    Lignin is known to hinder efficient enzymatic conversion of lignocellulose in biorefining processes. In particular, nonproductive adsorption of cellulases onto lignin is considered a key mechanism to explain how lignin retards enzymatic cellulose conversion in extended reactions. Lignin-rich resi...

  17. Multiscale time irreversibility of heart rate and blood pressure variability during orthostasis

    International Nuclear Information System (INIS)

    Chladekova, L; Czippelova, B; Turianikova, Z; Tonhajzerova, I; Calkovska, A; Javorka, M; Baumert, M

    2012-01-01

    Time irreversibility is a characteristic feature of non-equilibrium, complex systems such as the cardiovascular control mediated by the autonomic nervous system (ANS). Time irreversibility analysis of heart rate variability (HRV) and blood pressure variability (BPV) represents a new approach to assess cardiovascular regulatory mechanisms. The aim of this paper was to assess the changes in HRV and BPV irreversibility during the active orthostatic test (a balance of ANS shifted towards sympathetic predominance) in 28 healthy young subjects. We used three different time irreversibility indices—Porta’s, Guzik's and Ehler's indices (P%, G% and E, respectively) derived from data segments containing 1000 beat-to-beat intervals on four timescales. We observed an increase in the HRV and a decrease in the BPV irreversibility during standing compared to the supine position. The postural change in irreversibility was confirmed by surrogate data analysis. The differences were more evident in G% and E than P% and for higher scale factors. Statistical analysis showed a close relationship between G% and E. Contrary to this, the association between P% and G% and P% and E was not proven. We conclude that time irreversibility of beat-to-beat HRV and BPV is significantly altered during orthostasis, implicating involvement of the autonomous nervous system in its generation. (paper)

  18. Enzymatic transesterification of used frying oils

    Energy Technology Data Exchange (ETDEWEB)

    Kovacs, S.; Hancsok, J. (Univ. of Pannonia, Veszprem (HU)), Email: hancsokj@almos.uni-pannon.hu

    2009-07-01

    The research of converting used frying oils to less harmful products with much higher value was forced by environmental, human biological and economical reasons. One possible pathway of the transformation is the enzymatic transesterification. Through the research work used frying oils (UFO) and sunflower oils (SO) from different origins were first properly pre-treated. Then the previously mentioned feeds and different mixtures of them were transesterified in the presence of Novozym 435 enzyme catalyst under different process conditions. Characteristics of the produced methyl esters were evaluated according to the requirements of EN 14214:2009 standard. We determined that the transesterification of used frying oils is not expediential in the presence of enzyme catalyst because the significant decreasing of catalyst activity. We have found proper UFO and SO mixtures and combination of process conditions (pressure: atmospheric, temperature: 54 +-1 deg C; methanol to triglyceride molar ratio: 4:1; reaction time: 16 hours) resulting in high (>90 %) yield of monoesters. We clearly established that the best results through the enzymatic transesterification were obtained with the improved sunflower oils containing the highest amount (>88 %) of oleic acid and the used frying oils originated from this source. (orig.)

  19. Irreversibility and conditional probability

    International Nuclear Information System (INIS)

    Stuart, C.I.J.M.

    1989-01-01

    The mathematical entropy - unlike physical entropy - is simply a measure of uniformity for probability distributions in general. So understood, conditional entropies have the same logical structure as conditional probabilities. If, as is sometimes supposed, conditional probabilities are time-reversible, then so are conditional entropies and, paradoxically, both then share this symmetry with physical equations of motion. The paradox is, of course that probabilities yield a direction to time both in statistical mechanics and quantum mechanics, while the equations of motion do not. The supposed time-reversibility of both conditionals seems also to involve a form of retrocausality that is related to, but possibly not the same as, that described by Costa de Beaurgard. The retrocausality is paradoxically at odds with the generally presumed irreversibility of the quantum mechanical measurement process. Further paradox emerges if the supposed time-reversibility of the conditionals is linked with the idea that the thermodynamic entropy is the same thing as 'missing information' since this confounds the thermodynamic and mathematical entropies. However, it is shown that irreversibility is a formal consequence of conditional entropies and, hence, of conditional probabilities also. 8 refs. (Author)

  20. Enzymatic hydrolysis of lactose of whey permeate

    Directory of Open Access Journals (Sweden)

    Karina Nascimento de Almeida

    2015-09-01

    Full Text Available The whey permeate is the residual of the concentration process of the whey proteins by ultrafiltration method. It contains important nutrients such as lactose, minerals and some proteins and lipids. It is without an ending industrial waste that causes serious damage to the environment. For its full use the lactose must be hydrolyzed to enable its consumption by intolerant people. The enzymatic hydrolysis by lactase (β-galactosidase of Kluyveromyces lactis yeast is a safe method that does not compromise the integrity of other nutrients, enabling further use of the permeate as a raw material. This study aimed to perform tests of enzymatic hydrolysis of lactose in whey permeate formulations in a concentration of 0.2%, 0.7% and 1% at 30, 60 and 90 minutes with pH 6.3 medium and 37 °C. The reactions were monitored by high performance liquid chromatography which showed that the enzyme concentration of 0.7% at time 30 minutes formulations became safe for consumption by lactose intolerant people, according to minimum levels established by law.

  1. Performance Optimization of Irreversible Air Heat Pumps Considering Size Effect

    Science.gov (United States)

    Bi, Yuehong; Chen, Lingen; Ding, Zemin; Sun, Fengrui

    2018-06-01

    Considering the size of an irreversible air heat pump (AHP), heating load density (HLD) is taken as thermodynamic optimization objective by using finite-time thermodynamics. Based on an irreversible AHP with infinite reservoir thermal-capacitance rate model, the expression of HLD of AHP is put forward. The HLD optimization processes are studied analytically and numerically, which consist of two aspects: (1) to choose pressure ratio; (2) to distribute heat-exchanger inventory. Heat reservoir temperatures, heat transfer performance of heat exchangers as well as irreversibility during compression and expansion processes are important factors influencing on the performance of an irreversible AHP, which are characterized with temperature ratio, heat exchanger inventory as well as isentropic efficiencies, respectively. Those impacts of parameters on the maximum HLD are thoroughly studied. The research results show that HLD optimization can make the size of the AHP system smaller and improve the compactness of system.

  2. Kinetic theory of nonequilibrium ensembles, irreversible thermodynamics, and generalized hydrodynamics

    CERN Document Server

    Eu, Byung Chan

    2016-01-01

    This book presents the fundamentals of irreversible thermodynamics for nonlinear transport processes in gases and liquids, as well as for generalized hydrodynamics extending the classical hydrodynamics of Navier, Stokes, Fourier, and Fick. Together with its companion volume on relativistic theories, it provides a comprehensive picture of the kinetic theory formulated from the viewpoint of nonequilibrium ensembles in both nonrelativistic and, in Vol. 2, relativistic contexts. Theories of macroscopic irreversible processes must strictly conform to the thermodynamic laws at every step and in all approximations that enter their derivation from the mechanical principles. Upholding this as the inviolable tenet, the author develops theories of irreversible transport processes in fluids (gases or liquids) on the basis of irreversible kinetic equations satisfying the H theorem. They apply regardless of whether the processes are near to or far removed from equilibrium, or whether they are linear or nonlinear with respe...

  3. Synthesizing aspartyl-phenylalanine methyl precursor by enzymatic method. Kosoho ni yoru asuparutemu zenkutai no gosei

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, M. (Waseda University, Tokyo (Japan)); Hirata, A. (Waseda University, Tokyo (Japan). School of Science and Engineering)

    1991-10-01

    Demand for aspartyl-phenylalanine methyl, an amino acid based artificial sweetener, is increasing for use by people on diet. The material is manufactured by making a precursor through dehydrating and condensing N-protective{sub L}-asparagine acid and {sub L}-phenylalanine methyl ester, and then removing the protective group. While the manufacturing methods include chemical process and enzymatic process, this paper introduces various researches done mainly by the latter process. The enzymatic process is simpler and safer than the chemical process, allowing experiments to be carried out easily. However, since the reaction equilibrium is biased more on the decomposition side than the synthesis side, it should be shifted to the synthesis side. Such operations may be carried out as separating the products simultaneously with the reaction, adding organic solvents, and operating the reaction in an organic solvent. The last operation, for example, reduces the concentration of liquid produced by the reaction by use of either water soluble or slightly soluble organic solvent, and improves the yield. It also has an advantage that relatively stable fixing enzymes can be adjusted by use of hydrophilic carriers. 68 refs., 8 figs.

  4. Suppression of acyl migration in enzymatic production of structured lipids through temperature programming

    DEFF Research Database (Denmark)

    Yang, Tiankui; Fruekilde, Maj-Britt; Xu, Xuebing

    2005-01-01

    Acyl migration in the glycerol backbone often leads to the increase of by-products in the enzymatic production of specific structured lipids. Acyl migration is a thermodynamic process and is very difficult to stop fully in actual reactions. The objective of this study was to investigate...

  5. Analysis of Brownian Dynamics Simulations of Reversible Bimolecular Reactions

    KAUST Repository

    Lipková, Jana

    2011-01-01

    A class of Brownian dynamics algorithms for stochastic reaction-diffusion models which include reversible bimolecular reactions is presented and analyzed. The method is a generalization of the λ-bcȳ model for irreversible bimolecular reactions which was introduced in [R. Erban and S. J. Chapman, Phys. Biol., 6(2009), 046001]. The formulae relating the experimentally measurable quantities (reaction rate constants and diffusion constants) with the algorithm parameters are derived. The probability of geminate recombination is also investigated. © 2011 Society for Industrial and Applied Mathematics.

  6. Enzymatic browning and after-cooking darkening of Jerusalem artichoke tubers (Helianthus tuberosus L.).

    Science.gov (United States)

    Bach, Vibe; Jensen, Sidsel; Clausen, Morten R; Bertram, Hanne C; Edelenbos, Merete

    2013-11-15

    Jerusalem artichoke tubers (Helianthus tuberosus L.) undergo enzymatic browning when peeled or cut, and turn grey after boiling, due to after-cooking darkening reactions between iron and phenolic acids. In an attempt to reveal the components responsible for these discolouration reactions, sensory evaluation and instrumental colour measurements were related to contents of total phenolics, phenolic acids, organic acids and iron in three varieties of raw and boiled Jerusalem artichoke tubers harvested in the autumn and the spring. No differences were found between varieties in sensory evaluated enzymatic browning, but Rema and Draga had higher scores than Mari in after-cooking darkening. Jerusalem artichoke tubers had higher contents of total phenolics, phenolic acids and citric acid in the autumn and low contents in the spring, while it was the opposite for malic acid. None of the chemical parameters investigated could explain the discolouration of the Jerusalem artichoke tubers. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Transition to Clean Capital, Irreversible Investment and Stranded Assets

    OpenAIRE

    Rozenberg, Julie; Vogt-Schilb, Adrien; Hallegatte, Stephane

    2014-01-01

    This paper uses a Ramsey model with two types of capital to analyze the optimal transition to clean capital when polluting investment is irreversible. The cost of climate mitigation decomposes as a technical cost of using clean instead of polluting capital and a transition cost from the irreversibility of pre-existing polluting capital. With a carbon price, the transition cost can be limit...

  8. Kinetics of irreversible thermal decomposition of dissociating nitrogen dioxide with nitrogen oxide or oxygen additions

    International Nuclear Information System (INIS)

    Gvozdev, A.A.

    1987-01-01

    The effect of NO or O 2 admixtures on kinetics of the irreversible thermal decomposition of nitrogen dioxide at temperatures 460-520 deg C and pressures 4-7 MPa has been studied. It follows from experimental data that the rate of N 2 O 4 formation reduces with the increase of partial pressure of oxygen or decrease of partial pressure of nitrogen oxide. The same regularity is seen for the rate of nitrogen formation. The rate constants of N 2 O formation in dissociating nitrogen tetroxide with oxygen or nitrogen oxide additions agree satisfactorily with previously published results, obtained in stoichiometric mixtures. The appreciable discrepancy at 520 deg C is bind with considerable degree of nitrogen oxide transformation which constitutes approximately 14%. It is determined that the kinetics of formation of the products of irreversible N 2 O and N 2 decomposition in stoichiometric and non-stoichiometric 2NO 2 ↔ 2NO+O 2 mixtures is described by identical 3NO → N 2 O+NO 2 and N 2 O+NO → N 2 +NO 2 reactions

  9. Spectral line intensity irreversibility in circulatory plasma magnetization processes

    Science.gov (United States)

    Qu, Z. Q.; Dun, G. T.

    2012-01-01

    Spectral line intensity variation is found to be irreversible in circulatory plasma magnetization process by experiments described in this paper, i.e., the curves illustrating spectral line photon fluxes irradiated from a light source immerged in a magnetic field by increasing the magnetic induction cannot be reproduced by decreasing the magnetic induction within the errors. There are two plasma magnetization patterns found. One shows that the intensities are greater at the same magnetic inductions during the magnetic induction decreasing process after the increasing, and the other gives the opposite effect. This reveals that the magneto-induced excitation and de-excitation process is irreversible like ferromagnetic magnetization. But the two irreversible processes are very different in many aspects stated in the text.

  10. Behavior of the irreversibility line in the new superconductor La{sub 1.5+x}Ba{sub 1.5+x-y}Ca{sub y}Cu{sub 3}O{sub z}

    Energy Technology Data Exchange (ETDEWEB)

    Parra Vargas, C.A. [Grupo de Fisica de Materiales, Escuela de Fisica, Universidad Pedagogica y Tecnologica de Colombia, Tunja (Colombia); Pimentel, J.L.; Pureur, P. [Instituto de Fisica, Universidade Federal do Rio Grande do Sul, 91501-970 Porto Alegre, RS (Brazil); Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, AA 5997, Bogota DC (Colombia); Roa-Rojas, J., E-mail: carlos.parra@uptc.edu.co [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, AA 5997, Bogota DC (Colombia)

    2012-08-15

    The irreversibility properties of high-T{sub c} superconductors are of major importance for technological applications. For example, a high irreversibility magnetic field is a more desirable quality for a superconductor . The irreversibility line in the H-T plane is constituted by experimental points, which divides the irreversible and reversible behavior of the magnetization. The irreversibility lines for series of La{sub 1.5+x}Ba{sub 1.5+x-y}Ca{sub y}Cu{sub 3}O{sub z} polycrystalline samples with different doping were investigated. The samples were synthesized using the usual solid estate reaction method. Rietveld-type refinement of x-ray diffraction patterns permitted to determine the crystallization of material in a tetragonal structure. Curves of magnetization ZFC-FC for the system La{sub 1.5+x}Ba{sub 1.5+x-y}Ca{sub y}Cu{sub 3}O{sub z}, were measured in magnetic fields of the 10-20,000 Oe, and allowed to obtain the values for the irreversibility and critical temperatures. The data of irreversibility temperature allowed demarcating the irreversibility line, T{sub irr}(H). Two main lines are used for the interpretation of the irreversibility line: one of those which suppose that the vortexes are activated thermally and the other proposes that associated to T{sub irr} a phase transition occurs. The irreversibility line is described by a power law. The obtained results allow concluding that in the system La{sub 1.5+x}Ba{sub 1.5+x-y}Ca{sub y}Cu{sub 3}O{sub z} a characteristic bend of the Almeida-Thouless (AT) tendency is dominant for low fields and a bend Gabay-Toulouse (GT) behavior for high magnetic fields. This feature of the irreversibility line has been reported as a characteristic of granular superconductors and it corroborates the topological effects of vortexes mentioned by several authors .

  11. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  12. Ecological optimization and parametric study of irreversible Stirling and Ericsson heat pumps

    International Nuclear Information System (INIS)

    Tyagi, S.K.; Kaushik, S.C.; Salohtra, R.

    2002-01-01

    This communication presents the ecological optimization and parametric study of irreversible Stirling and Ericsson heat pump cycles, in which the external irreversibility is due to finite temperature difference between working fluid and external reservoirs while the internal irreversibilities are due to regenerative heat loss and other entropy generations within the cycle. The ecological function is defined as the heating load minus the irreversibility (power loss) which is ambient temperature times the entropy generation. The ecological function is optimized with respect to working fluid temperatures, and the expressions for various parameters at the optimal operating condition are obtained. The effects of different operating parameters on the performance of these cycles have been studied. It is found that the effect of internal irreversibility parameter is more pronounced than the other parameters on the performance of these cycles. (author)

  13. Ictal time-irreversible intracranial EEG signals as markers of the epileptogenic zone.

    Science.gov (United States)

    Schindler, Kaspar; Rummel, Christian; Andrzejak, Ralph G; Goodfellow, Marc; Zubler, Frédéric; Abela, Eugenio; Wiest, Roland; Pollo, Claudio; Steimer, Andreas; Gast, Heidemarie

    2016-09-01

    To show that time-irreversible EEG signals recorded with intracranial electrodes during seizures can serve as markers of the epileptogenic zone. We use the recently developed method of mapping time series into directed horizontal graphs (dHVG). Each node of the dHVG represents a time point in the original intracranial EEG (iEEG) signal. Statistically significant differences between the distributions of the nodes' number of input and output connections are used to detect time-irreversible iEEG signals. In 31 of 32 seizure recordings we found time-irreversible iEEG signals. The maximally time-irreversible signals always occurred during seizures, with highest probability in the middle of the first seizure half. These signals spanned a large range of frequencies and amplitudes but were all characterized by saw-tooth like shaped components. Brain regions removed from patients who became post-surgically seizure-free generated significantly larger time-irreversibilities than regions removed from patients who still had seizures after surgery. Our results corroborate that ictal time-irreversible iEEG signals can indeed serve as markers of the epileptogenic zone and can be efficiently detected and quantified in a time-resolved manner by dHVG based methods. Ictal time-irreversible EEG signals can help to improve pre-surgical evaluation in patients suffering from pharmaco-resistant epilepsies. Copyright © 2016 International Federation of Clinical Neurophysiology. Published by Elsevier Ireland Ltd. All rights reserved.

  14. Irreversible properties of YBCO coated conductors

    International Nuclear Information System (INIS)

    Vostner, A.

    2001-02-01

    Over the past few years substantial efforts were made to optimize the fabrication techniques of various high temperature superconductors for commercial applications. In addition to Bi-2223 tapes, Y-123 coated conductors have the potential for large-scale production and are considered as the second generation of superconducting 'wires' for high current applications. This work reports on magnetic and transport current investigations of Y-123 thick films deposited on either single crystalline substrates by liquid phase epitaxy (LPE) or on metallic substrates by pulsed laser deposition (PLD). At the beginning, a short introduction of the general idea of a coated conductor and of the different production techniques is presented, followed by a description of the different experimental set-ups and the evaluation methods. The main part starts with the results obtained from SQUID magnetometry and ac-susceptibility measurements including the transition temperatures T c , the field dependence of the magnetic critical current densities and the irreversibility lines. In addition, some issues concerning the granular structure and the inter- and intragranular current distribution of the superconducting films are discussed. The investigations by transport currents are focused on the behavior of the application relevant irreversible parameters. These are the angular and the field dependence of the critical transport current densities at 77 and 60 K, as well as the temperature dependence of the irreversibility fields up to 6 T. To gain more insight into the defect structure of the films, neutron irradiation studies were performed on some samples. The introduction of these artificial pinning centers causes large enhancements of the magnetic J c in LPE specimens for the field parallel to the c-axis (H//c) at higher temperatures and magnetic fields. The granular structure of the samples does not change up to the highest neutron fluences. However, the enhancements of the transport J c

  15. Irreversibility analysis in the process of solar distillation

    International Nuclear Information System (INIS)

    Chávez, S; Terres, H; Lizardi, A; López, R; Lara, A

    2017-01-01

    In this work an irreversibility analysis for the thermal process of solar distillation of three different substances is presented, for which it employs a solar still of a slope where three experimental tests with 5.5 L of brine, river water and MgCl 2 were performed. Temperature data principally in the glass cover, absorber plate, fluid, environment and the incident solar radiation on the device were obtained. With measurements of temperature, solar radiation and exergetic balance, irreversibilities are found on the device. The results show that the highest values of irreversibilities are concentrated in the absorber plate with an average of 321 W, 342 W and 276 W, followed by the cover glass with an average of 75.8 W, 80.4 W and 86.7 W and finally the fluid with 15.3 W, 15.9 W and 16 W, for 5.5 L of brine, river water and MgCl 2 . (paper)

  16. Kinetics based reaction optimization of enzyme catalysed reduction of formaldehyde to methanol with synchronous cofactor regeneration

    DEFF Research Database (Denmark)

    Marpani, Fauziah Binti; Sárossy, Zsuzsa; Pinelo, Manuel

    2017-01-01

    regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor...... regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization...... experiments were conducted to verify the kinetically modelled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes...

  17. Performance of an irreversible quantum Ericsson cooler at low temperature limit

    International Nuclear Information System (INIS)

    Wu Feng; Chen Lingen; Wu Shuang; Sun Fengrui

    2006-01-01

    The purpose of this paper is to investigate the effect of quantum properties of the working medium on the performance of an irreversible quantum Ericsson cooler with spin-1/2. The cooler is studied with the losses of heat resistance, heat leakage and internal irreversibility. The optimal relationship between the dimensionless cooling load R * versus the coefficient of performance ε for the irreversible quantum Ericsson cooler is derived. In particular, the performance characteristics of the cooler at the low temperature limit are discussed

  18. Conversion of Cassava Starch to Produce Glucose and Fructose by Enzymatic Process Using Microwave Heating

    Directory of Open Access Journals (Sweden)

    Sumardiono Siswo

    2018-01-01

    Full Text Available In this study, variation of glycosidase enzyme concentration and saccharification time on enzymatic hydrolysis using microwave have been investigated. Concentration and kinetic parameters rate of glucose and fructose were analyzed. Cassava starch was liquefied and gelatinized by microwave at 80°C. The gelatinized starch was saccharified at 60°C using (0.2;0.4;0.6;0.8;1% (w/v glycosidase enzyme for 24, 48 and 72 hours. The glucose which has been saccharified with 1% glycosidase enzyme for 72 hours gave highest conversion 66.23 %. The optimization process by multilevel reaction gave the highest conversion at enzyme concentrations 0.88 %and saccharification time 29 hours that 68.82%. The highest conversion of glucose was isomerized to fructose. The fructose which has been isomerized for 180 minutes gave highest conversion 20.05 %. The kinetics enzymatic reaction was approached and determined by Michaelis - Menten equation, Km and Vmax of reaction for glucose 22.94 g/L; 2.70 g/L hours and for fructose 3.39 g/L; 0.38 g/L. min respectively.

  19. Kinetic study of batch and fed-batch enzymatic saccharification of pretreated substrate and subsequent fermentation to ethanol

    Directory of Open Access Journals (Sweden)

    Gupta Rishi

    2012-03-01

    Full Text Available Abstract Background Enzymatic hydrolysis, the rate limiting step in the process development for biofuel, is always hampered by its low sugar concentration. High solid enzymatic saccharification could solve this problem but has several other drawbacks such as low rate of reaction. In the present study we have attempted to enhance the concentration of sugars in enzymatic hydrolysate of delignified Prosopis juliflora, using a fed-batch enzymatic hydrolysis approach. Results The enzymatic hydrolysis was carried out at elevated solid loading up to 20% (w/v and a comparison kinetics of batch and fed-batch enzymatic hydrolysis was carried out using kinetic regimes. Under batch mode, the actual sugar concentration values at 20% initial substrate consistency were found deviated from the predicted values and the maximum sugar concentration obtained was 80.78 g/L. Fed-batch strategy was implemented to enhance the final sugar concentration to 127 g/L. The batch and fed-batch enzymatic hydrolysates were fermented with Saccharomyces cerevisiae and ethanol production of 34.78 g/L and 52.83 g/L, respectively, were achieved. Furthermore, model simulations showed that higher insoluble solids in the feed resulted in both smaller reactor volume and shorter residence time. Conclusion Fed-batch enzymatic hydrolysis is an efficient procedure for enhancing the sugar concentration in the hydrolysate. Restricting the process to suitable kinetic regimes could result in higher conversion rates.

  20. Kinetic study of batch and fed-batch enzymatic saccharification of pretreated substrate and subsequent fermentation to ethanol

    Science.gov (United States)

    2012-01-01

    Background Enzymatic hydrolysis, the rate limiting step in the process development for biofuel, is always hampered by its low sugar concentration. High solid enzymatic saccharification could solve this problem but has several other drawbacks such as low rate of reaction. In the present study we have attempted to enhance the concentration of sugars in enzymatic hydrolysate of delignified Prosopis juliflora, using a fed-batch enzymatic hydrolysis approach. Results The enzymatic hydrolysis was carried out at elevated solid loading up to 20% (w/v) and a comparison kinetics of batch and fed-batch enzymatic hydrolysis was carried out using kinetic regimes. Under batch mode, the actual sugar concentration values at 20% initial substrate consistency were found deviated from the predicted values and the maximum sugar concentration obtained was 80.78 g/L. Fed-batch strategy was implemented to enhance the final sugar concentration to 127 g/L. The batch and fed-batch enzymatic hydrolysates were fermented with Saccharomyces cerevisiae and ethanol production of 34.78 g/L and 52.83 g/L, respectively, were achieved. Furthermore, model simulations showed that higher insoluble solids in the feed resulted in both smaller reactor volume and shorter residence time. Conclusion Fed-batch enzymatic hydrolysis is an efficient procedure for enhancing the sugar concentration in the hydrolysate. Restricting the process to suitable kinetic regimes could result in higher conversion rates. PMID:22433563

  1. Internet Databases of the Properties, Enzymatic Reactions, and Metabolism of Small Molecules—Search Options and Applications in Food Science

    Directory of Open Access Journals (Sweden)

    Piotr Minkiewicz

    2016-12-01

    Full Text Available Internet databases of small molecules, their enzymatic reactions, and metabolism have emerged as useful tools in food science. Database searching is also introduced as part of chemistry or enzymology courses for food technology students. Such resources support the search for information about single compounds and facilitate the introduction of secondary analyses of large datasets. Information can be retrieved from databases by searching for the compound name or structure, annotating with the help of chemical codes or drawn using molecule editing software. Data mining options may be enhanced by navigating through a network of links and cross-links between databases. Exemplary databases reviewed in this article belong to two classes: tools concerning small molecules (including general and specialized databases annotating food components and tools annotating enzymes and metabolism. Some problems associated with database application are also discussed. Data summarized in computer databases may be used for calculation of daily intake of bioactive compounds, prediction of metabolism of food components, and their biological activity as well as for prediction of interactions between food component and drugs.

  2. Efficient sugar release by acetic acid ethanol-based organosolv pretreatment and enzymatic saccharification.

    Science.gov (United States)

    Zhang, Hongdan; Wu, Shubin

    2014-12-03

    Acetic acid ethanol-based organosolv pretreatment of sugar cane bagasse was performed to enhance enzymatic hydrolysis. The effect of different parameters (including temperature, reaction time, solvent concentration, and acid catalyst dose) on pretreatment prehydrolyzate and subsequent enzymatic digestibility was determined. During the pretreatment process, 11.83 g of xylose based on 100 g of raw material could be obtained. After the ethanol-based pretreatment, the enzymatic hydrolysis was enhanced and the highest glucose yield of 40.99 g based on 100 g of raw material could be obtained, representing 93.8% of glucose in sugar cane bagasse. The maximum total sugar yields occurred at 190 °C, 45 min, 60:40 ethanol/water, and 5% dosage of acetic acid, reaching 58.36 g (including 17.69 g of xylose and 40.67 g of glucose) based on 100 g of raw material, representing 85.4% of total sugars in raw material. Furthermore, characterization of the pretreated sugar cane bagasse using X-ray diffraction and scanning electron microscopy analyses were also developed. The results suggested that ethanol-based organosolv pretreatment could enhance enzymatic digestibilities because of the delignification and removal of xylan.

  3. Distribution, industrial applications, and enzymatic synthesis of D-amino acids.

    Science.gov (United States)

    Gao, Xiuzhen; Ma, Qinyuan; Zhu, Hailiang

    2015-04-01

    D-Amino acids exist widely in microbes, plants, animals, and food and can be applied in pharmaceutical, food, and cosmetics. Because of their widespread applications in industry, D-amino acids have recently received more and more attention. Enzymes including D-hydantoinase, N-acyl-D-amino acid amidohydrolase, D-amino acid amidase, D-aminopeptidase, D-peptidase, L-amino acid oxidase, D-amino acid aminotransferase, and D-amino acid dehydrogenase can be used for D-amino acids synthesis by kinetic resolution or asymmetric amination. In this review, the distribution, industrial applications, and enzymatic synthesis methods are summarized. And, among all the current enzymatic methods, D-amino acid dehydrogenase method not only produces D-amino acid by a one-step reaction but also takes environment and atom economics into consideration; therefore, it is deserved to be paid more attention.

  4. Enzymatic biodiesel synthesis. Key factors affecting efficiency of the process

    Energy Technology Data Exchange (ETDEWEB)

    Szczesna Antczak, Miroslawa; Kubiak, Aneta; Antczak, Tadeusz; Bielecki, Stanislaw [Institute of Technical Biochemistry, Faculty of Biotechnology and Food Sciences, Technical University of Lodz, Stefanowskiego 4/10, 90-924 Lodz (Poland)

    2009-05-15

    Chemical processes of biodiesel production are energy-consuming and generate undesirable by-products such as soaps and polymeric pigments that retard separation of pure methyl or ethyl esters of fatty acids from glycerol and di- and monoacylglycerols. Enzymatic, lipase-catalyzed biodiesel synthesis has no such drawbacks. Comprehension of the latter process and an appreciable progress in production of robust preparations of lipases may soon result in the replacement of chemical catalysts with enzymes in biodiesel synthesis. Engineering of enzymatic biodiesel synthesis processes requires optimization of such factors as: molar ratio of substrates (triacylglycerols: alcohol), temperature, type of organic solvent (if any) and water activity. All of them are correlated with properties of lipase preparation. This paper reports on the interplay between the crucial parameters of the lipase-catalyzed reactions carried out in non-aqueous systems and the yield of biodiesel synthesis. (author)

  5. Influence of enzymatic reactions on the electrochemical behavior of EN X2CrNiMo17-11-2 (AISI 316L) stainless steel in bio-corrosion: role of interfacial processes on the modification of the passive layer

    International Nuclear Information System (INIS)

    Landoulsi, J.

    2008-01-01

    The outstanding corrosion behavior of stainless steels (SS) results from the presence of thin oxide layer (some nanometers). In non sterile aqueous media, stainless steels may exhibit a non stable behavior resulting from interactions between microbial species and passive film. In fact, microorganisms can be deeply involved in the corrosion processes usually reported as Microbial Influenced Corrosion (MIC). They can induce the initiation or the acceleration of this phenomenon and they do so when organized in bio-films. From the electrochemical point of view, stainless steels showed an increase of the free corrosion potential (Ecorr) attributed to the bio-film settlement. The Eco' ennoblement was broadly reported in seawater and seems to be confirmed in fresh water according to recent findings. A considerable progress in the comprehension of MIC processes was related to the role of extracellular species, essentially enzymes. Many enzymatic reactions occurring in bio-films consist on using oxygen as electron acceptor to generate hydrogen peroxide and related species. The aim of this work is to understand the mechanisms involved in the electrochemical behavior of stainless steel according to an enzymatic approach in medium simulating fresh water. To this end, glucose oxidase was chosen to globalize aerobic activities of bio-films. Electrochemical measurements in situ and surface analysis allow the comprehension of the role and the nature of interfacial processes. Surface characterization was performed with the help of a new quantitative utilization of XPS analysis and AFM. Results show a significant evolution in term of morphology (surface organization), (ii) chemical composition (passive layer, adsorbed organic species) and (iii) chemical reaction (oxidation, dissolution, effect of enzyme). Finally, a new enzymatic system is proposed to mimic specific physicochemical conditions at the SS / bio-film interface, in particular enzymatic generation of oxidant species in

  6. Enzymatic Synthesis of Highly Fluorescent 8-Azapurine Ribosides Using a Purine Nucleoside Phosphorylase Reverse Reaction: Variable Ribosylation Sites

    Directory of Open Access Journals (Sweden)

    Goran Mikleušević

    2013-10-01

    Full Text Available Various forms of purine-nucleoside phosphorylase (PNP were used as catalysts of enzymatic ribosylation of selected fluorescent 8-azapurines. It was found that the recombinant calf PNP catalyzes ribosylation of 2,6-diamino-8-azapurine in a phosphate-free medium, with ribose-1-phosphate as ribose donor, but the ribosylation site is predominantly N7 and N8, with the proportion of N8/N7 ribosylated products markedly dependent on the reaction conditions. Both products are fluorescent. Application of the E. coli PNP gave a mixture of N8 and N9-substituted ribosides. Fluorescence of the ribosylated 2,6-diamino-8-azapurine has been briefly characterized. The highest quantum yield, ~0.9, was obtained for N9-β-d-riboside (λmax 365 nm, while for N8-β-d-riboside, emitting at ~430 nm, the fluorescence quantum yield was found to be close to 0.4. Ribosylation of 8-azaguanine with calf PNP as a catalyst goes exclusively to N9. By contrast, the E. coli PNP ribosylates 8-azaGua predominantly at N9, with minor, but highly fluorescent products ribosylated at N8/N7.

  7. The thermomechanics of nonlinear irreversible behaviors an introduction

    CERN Document Server

    Maugin, Gérard A

    1999-01-01

    In this invaluable book, macroscopic irreversible thermodynamics is presented in its realm and its splendor by appealing to the notion of internal variables of state. This applies to both fluids and solids with or without microstructures of mechanical or electromagnetic origin. This unmatched richness of essentially nonlinear behaviors is the result of the use of modern mathematical techniques such as convex analysis in a clear-cut framework which allows one to put under the umbrella of "irreversible thermodynamics" behaviors which until now have been commonly considered either not easily cove

  8. Directing filtration to narrow molecular weight distribution of oligodextran in an enzymatic membrane reactor

    DEFF Research Database (Denmark)

    Su, Ziran; Luo, Jianquan; Pinelo, Manuel

    2018-01-01

    ) should be minimized to reduce accumulation of large oligodextran molecules on the membrane surface, which might diffuse through the membrane and thus broaden the Mw distribution of the products in the permeate. Both dextranase and dextran caused membrane irreversible fouling. The fouling caused...... product, hypersaline wastewater discharge and potential safety hazards. In this work, a novel enzymatic membrane reactor (EMR) system to produce oligodextran is proposed, whereby in-situ product recovery can be manipulated to control the Mw distribution of the resulting products. Results showed...... that the membrane material played an important role in the permeate flux and transmission of oligodextran. Among the tested membranes, a 20kDa polyethersulfone (PES) membrane was found to be optimal for building up the EMR, as it successfully controlled the oligodextran Mw within the desired range with a relatively...

  9. Time in Science: Reversibility vs. Irreversibility

    Science.gov (United States)

    Pomeau, Yves

    To discuss properly the question of irreversibility one needs to make a careful distinction between reversibility of the equations of motion and the choice of the initial conditions. This is also relevant for the rather confuse philosophy of the wave packet reduction in quantum mechanics. The explanation of this reduction requires also to make precise assumptions on what initial data are accessible in our world. Finally I discuss how a given (and long) time record can be shown in an objective way to record an irreversible or reversible process. Or: can a direction of time be derived from its analysis? This leads quite naturally to examine if there is a possible spontaneous breaking of the time reversal symmetry in many body systems, a symmetry breaking that would be put in evidence objectively by looking at certain specific time correlations.

  10. THE KINETICS OF THE REACTIONS CATALYZED BY AN ENZYMATIC PREPARATION PRODUCED BY A BACILLUS LICHENIFORMIS STRAIN

    Directory of Open Access Journals (Sweden)

    MONICA DRAGOMIRESCU

    2007-05-01

    Full Text Available Robust immobilization techniques that preserve the activity of biomolecules have manypotential applications. In recent years, a number of new bioimobilisation methods in solgel-derived materials were reported. The interactions between the biomolecule and theinorganic material determine the degree to which the biomolecule retains its nativeproperties. The newer technological developments in the field of immobilizedbiocatalysts can offer the possibility of a wider and more economical exploitation ofbiocatalysts in biological applications, food and feed industry, medicine, and in thedevelopment of bioprocess monitoring devices, like the biosensors.The aim of this study was to obtain immobilized enzymatic preparations by methodswhich affect enzyme conformations and kinetic parameters as less as possible. Weimmobilized the enzymatic preparation with protease activity produced by a Bacilluslicheniformis B 40 local strain by physical bonding on ceramics and entrapment into solgel-derived glasses obtained from tetraethyl orthosilicate (TEOS, deposited in thin layeron a ceramic support (entrapment/deposition. Both physically adsorbed andentrapped/deposited enzymes follow Michaelis-Menten kinetics, similar with the solubleenzyme. In the case of immobilized enzymes, the apparent Michaelis constant, Km, wasgreater than that of the native one, as it was expected. The kinetic parameters indicatethat the enzymatic preparations adsorbed on ceramic support and entrapped/depositedshow less affinity for the substrate, Km being 1.3 and 2.1 times higher than that of thenative enzyme, respectively. The maximum velocity increased also by 3.5 and 7.9 timesrespectively, compared with the free counterpart (according to Lineweaver-Burklinearization.

  11. Modular rate laws for enzymatic reactions: thermodynamics, elasticities and implementation.

    Science.gov (United States)

    Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

    2010-06-15

    Standard rate laws are a key requisite for systematically turning metabolic networks into kinetic models. They should provide simple, general and biochemically plausible formulae for reaction velocities and reaction elasticities. At the same time, they need to respect thermodynamic relations between the kinetic constants and the metabolic fluxes and concentrations. We present a family of reversible rate laws for reactions with arbitrary stoichiometries and various types of regulation, including mass-action, Michaelis-Menten and uni-uni reversible Hill kinetics as special cases. With a thermodynamically safe parameterization of these rate laws, parameter sets obtained by model fitting, sampling or optimization are guaranteed to lead to consistent chemical equilibrium states. A reformulation using saturation values yields simple formulae for rates and elasticities, which can be easily adjusted to the given stationary flux distributions. Furthermore, this formulation highlights the role of chemical potential differences as thermodynamic driving forces. We compare the modular rate laws to the thermodynamic-kinetic modelling formalism and discuss a simplified rate law in which the reaction rate directly depends on the reaction affinity. For automatic handling of modular rate laws, we propose a standard syntax and semantic annotations for the Systems Biology Markup Language. An online tool for inserting the rate laws into SBML models is freely available at www.semanticsbml.org. Supplementary data are available at Bioinformatics online.

  12. Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

    Science.gov (United States)

    Naumov, Sergej; von Sonntag, Clemens

    2011-11-01

    Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

  13. [Response surface method optimize of nano-silica solid dispersion technology assistant enzymatic hydrolysis preparation genistein].

    Science.gov (United States)

    Jin, Xin; Zhang, Zhen-Hai; Zhu, Jing; Sun, E; Yu, Dan-Hong; Chen, Xiao-Yun; Liu, Qi-Yuan; Ning, Qing; Jia, Xiao-Bin

    2012-04-01

    This article reports that nano-silica solid dispersion technology was used to raise genistein efficiency through increasing the enzymatic hydrolysis rate. Firstly, genistin-nano-silica solid dispersion was prepared by solvent method. And differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) were used to verify the formation of solid dispersion, then enzymatic hydrolysis of solid dispersion was done by snailase to get genistein. With the conversion of genistein as criteria, single factor experiments were used to study the different factors affecting enzymatic hydrolysis of genistin and its solid dispersion. And then, response surface method was used to optimize of nano-silica solid dispersion technology assistant enzymatic hydrolysis. The optimum condition to get genistein through enzymatic hydrolysis of genistin-nano-silica solid dispersion was pH 7.1, temperature 52.2 degrees C, enzyme concentration 5.0 mg x mL(-1) and reaction time 7 h. Under this condition, the conversion of genistein was (93.47 +/- 2.40)%. Comparing with that without forming the genistin-nano-silica solid dispersion, the conversion increased 2.62 fold. At the same time, the product of hydrolysis was purified to get pure genistein. The method of enzymatic hydrolysis of genistin-nano-silica solid dispersion by snailase to obtain genistein is simple, efficiency and suitable for the modern scale production.

  14. Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Schuenemann, V. [University of Luebeck, Institute of Physics (Germany); Jung, C. [Max-Delbrueck-Center for Molecular Medicine (Germany); Lendzian, F. [Technical University, PC 14, Max-Volmer Laboratory for Biophysical Chemistry (Germany); Barra, A.-L. [Grenoble High Magnetic Field Laboratory (France); Teschner, T.; Trautwein, A. X. [University of Luebeck, Institute of Physics (Germany)

    2004-12-15

    In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

  15. Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

    International Nuclear Information System (INIS)

    Schuenemann, V.; Jung, C.; Lendzian, F.; Barra, A.-L.; Teschner, T.; Trautwein, A. X.

    2004-01-01

    In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

  16. Enzymatic Hydrolysis of Alkaline Pretreated Coconut Coir

    Directory of Open Access Journals (Sweden)

    Akbarningrum Fatmawati

    2013-06-01

    Full Text Available The purpose of this research is to study the effect of concentration and temperature on the cellulose and lignin content, and the reducing sugars produced in the enzymatic hydrolysis of coconut coir. In this research, the coconut coir is pretreated using 3%, 7%, and 11% NaOH solution at 60oC, 80oC, and 100oC. The pretreated coir were assayed by measuring the amount of cellulose and lignin and then hydrolysed using Celluclast and Novozyme 188 under various temperature (30oC, 40oC, 50oC and pH (3, 4, 5. The hydrolysis results were assayed for the reducing sugar content. The results showed that the alkaline delignification was effective to reduce lignin and to increase the cellulose content of the coir. The best delignification condition was observed at 11% NaOH solution and 100oC which removed 14,53% of lignin and increased the cellulose content up to 50,23%. The best condition of the enzymatic hydrolysis was obtained at 50oC and pH 4 which produced 7,57 gr/L reducing sugar. © 2013 BCREC UNDIP. All rights reservedReceived: 2nd October 2012; Revised: 31st January 2013; Accepted: 6th February 2013[How to Cite: Fatmawati, A., Agustriyanto, R., Liasari, Y. (2013. Enzymatic Hydrolysis of Alkaline Pre-treated Coconut Coir. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 34-39 (doi:10.9767/bcrec.8.1.4048.34-39[Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4048.34-39] | View in  |

  17. Enzymatically interesterified fats based on mutton tallow and walnut oil suitable for cosmetic emulsions.

    Science.gov (United States)

    Kowalska, M; Mendrycka, M; Zbikowska, A; Stawarz, S

    2015-02-01

    Formation of emulsion systems based on interesterified fats was the objective of the study. Enzymatic interesterification was carried out between enzymatic mutton tallow and walnut oil in the proportions 2 : 3 (w/w) to produce fats not available in nature. At the beginning of the interesterification process, the balance between the interesterification and fat hydrolysis was intentionally disturbed by adding more water to the catalyst (Lipozyme IR MR) of the reaction to produce more of the polar fraction monoacylglycerols [MAGs] and diacylglycerols [DAGs]. To obtain a greater quantity of MAGs and DAGs in the reaction environment via hydrolysis, water was added (11, 13, 14, 16 w-%) to the enzymatic preparation. The obtained fats were used to form emulsions. The emulsions were evaluated with respect to sensory and skin moisturizing properties by 83 respondents. Determination of emulsion stability using temperature and centrifugal tests was carried out. Morphology and the type of emulsions were determined. The respondents described the skin to which the emulsions in testing were applied as smooth, pleasant to touch and adequately moisturized. The work has demonstrated that interesterification of a mutton tallow and walnut oil blend resulted in new fats with very interesting characteristics of triacylglycerols that are not present in the environment. The results of the present work indicate the possibility of application of fats with the largest quantity of MAGs and DAGs as a fat base of emulsions in the cosmetic industries. The hypothesis assumed in this work of producing additional quantities of MAGs and DAGs (in the process of enzymatic interesterification) responsible for the stability of the system was confirmed. It should be pointed out that the emulsions based on interesterified fats exhibited a greater level of moisturization of the skin than the emulsions containing non-interesterified fat. Also, in the respondents' opinion, the emulsion containing fat, which

  18. Reaction rate of hydrolysis of iodine

    International Nuclear Information System (INIS)

    Miyake, Yoshikazu; Eguchi, Wataru; Adachi, Motonari

    1979-01-01

    Absorption rates of dilute iodine vapor contained in air by aqueous mixtures of sodium hydroxide and boric acid were measured using a laminar liquid jet column absorber at 298 K. Absorption rates in this system are controlled by a series of complex reactions taking place in the liquid phase. The reaction rate constant of iodine hydrolysis in the aqueous phase was determined from the absorption rates observed under the conditions that the base-catalytic hydrolysis reaction of iodine can be considered to be irreversible and that other reactions can be neglected. The absorption rates calculated theoretically with the rate constant value obtained above were in good accordance with the whole experimental data observed for a wide range of experimental conditions. (author)

  19. Irreversibility and Action of the Heat Conduction Process

    Directory of Open Access Journals (Sweden)

    Yu-Chao Hua

    2018-03-01

    Full Text Available Irreversibility (that is, the “one-sidedness” of time of a physical process can be characterized by using Lyapunov functions in the modern theory of stability. In this theoretical framework, entropy and its production rate have been generally regarded as Lyapunov functions in order to measure the irreversibility of various physical processes. In fact, the Lyapunov function is not always unique. In the represent work, a rigorous proof is given that the entransy and its dissipation rate can also serve as Lyapunov functions associated with the irreversibility of the heat conduction process without the conversion between heat and work. In addition, the variation of the entransy dissipation rate can lead to Fourier’s heat conduction law, while the entropy production rate cannot. This shows that the entransy dissipation rate, rather than the entropy production rate, is the unique action for the heat conduction process, and can be used to establish the finite element method for the approximate solution of heat conduction problems and the optimization of heat transfer processes.

  20. Effect of room temperature ionic liquid structure on the enzymatic acylation of flavonoids

    DEFF Research Database (Denmark)

    Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

    2010-01-01

    Enzymatic acylation reactions of flavonoids (rutin, esculin) with long chain fatty acids (palmitic, oleic acids) were carried out in 14 different ionic liquid media containing a range of cation and anion structures. Classification of RTILs according to flavonoid solubility (using COSMO...... must be struck that maximized flavonoid solubility with minimum negative impact on lipase activity. The process also benefitted from an increased reaction temperature which may have helped to reduced mass transfer limitations. Keywords: Room temperature ionic liquids (RTILs); Biosynthesis; Acylation......; Flavonoids; Lipase; Long chain fatty acids...

  1. Development and Validation of an Enzymatic Method To Determine Stevioside Content from Stevia rebaudiana.

    Science.gov (United States)

    Udompaisarn, Somsiri; Arthan, Dumrongkiet; Somana, Jamorn

    2017-04-19

    An enzymatic method for specific determination of stevioside content was established. Recombinant β-glucosidase BT_3567 (rBT_3567) from Bacteroides thetaiotaomicron HB-13 exhibited selective hydrolysis of stevioside at β-1,2-glycosidic bond to yield rubusoside and glucose. Coupling of this enzyme with glucose oxidase and peroxidase allowed for quantitation of stevioside content in Stevia samples by using a colorimetric-based approach. The series of reactions for stevioside determination can be completed within 1 h at 37 °C. Stevioside determination using the enzymatic assay strongly correlated with results obtained from HPLC quantitation (r 2 = 0.9629, n = 16). The percentages of coefficient variation (CV) of within day (n = 12) and between days (n = 12) assays were lower than 5%, and accuracy ranges were 95-105%. This analysis demonstrates that the enzymatic method developed in this study is specific, easy to perform, accurate, and yields reproducible results.

  2. Immobilization of Lipase using Alginate Hydrogel Beads and Enzymatic Evaluation in Hydrolysis of p-Nitrophenol Butyrate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuang; Shang, Wenting; Yang, Xiaoxi; Zhang, Shujuan; Zhang, Xiaogang; Chen, Jiawei [Renmin Univ. of China, Beijing (China)

    2013-09-15

    The immobilization of enzyme is one of the key issues both in the field of enzymatic research and industrialization. In this work, we reported a facile method to immobilize Candida Antarctica lipase B (CALB) in alginate carrier. In the presence of calcium cation, the enzyme-alginate suspension could be cross-linked to form beads with porous structure at room temperature, and the enzyme CALB was dispersed in the beads. Activity of the enzyme-alginate composite was verified by enzymatic hydrolysis reaction of p-nitrophenol butyrate in aqueous phase. The effects of reaction parameters such as temperature, pH, embedding and lyophilized time on the reactive behavior were discussed. Reuse cycle experiments for the hydrolysis of p-nitrophenol butyrate demonstrated that activity of the enzyme-alginate composite was maintained without marked deactivation up to 6 repeated cycles.

  3. Multiscale Analysis of Time Irreversibility Based on Phase-Space Reconstruction and Horizontal Visibility Graph Approach

    Science.gov (United States)

    Zhang, Yongping; Shang, Pengjian; Xiong, Hui; Xia, Jianan

    Time irreversibility is an important property of nonequilibrium dynamic systems. A visibility graph approach was recently proposed, and this approach is generally effective to measure time irreversibility of time series. However, its result may be unreliable when dealing with high-dimensional systems. In this work, we consider the joint concept of time irreversibility and adopt the phase-space reconstruction technique to improve this visibility graph approach. Compared with the previous approach, the improved approach gives a more accurate estimate for the irreversibility of time series, and is more effective to distinguish irreversible and reversible stochastic processes. We also use this approach to extract the multiscale irreversibility to account for the multiple inherent dynamics of time series. Finally, we apply the approach to detect the multiscale irreversibility of financial time series, and succeed to distinguish the time of financial crisis and the plateau. In addition, Asian stock indexes away from other indexes are clearly visible in higher time scales. Simulations and real data support the effectiveness of the improved approach when detecting time irreversibility.

  4. Method and device for thermal control of biological and chemical reactions using magnetic particles or magnetic beads and variable magnetic fields

    OpenAIRE

    Zilch, C.; Gerdes, W.; Bauer, J.; Holschuh, K.

    2009-01-01

    The invention relates to a method for the thermal control of at least one temperature-dependent enzymatic reaction in the presence of magnetic particles, particularly nanoparticles, or magnetic beads, in vitro by heating the magnetic beads or magnetic particles to at least one defined target temperature using alternating magnetic fields. The thermally controllable enzymatic reaction carried out with the method according to the invention is preferably a PCR reaction or another reaction for elo...

  5. Antibiotics are not useful to reduce pain associated with irreversible pulpitis.

    Science.gov (United States)

    Hoskin, Eileen; Veitz-Keenan, Analia

    2016-09-01

    Data sourcesCochrane Oral Health Group's Trials Register, the Cochrane Central Register of Controlled Trials, MEDLINE, EMBASE, Clinical Trials.gov and the WHO International Clinical Trials Registry Platform. There were no language restrictions.Study selectionRandomised controlled trials which compared the relief of pain with systemic antibiotics and analgesics against placebo and analgesics in the preoperative phase of irreversible pulpitis. The primary interest was pain control with an antibiotic or without one in the presence of analgesics. The secondary outcomes were type, dose and frequency of medication for pain relief and any adverse effects related to hypersensitivity or other reactions to either the antibiotic or analgesics.Data extraction and synthesisTwo authors independently assessed the results of the searches. Data extraction and risk bias assessment were also carried out independently. A third reviewer settled any disagreement on inclusion. Since only one study was included a meta-analysis could not be performed.ResultsOnly one double blind randomised clinical trial involving 40 participants with a diagnosis of irreversible pulpitis in one of their teeth was included in this review. This was a low risk, well-constructed double blind study. Half of the participants were treated with penicillin 500 mg, the other with a placebo every six hours over a seven- day period. In addition, all the participants were instructed to initially take one tablet of ibuprofen every 4-6 hours as needed and to take acetaminophen with codeine (two tablets every 4-6 hours) only if the ibuprofen did not relieve the pain.There was no significant difference in the mean total number of ibuprofen tablets over the study period; 9.2(standard deviation (SD) 6.02) in the penicillin group versus, 9.6 (SD 6.34) in the placebo group; mean difference -0.40 (95% CI -4.23 to 3.43); P value = 0.84.The mean total number of Tylenol tablets, 6.9 (SD 6.87), used in the penicillin group versus 4

  6. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Rueping, Magnus

    2017-01-01

    . By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high

  7. A kinetic equation for irreversible aggregation

    International Nuclear Information System (INIS)

    Zanette, D.H.

    1990-09-01

    We introduce a kinetic equation for describing irreversible aggregation in the ballistic regime, including velocity distributions. The associated evolution for the macroscopic quantities is studied, and the general solution for Maxwell interaction models is obtained in the Fourier representation. (author). 23 refs

  8. Anisotropic shift of the irreversibility line by neutron irradiation

    International Nuclear Information System (INIS)

    Sauerzopf, F.M.; Wiesinger, H.P.; Weber, H.W.; Crabtree, G.W.; Frischherz, M.C.; Kirk, M.A.

    1991-09-01

    The irreversibility line of high-T c superconductors is shifted considerably by irradiating the material with fast neutrons. The anisotropic and non-monotonous shift is qualitatively explained by a simple model based on an interaction between three pinning mechanisms, the intrinsic pinning by the ab-planes, the weak pinning by the pre-irradiation defect structure, and strong pinning by neutron induced defect cascades. A correlation between the cascade density and the position of the irreversibility line is observed

  9. Optimization of Pretreatment and Enzymatic Saccharification of Cogon Grass Prior Ethanol Production

    OpenAIRE

    Jhalique Jane R. Fojas; Ernesto J. Del Rosario

    2013-01-01

    The dilute acid pretreatment and enzymatic saccharification of lignocellulosic substrate, cogon grass (Imperata cylindrical, L.) was optimized prior ethanol fermentation using simultaneous saccharification and fermentation (SSF) method. The optimum pretreatment conditions, temperature, sulfuric acid concentration, and reaction time were evaluated by determining the maximum sugar yield at constant enzyme loading. Cogon grass, at 10% w/v substrate loading, has optimum pretr...

  10. Measures of thermodynamic irreversibility in deterministic and stochastic dynamics

    International Nuclear Information System (INIS)

    Ford, Ian J

    2015-01-01

    It is generally observed that if a dynamical system is sufficiently complex, then as time progresses it will share out energy and other properties amongst its component parts to eliminate any initial imbalances, retaining only fluctuations. This is known as energy dissipation and it is closely associated with the concept of thermodynamic irreversibility, measured by the increase in entropy according to the second law. It is of interest to quantify such behaviour from a dynamical rather than a thermodynamic perspective and to this end stochastic entropy production and the time-integrated dissipation function have been introduced as analogous measures of irreversibility, principally for stochastic and deterministic dynamics, respectively. We seek to compare these measures. First we modify the dissipation function to allow it to measure irreversibility in situations where the initial probability density function (pdf) of the system is asymmetric as well as symmetric in velocity. We propose that it tests for failure of what we call the obversibility of the system, to be contrasted with reversibility, the failure of which is assessed by stochastic entropy production. We note that the essential difference between stochastic entropy production and the time-integrated modified dissipation function lies in the sequence of procedures undertaken in the associated tests of irreversibility. We argue that an assumed symmetry of the initial pdf with respect to velocity inversion (within a framework of deterministic dynamics) can be incompatible with the Past Hypothesis, according to which there should be a statistical distinction between the behaviour of certain properties of an isolated system as it evolves into the far future and the remote past. Imposing symmetry on a velocity distribution is acceptable for many applications of statistical physics, but can introduce difficulties when discussing irreversible behaviour. (paper)

  11. On the Effect of Microwave Energy on Lipase-Catalyzed Polycondensation Reactions

    Directory of Open Access Journals (Sweden)

    Alessandro Pellis

    2016-09-01

    Full Text Available Microwave energy (MWe is, nowadays, widely used as a clean synthesis tool to improve several chemical reactions, such as drug molecule synthesis, carbohydrate conversion and biomass pyrolysis. On the other hand, its exploitation in enzymatic reactions has only been fleetingly investigated and, hence, further study of MWe is required to reach a precise understanding of its potential in this field. Starting from the authors’ experience in clean synthesis and biocatalyzed reactions, this study sheds light on the possibility of using MWe for enhancing enzyme-catalyzed polycondensation reactions and pre-polymer formation. Several systems and set ups were investigated involving bulk and organic media (solution phase reactions, different enzymatic preparations and various starting bio-based monomers. Results show that MWe enables the biocatalyzed synthesis of polyesters and pre-polymers in a similar way to that reported using conventional heating with an oil bath, but in a few cases, notably bulk phase polycondensations under intense microwave irradiation, MWe leads to a rapid enzyme deactivation.

  12. Real-Time Model Based Process Monitoring of Enzymatic Biodiesel Production

    DEFF Research Database (Denmark)

    Price, Jason Anthony; Nordblad, Mathias; Woodley, John

    2015-01-01

    In this contribution we extend our modelling work on the enzymatic production of biodiesel where we demonstrate the application of a Continuous-Discrete Extended Kalman Filter (a state estimator). The state estimator is used to correct for mismatch between the process data and the process model...... for Fed-batch production of biodiesel. For the three process runs investigated, using a single tuning parameter, qx=2 x 10-2 which represents the uncertainty in the process model, it was possible over the entire course of the reaction to reduce the overall mean and standard deviation of the error between......, there was over a ten-fold decrease in the overall mean error for the state estimator prediction compared with the predictions from the pure model simulations. It is also shown that the state estimator can be used as a tool for detection of outliers in the measurement data. For the enzymatic biodiesel process...

  13. Optimization of enzymatic hydrolysis of guar gum using response surface methodology.

    Science.gov (United States)

    Mudgil, Deepak; Barak, Sheweta; Khatkar, B S

    2014-08-01

    Guar gum is a polysaccharide obtained from guar seed endosperm portion. Enzymatically hydrolyzed guar gum is low in viscosity and has several health benefits as dietary fiber. In this study, response surface methodology was used to determine the optimum conditions for hydrolysis that give minimum viscosity of guar gum. Central composite was employed to investigate the effects of pH (3-7), temperature (20-60 °C), reaction time (1-5 h) and cellulase concentration (0.25-1.25 mg/g) on viscosity during enzymatic hydrolysis of guar (Cyamopsis tetragonolobus) gum. A second order polynomial model was developed for viscosity using regression analysis. Results revealed statistical significance of model as evidenced from high value of coefficient of determination (R(2) = 0.9472) and P < 0.05. Viscosity was primarily affected by cellulase concentration, pH and hydrolysis time. Maximum viscosity reduction was obtained when pH, temperature, hydrolysis time and cellulase concentration were 6, 50 °C, 4 h and 1.00 mg/g, respectively. The study is important in optimizing the enzymatic process for hydrolysis of guar gum as potential source of soluble dietary fiber for human health benefits.

  14. Fundamental economic irreversibilities influence policies for enhancing international forest phytosanitary security

    Science.gov (United States)

    Thomas P. Holmes; Will Allen; Robert G. Haight; E. Carina H. Keskitalo; Mariella Marzano; Maria Pettersson; Christopher P. Quine; E. R. Langer

    2017-01-01

    National and international efforts to manage forest biosecurity create tension between opposing sources of ecological and economic irreversibility. Phytosanitary policies designed to protect national borders from biological invasions incur sunk costs deriving from economic and political irreversibilities that incentivizes wait-and-see decision-making. However, the...

  15. The use of TiO2 nanoparticles to reduce refrigerator ir-reversibility

    International Nuclear Information System (INIS)

    Padmanabhan, Venkataramana Murthy V.; Palanisamy, Senthilkumar

    2012-01-01

    Highlights: ► COP of hydrocarbons mixture VCRSs increases less when compared to R134a. ► Compressor ir-reversibility of VCRSs decreases by 33% (R134a), 14% (R436A and R436B). ► Total ir-reversibility of selected VCRSs decreases. ► Exergy efficiency of R134a is exceptionally low at lower reference temperature. ► Exergy efficiency of selected VCRSs increases. - Abstract: The ir-reversibility at the process of a vapour-compression refrigeration system (VCRS) with nanoparticles in the working fluid was investigated experimentally. Mineral oil (MO) with 0.1 g L −1 TiO 2 nanoparticles mixture were used as the lubricant instead of Polyol-ester (POE) oil in the R134a, R436A (R290/R600a-56/44-wt.%) and R436B (R290/R600a-52/48-wt.%)VCRSs. The VCRS ir-reversibility at the process with the nanoparticles was investigated using second law of thermodynamics. The results indicate that R134a, R436A and R436B and MO with TiO 2 nanoparticles work normally and safely in the VCRS. The VCRSs total ir-reversibility (529, 588 and 570 W) at different process was better than the R134a, R436A and R436B and POE oil system (777, 697 and 683 W). The same tests with Al 2 O 3 nanoparticles showed that the different nanoparticles properties have little effect on the VCRS ir-reversibility. Thus, TiO 2 nanoparticles can be used in VCRS with reciprocating compressor to considerably reduce ir-reversibility at the process.

  16. SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis

    Science.gov (United States)

    Ohashi, Masao; Liu, Fang; Hai, Yang; Chen, Mengbin; Tang, Man-Cheng; Yang, Zhongyue; Sato, Michio; Watanabe, Kenji; Houk, K. N.; Tang, Yi

    2017-09-01

    Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon-carbon bonds. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels-Alder reaction, and the Cope and the Claisen rearrangements) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels-Alder and hetero-Diels-Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin. Combined in vitro enzymatic characterization and computational studies provide insight into how LepI regulates these bifurcating biosynthetic reaction pathways by using SAM as the cofactor. These pathways converge to the desired biosynthetic end product via the (SAM-dependent) retro-Claisen rearrangement catalysed by LepI. We expect that more pericyclic biosynthetic enzymatic transformations remain to be discovered in naturally occurring enzyme ‘toolboxes’. The new role of the versatile cofactor SAM is likely to be found in other examples of enzyme catalysis.

  17. Role of conformational dynamics in kinetics of an enzymatic cycle in a nonequilibrium steady state

    Science.gov (United States)

    Min, Wei; Xie, X. Sunney; Bagchi, Biman

    2009-08-01

    Enzyme is a dynamic entity with diverse time scales, ranging from picoseconds to seconds or even longer. Here we develop a rate theory for enzyme catalysis that includes conformational dynamics as cycling on a two-dimensional (2D) reaction free energy surface involving an intrinsic reaction coordinate (X) and an enzyme conformational coordinate (Q). The validity of Michaelis-Menten (MM) equation, i.e., substrate concentration dependence of enzymatic velocity, is examined under a nonequilibrium steady state. Under certain conditions, the classic MM equation holds but with generalized microscopic interpretations of kinetic parameters. However, under other conditions, our rate theory predicts either positive (sigmoidal-like) or negative (biphasic-like) kinetic cooperativity due to the modified effective 2D reaction pathway on X-Q surface, which can explain non-MM dependence previously observed on many monomeric enzymes that involve slow or hysteretic conformational transitions. Furthermore, we find that a slow conformational relaxation during product release could retain the enzyme in a favorable configuration, such that enzymatic turnover is dynamically accelerated at high substrate concentrations. The effect of such conformation retainment in a nonequilibrium steady state is evaluated.

  18. Direct electron transfer based enzymatic fuel cells

    International Nuclear Information System (INIS)

    Falk, Magnus; Blum, Zoltan; Shleev, Sergey

    2012-01-01

    In this mini-review we briefly describe some historical developments made in the field of enzymatic fuel cells (FCs), discussing important design considerations taken when constructing mediator-, cofactor-, and membrane-less biological FCs (BFCs). Since the topic is rather extensive, only BFCs utilizing direct electron transfer (DET) reactions on both the anodic and cathodic sides are considered. Moreover, the performance of mostly glucose/oxygen biodevices is analyzed and compared. We also present some unpublished results on mediator-, cofactor-, and membrane-less glucose/oxygen BFCs recently designed in our group and tested in different human physiological fluids, such as blood, plasma, saliva, and tears. Finally, further perspectives for BFC applications are highlighted.

  19. Kinetic modelling of enzymatic starch hydrolysis

    NARCIS (Netherlands)

    Bednarska, K.A.

    2015-01-01

    Kinetic modelling of enzymatic starch hydrolysis – a summary

    K.A. Bednarska

    The dissertation entitled ‘Kinetic modelling of enzymatic starch hydrolysis’ describes the enzymatic hydrolysis and kinetic modelling of liquefaction and saccharification of wheat starch.

  20. Irreversible Local Markov Chains with Rapid Convergence towards Equilibrium

    Science.gov (United States)

    Kapfer, Sebastian C.; Krauth, Werner

    2017-12-01

    We study the continuous one-dimensional hard-sphere model and present irreversible local Markov chains that mix on faster time scales than the reversible heat bath or Metropolis algorithms. The mixing time scales appear to fall into two distinct universality classes, both faster than for reversible local Markov chains. The event-chain algorithm, the infinitesimal limit of one of these Markov chains, belongs to the class presenting the fastest decay. For the lattice-gas limit of the hard-sphere model, reversible local Markov chains correspond to the symmetric simple exclusion process (SEP) with periodic boundary conditions. The two universality classes for irreversible Markov chains are realized by the totally asymmetric SEP (TASEP), and by a faster variant (lifted TASEP) that we propose here. We discuss how our irreversible hard-sphere Markov chains generalize to arbitrary repulsive pair interactions and carry over to higher dimensions through the concept of lifted Markov chains and the recently introduced factorized Metropolis acceptance rule.

  1. A Fingerprint Encryption Scheme Based on Irreversible Function and Secure Authentication

    Directory of Open Access Journals (Sweden)

    Yijun Yang

    2015-01-01

    Full Text Available A fingerprint encryption scheme based on irreversible function has been designed in this paper. Since the fingerprint template includes almost the entire information of users’ fingerprints, the personal authentication can be determined only by the fingerprint features. This paper proposes an irreversible transforming function (using the improved SHA1 algorithm to transform the original minutiae which are extracted from the thinned fingerprint image. Then, Chinese remainder theorem is used to obtain the biokey from the integration of the transformed minutiae and the private key. The result shows that the scheme has better performance on security and efficiency comparing with other irreversible function schemes.

  2. Interactive forces between lignin and cellulase as determined by atomic force microscopy

    OpenAIRE

    Qin, Chengrong; Clarke, Kimberley; Li, Kecheng

    2014-01-01

    Background Lignin is a complex polymer which inhibits the enzymatic conversion of cellulose to glucose in lignocellulose biomass for biofuel production. Cellulase enzymes irreversibly bind to lignin, deactivating the enzyme and lowering the overall activity of the hydrolyzing reaction solution. Within this study, atomic force microscopy (AFM) is used to compare the adhesion forces between cellulase and lignin with the forces between cellulase and cellulose, and to study the moiety groups invo...

  3. An investigation of nitrile transforming enzymes in the chemo-enzymatic synthesis of the taxol sidechain.

    Science.gov (United States)

    Wilding, Birgit; Veselá, Alicja B; Perry, Justin J B; Black, Gary W; Zhang, Meng; Martínková, Ludmila; Klempier, Norbert

    2015-07-28

    Paclitaxel (taxol) is an antimicrotubule agent widely used in the treatment of cancer. Taxol is prepared in a semisynthetic route by coupling the N-benzoyl-(2R,3S)-3-phenylisoserine sidechain to the baccatin III core structure. Precursors of the taxol sidechain have previously been prepared in chemoenzymatic approaches using acylases, lipases, and reductases, mostly featuring the enantioselective, enzymatic step early in the reaction pathway. Here, nitrile hydrolysing enzymes, namely nitrile hydratases and nitrilases, are investigated for the enzymatic hydrolysis of two different sidechain precursors. Both sidechain precursors, an openchain α-hydroxy-β-amino nitrile and a cyanodihydrooxazole, are suitable for coupling to baccatin III directly after the enzymatic step. An extensive set of nitrilases and nitrile hydratases was screened towards their activity and selectivity in the hydrolysis of two taxol sidechain precursors and their epimers. A number of nitrilases and nitrile hydratases converted both sidechain precursors and their epimers.

  4. Optima and bounds for irreversible thermodynamic processes

    International Nuclear Information System (INIS)

    Hoffmann, K.H.

    1990-01-01

    In this paper bounds and optima for irreversible thermodynamic processes and their application in different fields are discussed. The tools of finite time thermodynamics are presented and especially optimal control theory is introduced. These methods are applied to heat engines, including models of the Diesel engine and a light-driven engine. Further bounds for irreversible processes are introduced, discussing work deficiency and its relation to thermodynamic length. Moreover the problem of dissipation in systems composed of several subsystems is studied. Finally, the methods of finite time thermodynamics are applied to thermodynamic processes described on a more microscopic level. The process used as an example is simulated annealing. It is shown how optimal control theory is applied to find the optimal cooling schedule for this important stochastic optimization method

  5. A minimal dissipation type-based classification in irreversible thermodynamics and microeconomics

    Science.gov (United States)

    Tsirlin, A. M.; Kazakov, V.; Kolinko, N. A.

    2003-10-01

    We formulate the problem of finding classes of kinetic dependencies in irreversible thermodynamic and microeconomic systems for which minimal dissipation processes belong to the same type. We show that this problem is an inverse optimal control problem and solve it. The commonality of this problem in irreversible thermodynamics and microeconomics is emphasized.

  6. Ketone Body Acetoacetate Buffers Methylglyoxal via a Non-enzymatic Conversion during Diabetic and Dietary Ketosis

    DEFF Research Database (Denmark)

    Salomon, Trine; Sibbersen, Christian; Hansen, Jakob

    2017-01-01

    now demonstrate that during ketosis, another meta- bolic route is operative via direct non-enzymatic aldol reaction between methylglyoxal and the ke- tone body acetoacetate, leading to 3-hydroxyhex- ane-2,5-dione. This novel metabolite is present at a concentration of 10%–20% of the methylglyoxal...

  7. The role of phosphate in a multistep enzymatic reaction: reactions of the substrate and intermediate in pieces.

    Science.gov (United States)

    Kholodar, Svetlana A; Allen, C Leigh; Gulick, Andrew M; Murkin, Andrew S

    2015-02-25

    Several mechanistically unrelated enzymes utilize the binding energy of their substrate's nonreacting phosphoryl group to accelerate catalysis. Evidence for the involvement of the phosphodianion in transition state formation has come from reactions of the substrate in pieces, in which reaction of a truncated substrate lacking its phosphorylmethyl group is activated by inorganic phosphite. What has remained unknown until now is how the phosphodianion group influences the reaction energetics at different points along the reaction coordinate. 1-Deoxy-D-xylulose-5-phosphate (DXP) reductoisomerase (DXR), which catalyzes the isomerization of DXP to 2-C-methyl-D-erythrose 4-phosphate (MEsP) and subsequent NADPH-dependent reduction, presents a unique opportunity to address this concern. Previously, we have reported the effect of covalently linked phosphate on the energetics of DXP turnover. Through the use of chemically synthesized MEsP and its phosphate-truncated analogue, 2-C-methyl-D-glyceraldehyde, the current study revealed a loss of 6.1 kcal/mol of kinetic barrier stabilization upon truncation, of which 4.4 kcal/mol was regained in the presence of phosphite dianion. The activating effect of phosphite was accompanied by apparent tightening of its interactions within the active site at the intermediate stage of the reaction, suggesting a role of the phosphodianion in disfavoring intermediate release and in modulation of the on-enzyme isomerization equilibrium. The results of kinetic isotope effect and structural studies indicate rate limitation by physical steps when the covalent linkage is severed. These striking differences in the energetics of the natural reaction and the reactions in pieces provide a deeper insight into the contribution of enzyme-phosphodianion interactions to the reaction coordinate.

  8. Optimization of the performance characteristics in an irreversible magnetic Brayton refrigeration cycle

    International Nuclear Information System (INIS)

    Wang Hao; Liu Sanqiu

    2008-01-01

    An irreversible cycle model of magnetic Brayton refrigerators is established, in which the thermal resistance and irreversibility in the two adiabatic processes are taken into account. Expressions for several important performance parameters, such as the coefficient of performance, cooling rate and power input are derived. Moreover, the optimal performance parameters are obtained at the maximum coefficient of performance. The optimization region (or criteria) for an irreversible magnetic Brayton refrigerator is obtained. The results obtained here have general significance and will be helpful to understand deeply the performance of a magnetic Brayton refrigeration cycle

  9. BNNT-mediated irreversible electroporatio: its potential on cancer cells

    Energy Technology Data Exchange (ETDEWEB)

    Vittoria Raffa, Cristina Riggio, Michael W. Smith, Kevin C. Jordan, Wei Cao, Alfred Cuschieri

    2012-10-01

    Tissue ablation, i.e., the destruction of undesirable tissues, has become an important minimally invasive technique alternative to resection surgery for the treatment of tumours. Several methods for tissue ablation are based on thermal techniques using cold, e.g. cryosurgery [1] or heat, e.g. radiofrequency [2] or high-intensity focused ultrasound [3] or nanoparticle-mediated irradiation [4]. Alternatively, irreversible electroporation (IRE) has been proposed as non thermal technique for minimally invasive tissue ablation based on the use of electrical pulses. When the electric field is applied to a cell, a change in transmembrane potential is induced, which can cause biochemical and physiological changes of the cell. When the threshold value of the transmembrane potential is exceeded, the cell membrane becomes permeable, thus allowing entrance of molecules that otherwise cannot cross the membrane [5]. A further increase in the electric field intensity may cause irreversible membrane permeabilization and cell death. These pulses create irreversible defects (pores) in the cell membrane lipid bilayer, causing cell death through loss of cell homeostasis [6]. This is desirable in tumour ablation in order to produce large cell death, without the use of cytostatic drugs. A study of Davalos, Mir and Rubinsky showed that IRE can ablate substantial volumes of tissue without inducing a thermal effect and therefore serve as an independent and new tissue ablation modality; this opened the way to the use of IRE in surgery [7]. Their finding was subsequently confirmed in studies on cells [8], small animal models [9] and in large animal models in the liver [10] and the heart [11]. The most important finding in these papers is that irreversible electroporation produces precisely delineated ablation zones with cell scale resolution between ablated and non-ablated areas, without zones in which the extent of damage changes gradually as during thermal ablation. Furthermore, it is

  10. BSA treatment to enhance enzymatic hydrolysis of cellulose in lignin containing substrates.

    Science.gov (United States)

    Yang, Bin; Wyman, Charles E

    2006-07-05

    Cellulase and bovine serum albumin (BSA) were added to Avicel cellulose and solids containing 56% cellulose and 28% lignin from dilute sulfuric acid pretreatment of corn stover. Little BSA was adsorbed on Avicel cellulose, while pretreated corn stover solids adsorbed considerable amounts of this protein. On the other hand, cellulase was highly adsorbed on both substrates. Adding a 1% concentration of BSA to dilute acid pretreated corn stover prior to enzyme addition at 15 FPU/g cellulose enhanced filter paper activity in solution by about a factor of 2 and beta-glucosidase activity in solution by about a factor of 14. Overall, these results suggested that BSA treatment reduced adsorption of cellulase and particularly beta-glucosidase on lignin. Of particular note, BSA treatment of pretreated corn stover solids prior to enzymatic hydrolysis increased 72 h glucose yields from about 82% to about 92% at a cellulase loading of 15 FPU/g cellulose or achieved about the same yield at a loading of 7.5 FPU/g cellulose. Similar improvements were also observed for enzymatic hydrolysis of ammonia fiber explosion (AFEX) pretreated corn stover and Douglas fir treated by SO(2) steam explosion and for simultaneous saccharification and fermentation (SSF) of BSA pretreated corn stover. In addition, BSA treatment prior to hydrolysis reduced the need for beta-glucosidase supplementation of SSF. The results are consistent with non-specific competitive, irreversible adsorption of BSA on lignin and identify promising strategies to reduce enzyme requirements for cellulose hydrolysis. (c) 2006 Wiley Periodicals, Inc.

  11. Identification of Maillard reaction induced chemical modifications on Ara h 1

    Science.gov (United States)

    The Maillard reaction is a non-enzymatic glycation reaction between proteins and reducing sugars that can modify nut allergens during thermal processing. These modifications can alter the structural and immunological properties of these allergens, and may result in increased IgE binding. Here, we ...

  12. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  13. Glycated Lysine Residues: A Marker for Non-Enzymatic Protein Glycation in Age-Related Diseases

    OpenAIRE

    Ansari, Nadeem A.; Moinuddin,; Ali, Rashid

    2011-01-01

    Nonenzymatic glycosylation or glycation of macromolecules, especially proteins leading to their oxidation, play an important role in diseases. Glycation of proteins primarily results in the formation of an early stage and stable Amadori-lysine product which undergo further irreversible chemical reactions to form advanced glycation endproducts (AGEs). This review focuses these products in lysine rich proteins such as collagen and human serum albumin for their role in aging and age-related dise...

  14. Fluctuation theorems in feedback-controlled open quantum systems: Quantum coherence and absolute irreversibility

    Science.gov (United States)

    Murashita, Yûto; Gong, Zongping; Ashida, Yuto; Ueda, Masahito

    2017-10-01

    The thermodynamics of quantum coherence has attracted growing attention recently, where the thermodynamic advantage of quantum superposition is characterized in terms of quantum thermodynamics. We investigate the thermodynamic effects of quantum coherent driving in the context of the fluctuation theorem. We adopt a quantum-trajectory approach to investigate open quantum systems under feedback control. In these systems, the measurement backaction in the forward process plays a key role, and therefore the corresponding time-reversed quantum measurement and postselection must be considered in the backward process, in sharp contrast to the classical case. The state reduction associated with quantum measurement, in general, creates a zero-probability region in the space of quantum trajectories of the forward process, which causes singularly strong irreversibility with divergent entropy production (i.e., absolute irreversibility) and hence makes the ordinary fluctuation theorem break down. In the classical case, the error-free measurement ordinarily leads to absolute irreversibility, because the measurement restricts classical paths to the region compatible with the measurement outcome. In contrast, in open quantum systems, absolute irreversibility is suppressed even in the presence of the projective measurement due to those quantum rare events that go through the classically forbidden region with the aid of quantum coherent driving. This suppression of absolute irreversibility exemplifies the thermodynamic advantage of quantum coherent driving. Absolute irreversibility is shown to emerge in the absence of coherent driving after the measurement, especially in systems under time-delayed feedback control. We show that absolute irreversibility is mitigated by increasing the duration of quantum coherent driving or decreasing the delay time of feedback control.

  15. Unified path integral approach to theories of diffusion-influenced reactions

    Science.gov (United States)

    Prüstel, Thorsten; Meier-Schellersheim, Martin

    2017-08-01

    Building on mathematical similarities between quantum mechanics and theories of diffusion-influenced reactions, we develop a general approach for computational modeling of diffusion-influenced reactions that is capable of capturing not only the classical Smoluchowski picture but also alternative theories, as is here exemplified by a volume reactivity model. In particular, we prove the path decomposition expansion of various Green's functions describing the irreversible and reversible reaction of an isolated pair of molecules. To this end, we exploit a connection between boundary value and interaction potential problems with δ - and δ'-function perturbation. We employ a known path-integral-based summation of a perturbation series to derive a number of exact identities relating propagators and survival probabilities satisfying different boundary conditions in a unified and systematic manner. Furthermore, we show how the path decomposition expansion represents the propagator as a product of three factors in the Laplace domain that correspond to quantities figuring prominently in stochastic spatially resolved simulation algorithms. This analysis will thus be useful for the interpretation of current and the design of future algorithms. Finally, we discuss the relation between the general approach and the theory of Brownian functionals and calculate the mean residence time for the case of irreversible and reversible reactions.

  16. Micro-mechanical model for the tension-stabilized enzymatic degradation of collagen tissues

    Science.gov (United States)

    Nguyen, Thao; Ruberti, Jeffery

    We present a study of how the collagen fiber structure influences the enzymatic degradation of collagen tissues. Experiments of collagen fibrils and tissues show that mechanical tension can slow and halt enzymatic degradation. Tissue-level experiments also show that degradation rate is minimum at a stretch level coincident with the onset of strain-stiffening in the stress response. To understand these phenomena, we developed a micro-mechanical model of a fibrous collagen tissue undergoing enzymatic degradation. Collagen fibers are described as sinusoidal elastica beams, and the tissue is described as a distribution of fibers. We assumed that the degradation reaction is inhibited by the axial strain energy of the crimped collagen fibers. The degradation rate law was calibrated to experiments on isolated single fibrils from bovine sclera. The fiber crimp and properties were fit to uniaxial tension tests of tissue strips. The fibril-level kinetic and tissue-level structural parameters were used to predict tissue-level degradation-induced creep rate under a constant applied force. We showed that we could accurately predict the degradation-induce creep rate of the pericardium and cornea once we accounted for differences in the fiber crimp structure and properties.

  17. Port contact systems for irreversible thermodynamical systems

    NARCIS (Netherlands)

    Eberard, D.; Maschke, B.M.; Schaft, A.J. van der

    2005-01-01

    In this paper we propose a definition of control contact systems, generalizing input-output Hamiltonian systems, to cope with models arising from irreversible Thermodynamics. We exhibit a particular subclass of these systems, called conservative, that leaves invariant some Legendre submanifold (the

  18. Enzymatic spectrophotometric reaction rate determination of aspartame

    Directory of Open Access Journals (Sweden)

    Trifković Kata T.

    2015-01-01

    Full Text Available Aspartame is an artificial sweetener of low caloric value (approximately 200 times sweeter than sucrose. Aspartame is currently permitted for use in food and beverage production in more than 90 countries. The application of aspartame in food products requires development of rapid, inexpensive and accurate method for its determination. The new assay for determination of aspartame was based on set of reactions that are catalyzed by three different enzymes: α-chymotrypsin, alcohol oxidase and horseradish peroxidase. Optimization of the proposed method was carried out for: (i α-chymotrypsin activity; (ii time allowed for α-chymotrypsin action, (iii temperature. Evaluation of the developed method was done by determining aspartame content in “diet” drinks, as well as in artificial sweetener pills. [Projekat Ministarstva nauke Republike Srbije, br. III46010

  19. Classical many-body theory with retarded interactions: Dynamical irreversibility and determinism without probabilities

    Energy Technology Data Exchange (ETDEWEB)

    Zakharov, A.Yu., E-mail: Anatoly.Zakharov@novsu.ru; Zakharov, M.A., E-mail: ma_zakharov@list.ru

    2016-01-28

    The exact equations of motion for microscopic density of classical many-body system with account of inter-particle retarded interactions is derived. It is shown that interactions retardation leads to irreversible behavior of many-body systems. - Highlights: • A new form of equation of motion of classical many-body system is proposed. • Interactions retardation as one of the mechanisms of many-body system irreversibility. • Irreversibility and determinism without probabilities. • The possible way to microscopic foundation of thermodynamics.

  20. THEORY DEVELOPMENT OF ENZYMATIC AROMA RECOVERY

    Directory of Open Access Journals (Sweden)

    G. E. Dubova

    2014-01-01

    Full Text Available Summary. The fruit and vegetable pretreatment conditions and subsequent environment in which enzymatic reactions take place can be considered as potential factors in the formation of fresh flavors. The synthesis of aromatic components of fresh grass and green leaves occurs involving vegetable lipoxygenases. The molecules of a precursor-compound can withstand the processing modes, while enzymes and aromatic compounds break down frequently. Vegetable homogenates are potential sources of enzymes which produce natural aromatic substances. Formation of fresh favors is the most perceptible when it occurs as the result of the reaction between poliunsaturated fatty acids of cytoplasmic membranes and lipoxygenases and hydroperoxide lyase of plant material. Pre-treatment of samples positively influences binding energy in the complex of enzyme-substrate. The change of iodine number in treated homogenates, as compared to fresh ones, shows isomerization of flavor precursors. The minimal quantity of homogenates introduced (up to 20 g and the duration of aroma-restoring reaction (from 5 to 7 minutes were defined. Pre-cooling of homogenates activates enzymes, strengthens oxidability of the PUFA, and results in recovery of fresh aroma of plant material. Under conditions of enzyme inactivation, the synthesis of aromas is not possible. Conversely, production of aroma in food glazes and foams is possible in case of interphase activation between a substrate and enzymes.

  1. β-characterization by irreversibility analysis: A thermoeconomic diagnosis method

    International Nuclear Information System (INIS)

    Zaleta-Aguilar, Alejandro; Olivares-Arriaga, Abraham; Cano-Andrade, Sergio; Rodriguez-Alejandro, David A.

    2016-01-01

    This paper presents a reconciliation methodology for the diagnosis of energy systems. The methodology is based on the characterization of irreversibilities in the components of an energy system. These irreversibilities can be attributed to malfunctions or dysfunctions. The characterization of irreversibilities as presented here makes possible to reconcile the Actual Operating Condition (AOC) versus the Reference Operating Condition (ROC) of the energy system in a real-time manner. The diagnosis methodology introduces a parameter β, which represents the total exergy or useful work of a component in terms of its inlet and output streams at either design (full-load) or off-design (partial-load) conditions. The methodology is applied to the diagnosis of an actual Natural Gas Combined Cycle (NGCC) power plant. Data for the model is obtained directly from the plant by monitoring its performance at every time; thus, a real-time thermodynamic diagnosis for the system is obtained. Results show that the methodology presented here is able to detect and quantify the deviations on the performance of the NGCC power plant during its real-time operation. Based on the detection and quantification of these deviations, the user is able to make recommendations to schedule maintenance on the components where the irreversibilities are present. - Highlights: • A new methodology for thermoeconomic diagnosis of energy systems is presented. • A parameter β is defined for characterization of the components of an energy system. • The β characterization methodology is tested in a real 420 MW NGCC power plant. • Results show that the complexity of a diagnosis analysis is reduced substantially.

  2. Variability of Irreversible Poleward Transport in the Lower Stratosphere

    Science.gov (United States)

    Olsen, Mark; Douglass, Anne; Newman, Paul; Nash, Eric; Witte, Jacquelyn; Ziemke, Jerry

    2011-01-01

    The ascent and descent of the Brewer-Dobson circulation plays a large role in determining the distributions of many constituents in the extratropical lower stratosphere. However, relatively fast, quasi-horizontal transport out of the tropics and polar regions also significantly contribute to determining these distributions. The tropical tape recorder signal assures that there must be outflow from the tropics into the extratropical lower stratosphere. The phase of the quasi-biennial oscillation (QBO) and state of the polar vortex are known to modulate the transport from the tropical and polar regions, respectively. In this study we examine multiple years of ozone distributions in the extratropical lower stratosphere observed by the Aura Microwave Limb Sounder (MLS) and the Aura High Resolution Dynamic Limb Sounder (HIRDLS). The distributions are compared with analyses of irreversible, meridional isentropic transport. We show that there is considerable year-to-year seasonal variability in the amount of irreversible transport from the tropics, which is related to both the phase of the QBO and the state of the polar vortex. The reversibility of the transport is consistent with the number of observed breaking waves. The variability of the atmospheric index of refraction in the lower stratosphere is shown to be significantly correlated with the wave breaking and amount of irreversible transport. Finally, we will show that the seasonal extratropical stratosphere to troposphere transport of ozone can be substantially modulated by the amount of irreversible meridional transport in the lower stratosphere and we investigate how observable these differences are in data of tropospheric ozone.

  3. Statistical properties of multistep enzyme-mediated reactions

    OpenAIRE

    de Ronde, Wiet H.; Daniels, Bryan C.; Mugler, Andrew; Sinitsyn, Nikolai A.; Nemenman, Ilya

    2008-01-01

    Enzyme-mediated reactions may proceed through multiple intermediate conformational states before creating a final product molecule, and one often wishes to identify such intermediate structures from observations of the product creation. In this paper, we address this problem by solving the chemical master equations for various enzymatic reactions. We devise a perturbation theory analogous to that used in quantum mechanics that allows us to determine the first () and the second (variance) cumu...

  4. Enzymatic activity of the cellulolytic complex produced by trichoderma reesei. Enzymatic hydrolysis of cellulose

    International Nuclear Information System (INIS)

    Alfonsel Jaen, M.; Negro, M.J.; Saez, R.; Martin Moreno, C.

    1986-01-01

    The enzymatic activity characterization of the cellulolytic complex obtained from Trichoderma reese QM 9414 and the influence of the enzymatic hydrolysis conditions on the hydrolysis yield are studied. Pure cellulose and native or alkali pretreated biomass from Onopordum nervosum have been used as substrates. The values of pH, temperature, substrate concentration and enzyme-substrate ratio for the optimum activity of that complex, evaluated as glucose and reducing sugars productions, have been selected. Previous studies on enzymatic hydrolysis of O. nervosum have shown a remarkable effect of the alkaline pretreatments on the final hydrolysis yield. (author). 10 figs.; 10 refs

  5. Enzymatic activity of the cellulolytic complex produced by Trichoderma reesei. Enzymatic hydrolysis of cellulose

    International Nuclear Information System (INIS)

    Alfonsel J, M.; Negro A, M. J.; Saez A, R.; Martin M, C.

    1986-01-01

    The enzymatic activity characterization of the cellulolytic complex obtained from Trichoderma reesei QM 9414 and the influence of the enzymatic hydrolysis conditions on the hydrolysis yield are studied. Pure cellulose and native or alkali pretreated biomass Onopordum nervosum have been used as substrates. The values of pH, temperature, substrate concentration and enzyme-substrate ratio for the optimum activity of that complex, evaluated as glucose and reducing sugars production, have been selected. Previous studies on enzymatic hydrolysis of 0. nervosum have shown a remarkable effect of the alkaline pretreatments on the final hydrolysis yield. (Author) 10 refs

  6. Quantum thermodynamics: Microscopic foundations of entropy and of entropy generation by irreversibility

    Directory of Open Access Journals (Sweden)

    Beretta, Gian Paolo

    2008-02-01

    Full Text Available What is the physical significance of entropy? What is the physical origin of irreversibility? Do entropy and irreversibility exist only for complex and macroscopic systems? Most physicists still accept and teach that the rationalization of these fundamental questions is given by Statistical Mechanics. Indeed, for everyday laboratory physics, the mathematical formalism of Statistical Mechanics (canonical and grand-canonical, Boltzmann, Bose-Einstein and Fermi-Dirac distributions allows a successful description of the thermodynamic equilibrium properties of matter, including entropy values. However, as already recognized by Schrodinger in 1936, Statistical Mechanics is impaired by conceptual ambiguities and logical inconsistencies, both in its explanation of the meaning of entropy and in its implications on the concept of state of a system. An alternative theory has been developed by Gyftopoulos, Hatsopoulos and the present author to eliminate these stumbling conceptual blocks while maintaining the mathematical formalism so successful in applications. To resolve both the problem of the meaning of entropy and that of the origin of irreversibility we have built entropy and irreversibility into the laws of microscopic physics. The result is a theory, that we call Quantum Thermodynamics, that has all the necessary features to combine Mechanics and Thermodynamics uniting all the successful results of both theories, eliminating the logical inconsistencies of Statistical Mechanics and the paradoxes on irreversibility, and providing an entirely new perspective on the microscopic origin of irreversibility, nonlinearity (therefore including chaotic behavior and maximal-entropy-generation nonequilibrium dynamics. In this paper we discuss the background and formalism of Quantum Thermodynamics including its nonlinear equation of motion and the main general results. Our objective is to show in a not-too-technical manner that this theory provides indeed a

  7. Pressure Modulation of the Enzymatic Activity of Phospholipase A2, A Putative Membrane-Associated Pressure Sensor.

    Science.gov (United States)

    Suladze, Saba; Cinar, Suleyman; Sperlich, Benjamin; Winter, Roland

    2015-10-07

    Phospholipases A2 (PLA2) catalyze the hydrolysis reaction of sn-2 fatty acids of membrane phospholipids and are also involved in receptor signaling and transcriptional pathways. Here, we used pressure modulation of the PLA2 activity and of the membrane's physical-chemical properties to reveal new mechanistic information about the membrane association and subsequent enzymatic reaction of PLA2. Although the effect of high hydrostatic pressure (HHP) on aqueous soluble and integral membrane proteins has been investigated to some extent, its effect on enzymatic reactions operating at the water/lipid interface has not been explored, yet. This study focuses on the effect of HHP on the structure, membrane binding and enzymatic activity of membrane-associated bee venom PLA2, covering a pressure range up to 2 kbar. To this end, high-pressure Fourier-transform infrared and high-pressure stopped-flow fluorescence spectroscopies were applied. The results show that PLA2 binding to model biomembranes is not significantly affected by pressure and occurs in at least two kinetically distinct steps. Followed by fast initial membrane association, structural reorganization of α-helical segments of PLA2 takes place at the lipid water interface. FRET-based activity measurements reveal that pressure has a marked inhibitory effect on the lipid hydrolysis rate, which decreases by 75% upon compression up to 2 kbar. Lipid hydrolysis under extreme environmental conditions, such as those encountered in the deep sea where pressures up to the kbar-level are encountered, is hence markedly affected by HHP, rendering PLA2, next to being a primary osmosensor, a good candidate for a sensitive pressure sensor in vivo.

  8. Use of Enzymatic Bio-Fenton as a New Approach in Decolorization of Malachite Green

    Science.gov (United States)

    Karimi, Afzal; Aghbolaghy, Mostafa; Khataee, Alireza; Shoa Bargh, Shabnam

    2012-01-01

    An enzymatic reaction using glucose oxidase was applied for in situ production of hydrogen peroxide for use in simultaneously Fenton's reaction in decolorization of malachite green. It was found that decolorization rate increased by increasing of glucose concentration from 0.2 g/L to 1.5 g/L. Decolorization rate showed different behaviors versus temperature changes. Initial rate of decolorization process was increased by increasing of temperature; after 30 minutes, especially at temperatures above 30°C, the decolorization rate was gradually reduced. The pH value in the reaction media was decreased from natural to about pH = 3 which had synergic effect on the Fenton process by stabilizing of Fe2+ ions. PMID:22649310

  9. Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration.

    Science.gov (United States)

    Marpani, Fauziah; Sárossy, Zsuzsa; Pinelo, Manuel; Meyer, Anne S

    2017-12-01

    Enzymatic reduction of carbon dioxide (CO 2 ) to methanol (CH 3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH 3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO 2 to CH 3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH 3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH 3 OH, a TTN of 160 and BPR of 24 μmol CH 3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH 3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

  10. Fabrication of high surface area graphene electrodes with high performance towards enzymatic oxygen reduction

    International Nuclear Information System (INIS)

    Di Bari, Chiara; Goñi-Urtiaga, Asier; Pita, Marcos; Shleev, Sergey; Toscano, Miguel D.; Sainz, Raquel; De Lacey, Antonio L.

    2016-01-01

    High surface area graphene electrodes were prepared by simultaneous electrodeposition and electroreduction of graphene oxide. The electrodeposition process was optimized in terms of pH and conductivity of the solution and the obtained graphene electrodes were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy and electrochemical methods (cyclic voltammetry and impedance spectroscopy). Electrodeposited electrodes were further functionalized to carry out covalent immobilization of two oxygen-reducing multicopper oxidases: laccase and bilirubin oxidase. The enzymatic electrodes were tested as direct electron transfer based biocathodes and catalytic currents as high as 1 mA/cm 2 were obtained. Finally, the mechanism of the enzymatic oxygen reduction reaction was studied for both enzymes calculating the Tafel slopes and transfer coefficients.

  11. Sequential enzymatic epoxidation involved in polyether lasalocid biosynthesis.

    Science.gov (United States)

    Minami, Atsushi; Shimaya, Mayu; Suzuki, Gaku; Migita, Akira; Shinde, Sandip S; Sato, Kyohei; Watanabe, Kenji; Tamura, Tomohiro; Oguri, Hiroki; Oikawa, Hideaki

    2012-05-02

    Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene clusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis. © 2012 American Chemical Society

  12. Enzymatic production of ceramide from sphingomyelin

    DEFF Research Database (Denmark)

    Zhang, Long; Hellgren, Lars; Xu, Xuebing

    Ceramide is the key intermediate in the biosynthesis of all complex sphingolipids. Due to its major role in maintaining the water-retaining properties of the epidermis, ceramide is of great commercial potential in cosmetic and pharmaceuticals such as hair and skin care products. Currently, chemical...... contains a ceramide moiety, is a ubiquitous component of animal cell membranes, and dairy products or by-products is a rich source of sphingomyelin. It has been verified that enzymatic modification of sphingomyelin is a feasible approach for production of ceramide. The reaction system has been optimized...... through system evaluation and the optimization of several important factors. Sphingomyelin hydrolysis proved to be more efficient in two-phase (water: organic solvent) system than in one-phase (water-saturated organic solvent) system. Phospholipase C from Clostridium perfringens is the tested enzyme which...

  13. Non-Enzymatic biopolymerization reactions supported by heterogeneous media

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain

    2011-01-01

    Heterogeneous media, such as micro-structured aqueous environments, could offer an alternative approach to the synthesis of biopolymers with novel functions. Structured media are here defined as specialized, self-assembled structures that are formed, e.g, by amphiphiles, such as liposomes, emulsion...... compartments and lipid-bilayer lattices. Another kind of media is represented by co-existing, self-assembled phases in the reaction medium, e.g., in water-ice matrices. These media have the capacity to assemble chemical molecules or complex catalytic assemblies into unique configurations that are unstable...

  14. Extremum principles for irreversible processes

    International Nuclear Information System (INIS)

    Hillert, M.; Agren, J.

    2006-01-01

    Hamilton's extremum principle is a powerful mathematical tool in classical mechanics. Onsager's extremum principle may play a similar role in irreversible thermodynamics and may also become a valuable tool. His principle may formally be regarded as a principle of maximum rate of entropy production but does not have a clear physical interpretation. Prigogine's principle of minimum rate of entropy production has a physical interpretation when it applies, but is not strictly valid except for a very special case

  15. Response Surface Methodology to Optimize Enzymatic Preparation of Deapio-Platycodin D and Platycodin D from Radix Platycodi

    Directory of Open Access Journals (Sweden)

    Jian Liang

    2012-03-01

    Full Text Available In the present work, we reported the enzymatic preparation of deapio-platycodin D (dPD and platycodin D (PD optimized by response surface methodology (RSM from Radix Platycodi. During investigation of the hydrolysis of crude platycosides by various glycoside hydrolases, snailase showed a strong ability to transform deapio-platycoside E (dPE and platycoside E (PE into dPD and PD with 100% conversion. RSM was used to optimize the effects of the reaction temperature (35–45 °C, enzyme load (5–20%, and reaction time (4–24 h on the conversion process. Validation of the RSM model was verified by the good agreement between the experimental and the predicted values of dPD and PD conversion yield. The optimum preparation conditions were as follows: temperature, 43 °C; enzyme load, 15%; reaction time, 22 h. The biotransformation pathways were dPE→dPD3→dPD and PE→PD3→PD, respectively. The determined method may be highly applicable for the enzymatic preparation of dPD and PD for medicinal purposes and also for commercial use.

  16. Optimal information transfer in enzymatic networks: A field theoretic formulation

    Science.gov (United States)

    Samanta, Himadri S.; Hinczewski, Michael; Thirumalai, D.

    2017-07-01

    Signaling in enzymatic networks is typically triggered by environmental fluctuations, resulting in a series of stochastic chemical reactions, leading to corruption of the signal by noise. For example, information flow is initiated by binding of extracellular ligands to receptors, which is transmitted through a cascade involving kinase-phosphatase stochastic chemical reactions. For a class of such networks, we develop a general field-theoretic approach to calculate the error in signal transmission as a function of an appropriate control variable. Application of the theory to a simple push-pull network, a module in the kinase-phosphatase cascade, recovers the exact results for error in signal transmission previously obtained using umbral calculus [Hinczewski and Thirumalai, Phys. Rev. X 4, 041017 (2014), 10.1103/PhysRevX.4.041017]. We illustrate the generality of the theory by studying the minimal errors in noise reduction in a reaction cascade with two connected push-pull modules. Such a cascade behaves as an effective three-species network with a pseudointermediate. In this case, optimal information transfer, resulting in the smallest square of the error between the input and output, occurs with a time delay, which is given by the inverse of the decay rate of the pseudointermediate. Surprisingly, in these examples the minimum error computed using simulations that take nonlinearities and discrete nature of molecules into account coincides with the predictions of a linear theory. In contrast, there are substantial deviations between simulations and predictions of the linear theory in error in signal propagation in an enzymatic push-pull network for a certain range of parameters. Inclusion of second-order perturbative corrections shows that differences between simulations and theoretical predictions are minimized. Our study establishes that a field theoretic formulation of stochastic biological signaling offers a systematic way to understand error propagation in

  17. Enzymatic exchange of sulphur between cysteine and hydrogen sulphide in the yolk sac of an incubated bird's egg

    International Nuclear Information System (INIS)

    Chapeville, F.; Fromageot, P.

    1960-01-01

    Previous work has shown that the formation of cysteic acid from sulphate in incubated hen's eggs is due to the following reactions: a) reduction of sulphate to sulphite by the yolk sac endoderm cells; b) synthesis of cysteic acid from the sulphite in the presence of cysteine with liberation of hydrogen sulphide: HS-CH 2 -CH(NH 2 )-COOH + SO 3 H - → H 2 S + - O 3 S-CH 2 -CH(NH 2 )-COOH (1). The enzymatic system responsible for this reaction is localized on the yolk sac endoderm and in the yolk. It may be wondered whether reaction (1) is not made up of two consecutive reactions, one of which is reversible: HS-CH 2 -CH(NH 2 )-COOH ↔ H 2 S + organic chain (2) and organic chain + SO 3 H - → - O 3 S-CH 2 -CH(NH 2 )-COOH (3). It would then be clear why the addition of sulphite displaces the equilibrium towards the production of cysteic acid and hydrogen sulphide. If this is the case, the addition of ordinary cysteine and of marked hydrogen sulphide to the biological medium should make it possible to detect the formation of 35 S cysteine. The present work shows that the desulphurization of the cysteine (reaction 2) by the yolk sac + the yolk is in fact a reversible reaction, and that an enzymatic exchange occurs between the sulphur of the cysteine and that of the hydrogen sulphide. (author) [fr

  18. Modelling and operation of reactors for enzymatic biodiesel production

    DEFF Research Database (Denmark)

    Price, Jason Anthony

    to the production of high fructose corn syrup, upgrading of fats and oils and biodiesel production to name a few. Despite these examples of industrial enzymatic applications, it is still not “clear cut” how to implement biocatalyst in industry and how best to optimize the processes. This is because the processing...... aspects of the enzyme with reaction/reactor engineering is performed. This strategy is applied to a case study of biodiesel production catalysed by a liquid enzyme formulation. The use of enzymes for biodiesel production is still in its infancy with non-optimized process designs. Furthermore is it unclear...

  19. Irreversible performance of a quantum harmonic heat engine

    Science.gov (United States)

    Rezek, Yair; Kosloff, Ronnie

    2006-05-01

    The unavoidable irreversible loss of power in a heat engine is found to be of quantum origin. Following thermodynamic tradition, a model quantum heat engine operating in an Otto cycle is analysed, where the working medium is composed of an ensemble of harmonic oscillators and changes in volume correspond to changes in the curvature of the potential well. Equations of motion for quantum observables are derived for the complete cycle of operation. These observables are sufficient to determine the state of the system and with it all thermodynamical variables. Once the external controls are set, the engine settles to a limit cycle. Conditions for optimal work, power and entropy production are derived. At high temperatures and quasistatic operating conditions, the efficiency at maximum power coincides with the endoreversible result \\eta_q=1-\\sqrt{{T_c}/{T_h}} . The optimal compression ratio varies from {\\cal C} =\\sqrt{T_h/T_c} in the quasistatic limit where the irreversibility is dominated by heat conductance to {\\cal C} =(T_h/T_c)^{1/4} in the sudden limit when the irreversibility is dominated by friction. When the engine deviates from adiabatic conditions, the performance is subject to friction. The origin of this friction can be traced to the noncommutability of the kinetic and potential energy of the working medium.

  20. Kinetic study of enzymatic hydrolysis of potato starch

    Directory of Open Access Journals (Sweden)

    Óscar Fernando Castellanos Domínguez

    2004-01-01

    Full Text Available This article describes the kinetic study of potato starch enzymatic hydrolysis using soluble enzymes (Novo Nordisk. Different assays divided into four groups were used: reaction time (with which it was possible to reduce the 48-72 hour duration reported in the literature to 16 hours with comparable productivity levels; selecting the set of enzymes to be used (different types were evaluated - BAN and Termamyl as alfa-amylases during dextrinisation stage, and AMG, Promozyme and Fungamyl for sacarification reaction- identifying those presenting the best performance during hydrolysis.Reaction conditions were optimised for the process's two stages (destrinisation and sacarification. Enzyme dose, calcium cofactor concentration, pH, temperature and agitation speed were studied for the first stage. Enzyme ratio, pH and agitation speed were studied for sacarification; the latter parameter reported values having no antecedents in the literature (60 rpm and 30 rpm for first and second reactions, respectively. Michaelis Menten kinetics were calculated once conditions had been optimised, varying substrate from 10-50% P/V, obtaining km and Vmax kinetic parameters for each reaction. A kinetic model was found according to local working conditions which was able to explain potato starch conversion to glucose syrup, achieving 96 dextrose equivalents by the end of the reaction, being well within the maximum range reported in the literature (94-98.Laboratory equipment was constructed prior to carrying out assays which was able to reproduce and improve the conditions reported in the literature, making it a useful, reliable tool for use in assays returning good results.

  1. Risk Aversion, Price Uncertainty and Irreversible Investments

    NARCIS (Netherlands)

    van den Goorbergh, R.W.J.; Huisman, K.J.M.; Kort, P.M.

    2003-01-01

    This paper generalizes the theory of irreversible investment under uncertainty by allowing for risk averse investors in the absence of com-plete markets.Until now this theory has only been developed in the cases of risk neutrality, or risk aversion in combination with complete markets.Within a

  2. Effect of the steam explosion pretreatment on enzymatic hydrolysis of eucalyptus wood and sweet sorghum baggages

    International Nuclear Information System (INIS)

    Negro, M. J.; Martinez, J. M.; Manero, J.; Saez, F.; Martin, C.

    1991-01-01

    The effect of steam explosion treatment on the enzymatic hydrolysis yield of two different lignocellulosic substrates is studied. Raw materials have been pretreated in a pilot plant designed to work in batch and equipped with a reactor vessel of 2 1 working volume where biomass was heated at the desired temperature and then exploded and recovered in a cyclone. Temperatures from 190 to 230 degree celsius and reaction times from 2 to 8 min. have been assayed. The efficiency of the steam explosion treatment has been evaluated on the composition of the lignocellulosic materials as well as on their enzymatic hydrolysis yield using a cellulolytic complex from T. reesel. Results show a high solubilization rate of hemicelluloses and variable losses of cellulose and lignin depending on the conditions tested. Enzymatic hydrolysis yields of both substrates experimented remarkable increments, corresponding the highest values obtained to 210 degree celsius; 2 min. and 21O degree celsius; 4 min. for sorghum bagasse and eucalyptus wood respectively. (Author) 13 refs

  3. Effect of the steam explosion pretreatment on enzymatic hydrolysis of eucalyptus wood and sweet sorghum bagasse

    International Nuclear Information System (INIS)

    Negro, M.J.; Martinez, J.M.; Manero, J.; Saez, F.; Martin, C.

    1990-01-01

    The effect of steam explosion treatment on the enzymatic hydrolysis yield of two different lignocellulosic substrates is studied. Raw materials have been pretreated in a pilot plant designed to work in batch and equiped with a reactor vessel of 2 1 working volume where biomass was heated at the desired temperature and then exploded and recovered in a cyclone. Temperatures from 190 to 230 o C and reaction times from 2 to 8 min. have been assayed. The efficiency of the steam explosion treatment has been evaluated on the composition of the lignocellulosic materials as well as on their enzymatic hydrolysis yield using a cellulolytic complex from T. reesei. Results show a high solubilization rate of hemicelluloses ands variable losses of cellulose and lignin depending on the conditions tested. Enzymatic hydrolysis yields of both substrates experimented remarkable increments, correspondig the highest values obtained to 210 o C; 2 min. and 210 o C; 4 min. for sorghum bagasse and eucaliptus wood respectivelly. (Author). 13 refs

  4. Blocked Enzymatic Etching of Gold Nanorods: Application to Colorimetric Detection of Acetylcholinesterase Activity and Its Inhibitors.

    Science.gov (United States)

    Saa, Laura; Grinyte, Ruta; Sánchez-Iglesias, Ana; Liz-Marzán, Luis M; Pavlov, Valeri

    2016-05-04

    The anisotropic morphology of gold nanorods (AuNRs) has been shown to lead to nonuniform ligand distribution and preferential etching through their tips. We have recently demonstrated that this effect can be achieved by biocatalytic oxidation with hydrogen peroxide, catalyzed by the enzyme horseradish peroxidase (HRP). We report here that modification of AuNRs with thiol-containing organic molecules such as glutathione and thiocholine hinders enzymatic AuNR etching. Higher concentrations of thiol-containing molecules in the reaction mixture gradually decrease the rate of enzymatic etching, which can be monitored by UV-vis spectroscopy through changes in the AuNR longitudinal plasmon band. This effect can be applied to develop novel optical assays for acetylcholinesterase (AChE) activity. The biocatalytic hydrolysis of acetylthiocholine by AChE yields thiocholine, which prevents enzymatic AuNR etching in the presence of HRP. Additionally, the same bioassay can be used for the detection of nanomolar concentrations of AChE inhibitors such as paraoxon and galanthamine.

  5. Kinetics of enzymatic hydrolysis of methyl ricinoleate

    Directory of Open Access Journals (Sweden)

    Neeharika, T. S.V.R.

    2015-12-01

    Full Text Available Ricinoleic acid is an unsaturated hydroxy fatty acid that naturally occurs in castor oil in proportions of up to 85–90%. Ricinoleic acid is a potential raw material and finds several applications in coatings, lubricant formulations and pharmaceutical areas. Enzymatic hydrolysis of castor oil is preferred over conventional hydrolysis for the preparation of ricinoleic acid to avoid estolide formation. A kinetics analysis of the enzymatic hydrolysis of Methyl Ricinoleate in the presence of Candida antarctica Lipase B was carried out in this study by varying reaction temperature (40–60 °C and enzyme concentration (2–5%. The optimal conditions were found to be 6 h reaction time, temperature 60°C, buffer to methyl ricinoleate ratio 2:1(v/w and 4% enzyme concentration to achieve a maximum conversion of 98.5%. A first order reversible reaction kinetic model was proposed to describe this reaction and a good agreement was observed between the experimental data and the model values. The effect of temperature on the forward reaction rate constant was determined by fitting data to the Arrhenius equation. The activation energy for forward reaction was found to be 14.69 KJ·mol−1.El ácido ricinoleico es un hidroxiácido insaturado que se produce naturalmente en el aceite de ricino en proporciones de hasta el 85–90%. El ácido ricinoleico es una materia prima con gran potencial y tiene aplicaciones en revestimientos, formulaciones lubricantes y en áreas farmacéuticas. Para la preparación del ácido ricinoleico se prefiere la hidrólisis enzimática del aceite de ricino a la hidrólisis convencional, para evitar la formación de estólidos. En este estudio se llevó a cabo la cinética de la hidrólisis enzimática del ricinoleato de metilo en presencia de lipasa de Candida antarctica B mediante la variación de la temperatura de reacción (40–60 °C y la concentración de la enzima (2–5%. Las condiciones óptimas de la reacción para

  6. How to account for irreversibility in integrated assessment of climate change?

    International Nuclear Information System (INIS)

    Ha Duong, M.

    1998-04-01

    How to account for irreversibility in integrated assessment of climate change? This Ph. D. thesis in Economics balances discounting, technical progress and the inertia of existing capital stock against uncertainty and the inertia of socio-economic systems to examine the issue of near term limitations of greenhouse gases emissions. After a general overview in chapter 2, and a more historical presentation of the debates in chapter 3, chapter 4 proceeds to review a large number of integrated assessment models. Chapter 5 introduces a Model on the Dynamics of Inertia and Adaptability of energy systems: DIAM, used to discuss how much previous studies might have overestimated the long term costs of CO 2 limitations and underestimated adjustment costs. It shows that, given a target date for atmospheric CO 2 concentration stabilisation, a higher inertia implies a lower optimal concentration trajectory. In a sequential decision framework, chapter 6 shows that current uncertainties about which CO 2 concentration ceiling would not present dangerous interference with the climate system justifies precautionary action. Finally, chapter 7 uses the irreversibility effect theory to define formally situations of decision under controversy and compare the irreversibility of CO 2 accumulation with the irreversibility of investments needed to moderate it. An option value for greenhouse gases emissions limitations is computed. (author)

  7. Canonical formalism, fundamental equation, and generalized thermomechanics for irreversible fluids with heat transfer

    International Nuclear Information System (INIS)

    Sieniutycz, S.; Berry, R.S.

    1993-01-01

    A Lagrangian with dissipative (e.g., Onsager's) potentials is constructed for the field description of irreversible heat-conducting fluids, off local equilibrium. Extremum conditions of action yield Clebsch representations of temperature, chemical potential, velocities, and generalized momenta, including a thermal momentum introduced recently [R. L. Selinger and F. R. S. Whitham, Proc. R. Soc. London, Ser. A 302, 1 (1968); S. Sieniutycz and R. S. Berry, Phys. Rev. A 40, 348 (1989)]. The basic question asked is ''To what extent may irreversibility, represented by a given form of the entropy source, influence the analytical form of the conservation laws for the energy and momentum?'' Noether's energy for a fluid with heat flow is obtained, which leads to a fundamental equation and extended Hamiltonian dynamics obeying the second law of thermodynamics. While in the case of the Onsager potentials this energy coincides numerically with the classical energy E, it contains an extra term (vanishing along the path) still contributing to an irreversible evolution. Components of the energy-momentum tensor preserve all terms regarded standardly as ''irreversible'' (heat, tangential stresses, etc.) generalized to the case when thermodynamics includes the state gradients and the so-called thermal phase, which we introduce here. This variable, the Lagrange multiplier of the entropy generation balance, is crucial for consistent treatment of irreversible processes via an action formalism. We conclude with the hypothesis that embedding the first and second laws in the context of the extremal behavior of action under irreversible conditions may imply accretion of an additional term to the classical energy

  8. Enzymatic deconstruction of xylan for biofuel production

    Science.gov (United States)

    DODD, DYLAN; CANN, ISAAC K. O.

    2010-01-01

    The combustion of fossil-derived fuels has a significant impact on atmospheric carbon dioxide (CO2) levels and correspondingly is an important contributor to anthropogenic global climate change. Plants have evolved photosynthetic mechanisms in which solar energy is used to fix CO2 into carbohydrates. Thus, combustion of biofuels, derived from plant biomass, can be considered a potentially carbon neutral process. One of the major limitations for efficient conversion of plant biomass to biofuels is the recalcitrant nature of the plant cell wall, which is composed mostly of lignocellulosic materials (lignin, cellulose, and hemicellulose). The heteropolymer xylan represents the most abundant hemicellulosic polysaccharide and is composed primarily of xylose, arabinose, and glucuronic acid. Microbes have evolved a plethora of enzymatic strategies for hydrolyzing xylan into its constituent sugars for subsequent fermentation to biofuels. Therefore, microorganisms are considered an important source of biocatalysts in the emerging biofuel industry. To produce an optimized enzymatic cocktail for xylan deconstruction, it will be valuable to gain insight at the molecular level of the chemical linkages and the mechanisms by which these enzymes recognize their substrates and catalyze their reactions. Recent advances in genomics, proteomics, and structural biology have revolutionized our understanding of the microbial xylanolytic enzymes. This review focuses on current understanding of the molecular basis for substrate specificity and catalysis by enzymes involved in xylan deconstruction. PMID:20431716

  9. Health Technology Assessment of CEM Pulpotomy in Permanent Molars with Irreversible Pulpitis

    Science.gov (United States)

    Yazdani, Shahram; Jadidfard, Mohammad-Pooyan; Tahani, Bahareh; Kazemian, Ali; Dianat, Omid; Alim Marvasti, Laleh

    2014-01-01

    Introduction: Teeth with irreversible pulpitis usually undergo root canal therapy (RCT). This treatment modality is often considered disadvantageous as it removes vital pulp tissue and weakens the tooth structure. A relatively new concept has risen which suggests vital pulp therapy (VPT) for irreversible pulpitis. VPT with calcium enriched mixture (VPT/CEM) has demonstrated favorable treatment outcomes when treating permanent molars with irreversible pulpitis. This study aims to compare patient related factors, safety and organizational consideration as parts of health technology assessment (HTA) of the new VPT/CEM biotechnology when compared with RCT. Materials and Methods: Patient related factors were assessed by looking at short- and long-term clinical success; safety related factors were evaluated by a specialist committee and discussion board involved in formulating healthcare policies. Organizational evaluation was performed and the social implications were assessed by estimating the costs, availability, accessibility and acceptability. The impact of VPT/CEM biotechnology was assessed by investigating the incidence of irreversible pulpitis and the effect of this treatment on reducing the burden of disease. Results: VPT/CEM biotechnology was deemed feasible and acceptable like RCT; however, it was more successful, accessible, affordable, available and also safer than RCT. Conclusion: When considering socioeconomic implications on oral health status and oral health-related quality of life of VPT/CEM, the novel biotechnology can be more effective and more efficient than RCT in mature permanent molars with irreversible pulpitis. PMID:24396372

  10. Onsager's reciprocity theorem in extended irreversible thermodynamics

    International Nuclear Information System (INIS)

    Garcia-Colin, L.S.; Velasco, R.M.

    1992-01-01

    In this paper we shall discuss the Onsager relations for the transport coefficients in a dilute monatomic gas described by the extended irreversible thermodynamics. Our discussion is based on a 26 variables description of the system and its corresponding comparison with the kinetic reciprocity between coefficients is shown (Author)

  11. Mechano-Enzymatic Deconstruction with a New Enzymatic Cocktail to Enhance Enzymatic Hydrolysis and Bioethanol Fermentation of Two Macroalgae Species

    Directory of Open Access Journals (Sweden)

    Sameh Amamou

    2018-01-01

    Full Text Available The aim of this study was to explore the efficiency of a mechano-enzymatic deconstruction of two macroalgae species for sugars and bioethanol production, by using a new enzymatic cocktail (Haliatase and two types of milling modes (vibro-ball: VBM and centrifugal milling: CM. By increasing the enzymatic concentration from 3.4 to 30 g/L, the total sugars released after 72 h of hydrolysis increased (from 6.7 to 13.1 g/100 g TS and from 7.95 to 10.8 g/100 g TS for the green algae U. lactuca and the red algae G. sesquipedale, respectively. Conversely, total sugars released from G. sesquipedale increased (up to 126% and 129% after VBM and CM, respectively. The best bioethanol yield (6 geth/100 g TS was reached after 72 h of fermentation of U. lactuca and no increase was obtained after centrifugal milling. The latter led to an enhancement of the ethanol yield of G. sesquipedale (from 2 to 4 g/100 g TS.

  12. Use of Enzymatic Bio-Fenton as a New Approach in Decolorization of Malachite Green

    Directory of Open Access Journals (Sweden)

    Afzal Karimi

    2012-01-01

    Full Text Available An enzymatic reaction using glucose oxidase was applied for in situ production of hydrogen peroxide for use in simultaneously Fenton's reaction in decolorization of malachite green. It was found that decolorization rate increased by increasing of glucose concentration from 0.2 g/L to 1.5 g/L. Decolorization rate showed different behaviors versus temperature changes. Initial rate of decolorization process was increased by increasing of temperature; after 30 minutes, especially at temperatures above 30°C, the decolorization rate was gradually reduced. The pH value in the reaction media was decreased from natural to about pH=3 which had synergic effect on the Fenton process by stabilizing of Fe2+ ions.

  13. Structure of fungal oxyluciferin, the product of the bioluminescence reaction.

    Science.gov (United States)

    Purtov, K V; Osipova, Z M; Petushkov, V N; Rodionova, N S; Tsarkova, A S; Kotlobay, A A; Chepurnykh, T V; Gorokhovatsky, A Yu; Yampolsky, I V; Gitelson, J I

    2017-11-01

    The structure of fungal oxyluciferin was determined, the enzymatic bioluminescence reaction under substrate saturation conditions with discrete monitoring of formed products was conducted, and the structures of the end products of the reaction were established. On the basis of these studies, the scheme of oxyluciferin degradation to the end products was developed. The structure of fungal oxyluciferin was confirmed by counter synthesis.

  14. Lie-admissible invariant treatment of irreversibility for matter and antimatter at the classical and operator levels

    International Nuclear Information System (INIS)

    Santilli, R.M.

    2006-01-01

    It was generally believed throughout the 20th century that irreversibility is a purely classical event without operator counterpart. however, a classical irreversible system cannot be consistently decomposed into a finite number of reversible quantum particles (and. vive versa), thus establishing that the origin of irreversibility is basically unknown at the dawn of the 21-st century. To resolve this problem. we adopt the historical analytical representation of irreversibility by Lagrange and Hamilton, that with external terms in their analytic equations; we show that, when properly written, the brackets of the time evolution characterize covering Lie-admissible algebras; we prove that the formalism has fully consistent operator counterpart given by the Lie-admissible branch of hadronic mechanics; we identify mathematical and physical inconsistencies when irreversible formulations are treated with the conventional mathematics used for reversible systems; we show that when the dynamical equations are treated with a novel irreversible mathematics, Lie-admissible formulations are fully consistent because invariant at both the classical and operator levels; and we complete our analysis with a number of explicit applications to irreversible processes in classical mechanics, particle physics and thermodynamics. The case of closed-isolated systems verifying conventional total conservation laws, yet possessing an irreversible structure, is treated via the simpler Lie-isotopic branch of hadronic mechanics. The analysis is conducted for both matter and antimatter at the classical and operator levels to prevent insidious inconsistencies occurring for the sole study of matter or, separately, antimatter

  15. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  16. [Non-enzymatic glycosylation of dietary protein in vitro].

    Science.gov (United States)

    Bednykh, B S; Evdokimov, I A; Sokolov, A I

    2015-01-01

    Non-enzymatic glycosylation of proteins, based on discovered by Mayarn reaction of carbohydrate aldehyde group with a free amino group of a protein molecule, is well known to experts in biochemistry of food industry. Generated brown solid in some cases give the product marketable qualities--crackling bread--in others conversely, worsen the product. The biological effects of far-advanced products of non-enzymatic protein glycosylation reaction have not been studied enough, although it was reported previously that they are not split by digestive enzymes and couldn't be absorbed by animals. The objective of this work was to compare the depth of glycosylation of different food proteins of animal and vegetable origin. The objects of the study were proteins of animal (casein, lactoglobulin, albumin) and vegetable (soy isolate, proteins of rice flour, buckwheat, oatmeal) origin, glucose and fructose were selected as glycosylation agents, exposure 15 days at 37 degrees C. Lactoglobulin was glycosylated to a lesser extent among the proteins of animal origin while protein of oatmeal was glycosylated in the least degree among vegetable proteins. Conversely, such proteins as casein and soya isolate protein bound rather large amounts of carbohydrates. Fructose binding with protein was generally higher than the binding of glucose. The only exception was a protein of oatmeal. When of glucose and fructose simultaneously presented in the incubation medium, glucose binding usually increased while binding of fructose, in contrast, reduced. According to the total amount of carbohydrate (mcg), which is able to attach a protein (mg) the studied food proteins located in the following order: albumin (38) > soy protein isolate (23) > casein (15,) > whey protein rice flour protein (6) > protein from buckwheat flour (3) > globulin (2) > protein of oatmeal (0.3). The results obtained are to be used to select the optimal combination of proteins and carbohydrates, in which the glycosylation

  17. Spectral deformation techniques applied to the study of quantum statistical irreversible processes

    International Nuclear Information System (INIS)

    Courbage, M.

    1978-01-01

    A procedure of analytic continuation of the resolvent of Liouville operators for quantum statistical systems is discussed. When applied to the theory of irreversible processes of the Brussels School, this method supports the idea that the restriction to a class of initial conditions is necessary to obtain an irreversible behaviour. The general results are tested on the Friedrichs model. (Auth.)

  18. Aerosol-Forming Reactions of Glyoxal, Methylglyoxal and Amino Acids in Clouds

    Science.gov (United States)

    de Haan, D. O.; Smith, K. W.; Stroik, D. R.; Corrigan, A. L.; Lee, F. E.; Phan, J. T.; Conley, A. C.

    2008-12-01

    Glyoxal and methylglyoxal are two common aldehydes present in fog and cloud water. Amino acids are present in clouds at similar concentrations. Here we present bulk and aerosol mass spectroscopic data demonstrating that irreversible reactions between glyoxal and amino acids, triggered by droplet evaporation, produce N-derivatized imidazole compounds along with deeply colored Maillard reaction products. These reactions can occur in the dark and in the absence of oxidants. Reactions between methylglyoxal and amino acids produce analogous methylated products plus oligomers with masses up to m/z = 1000. These reactions, which go to completion on the 10-min-timescale of cloud processing, could be significant sources of secondary organic aerosol and humic-like substances (HULIS or brown carbon).

  19. Articaine for supplemental intraosseous anesthesia in patients with irreversible pulpitis.

    Science.gov (United States)

    Bigby, Jason; Reader, Al; Nusstein, John; Beck, Mike; Weaver, Joel

    2006-11-01

    The purpose of this study was to determine the anesthetic efficacy and heart rate effect of 4% articaine with 1:100,000 epinephrine for supplemental intraosseous injection in mandibular posterior teeth diagnosed with irreversible pulpitis. Thirty-seven emergency patients, diagnosed with irreversible pulpitis of a mandibular posterior tooth, received an inferior alveolar nerve block and had moderate-to-severe pain upon endodontic access. The Stabident system was used to administer 1.8 ml of 4% articaine with 1:100,000 epinephrine. Success of the intraosseous injection was defined as none or mild pain upon endodontic access or initial instrumentation. The results demonstrated that anesthetic success was obtained in 86% (32 of 37) of the patients. Maximum mean heart rate was increased 32 beats/minute during the intraosseous injection. We can conclude that when the inferior alveolar nerve block fails to provide profound pulpal anesthesia, the intraosseous injection of 4% articaine with 1:100,000 epinephrine would be successful 86% of the time in achieving pulpal anesthesia in mandibular posterior teeth of patients presenting with irreversible pulpitis.

  20. FINITE TIME THERMODYNAMIC MODELING AND ANALYSIS FOR AN IRREVERSIBLE ATKINSON CYCLE

    Directory of Open Access Journals (Sweden)

    Yanlin Ge

    2010-01-01

    Full Text Available Performance of an air-standard Atkinson cycle is analyzed by using finite-time thermodynamics. The irreversible cycle model which is more close to practice is founded. In this model, the non-linear relation between the specific heats of working fluid and its temperature, the friction loss computed according to the mean velocity of the piston, the internal irreversibility described by using the compression and expansion efficiencies, and heat transfer loss are considered. The relations between the power output and the compression ratio, between the thermal efficiency and the compression ratio, as well as the optimal relation between power output and the efficiency of the cycle are derived by detailed numerical examples. Moreover, the effects of internal irreversibility, heat transfer loss and friction loss on the cycle performance are analyzed. The results obtained in this paper may provide guidelines for the design of practical internal combustion engines.

  1. Irreversible endo-Selective Diels–Alder Reactions of Substituted Alkoxyfurans: A General Synthesis of endo-Cantharimides

    Science.gov (United States)

    Foster, Robert W; Benhamou, Laure; Porter, Michael J; Bučar, Dejan-Krešimir; Hailes, Helen C; Tame, Christopher J; Sheppard, Tom D

    2015-01-01

    The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels–Alder reaction. PMID:25756502

  2. Ecological optimization and performance study of irreversible Stirling and Ericsson heat engines

    International Nuclear Information System (INIS)

    Tyagi, S K; Kaushik, S C; Salhotra, R

    2002-01-01

    The concept of finite time thermodynamics is used to determine the ecological function of irreversible Stirling and Ericsson heat engine cycles. The ecological function is defined as the power output minus power loss (irreversibility), which is the ambient temperature times, the entropy generation rate. The ecological function is maximized with respect to cycle temperature ratio and the expressions for the corresponding power output and thermal efficiency are derived at the optimal operating conditions. The effect of different operating parameters, the effectiveness on the hot, cold and the regenerative side heat exchangers, the cycle temperature ratio, heat capacitance ratio and the internal irreversibility parameter on the maximum ecological function are studied. It is found that the effect of regenerator effectiveness is more than the hot and cold side heat exchangers and the effect of the effectiveness on cold side heat exchanger is more than the effectiveness on the hot side heat exchanger on the maximum ecological function. It is also found that the effect of internal irreversibility parameter is more than the other parameters not only on the maximum ecological function but also on the corresponding power output and the thermal efficiency

  3. Performance characteristics and parametric optimization of an irreversible magnetic Ericsson heat-pump

    International Nuclear Information System (INIS)

    Wei Fang; Lin Guoxing; Chen Jincan; Brueck, Ekkes

    2011-01-01

    Taking into account the finite-rate heat transfer in the heat-transfer processes, heat leak between the two external heat reservoirs, regenerative loss, regeneration time, and internal irreversibility due to dissipation of the cycle working substance, an irreversible magnetic Ericsson heat-pump cycle is presented. On the basis of the thermodynamic properties of magnetic materials, the performance characteristics of the irreversible magnetic Ericsson heat-pump are investigated and the relationship between the optimal heating load and the coefficient of performance (COP) is derived. Moreover, the maximum heating load and the corresponding COP as well as the maximum COP and the corresponding heating load are obtained. Furthermore, the other optimal performance characteristics are discussed in detail. The results obtained here may provide some new information for the optimal parameter design and the development of real magnetic Ericsson heat-pumps. -- Research Highlights: →The effects of multi-irreversibilities on the performance of a magnetic heat-pump are revealed. →Mathematical expressions of the heating load and the COP are derived and the optimal performance and operating parameters are analyzed and discussed. →Several important performance bounds are determined.

  4. Ecological optimization and performance study of irreversible Stirling and Ericsson heat engines

    Science.gov (United States)

    Tyagi, S. K.; Kaushik, S. C.; Salhotra, R.

    2002-10-01

    The concept of finite time thermodynamics is used to determine the ecological function of irreversible Stirling and Ericsson heat engine cycles. The ecological function is defined as the power output minus power loss (irreversibility), which is the ambient temperature times, the entropy generation rate. The ecological function is maximized with respect to cycle temperature ratio and the expressions for the corresponding power output and thermal efficiency are derived at the optimal operating conditions. The effect of different operating parameters, the effectiveness on the hot, cold and the regenerative side heat exchangers, the cycle temperature ratio, heat capacitance ratio and the internal irreversibility parameter on the maximum ecological function are studied. It is found that the effect of regenerator effectiveness is more than the hot and cold side heat exchangers and the effect of the effectiveness on cold side heat exchanger is more than the effectiveness on the hot side heat exchanger on the maximum ecological function. It is also found that the effect of internal irreversibility parameter is more than the other parameters not only on the maximum ecological function but also on the corresponding power output and the thermal efficiency.

  5. Enzymatic modification of natural and synthetic polymers using lipases and proteases

    Science.gov (United States)

    Chakraborty, Soma

    Enzymatic modification of natural/synthetic polymers [starch nanoparticles, poly (n-alkyl acrylates) and poly(vinyl formamide)] was studied. Enzymes used for catalysis were lipases and proteases. Starch nanoparticles (40nm diameter) were incorporated into AOT-coated reverse micelles. Reactions performed with the acylating agents vinyl stearate, epsilon-caprolactone and maleic anhydride in toluene in presence of Novozyme-435 at 40°C for 36h gave products with degrees of substitution of 0.8, 0.6 and 0.4 respectively. DEPT-135 NMR spectra revealed that the modification occurred regioselectively at the C-6 position of the glucose units. Infrared microspectroscopy showed that the surfactant coated starch nanoparticles diffuse into pores of Novozyme-435 beads, coming in close proximity with CALB to promote modification. The modified products retained nanoscale dimensions. Catalysis of amide bond formation between a low molar mass amine and ester side groups of poly(n-alkyl acrylates)[poly(ethyl acrylate), poly(methyl acrylate) and poly(butyl acrylate)] was also examined. The nucleophiles were mono and diamines. Among the poly(n-alkyl acrylates) and the lipases studied, poly(ethyl acrylate) was the preferred substrate and Novozyme-435 the most active lipase. Poly(ethyl acrylate) in 80% by-volume toluene was reacted with 1 equivalent per repeat unit of hexyl amine at 70°C in presence of Novozyme-435. The product contained 10.6 mol% amide groups. Attempts to increase the amidation beyond 10--11 mol% by increasing the reaction time or use of fresh enzyme were unsuccessful, showing that poly(ethylacrylate-co-10mol%hexylacrylamide) is a poor substrate for further acylation. When chiral amines ([R,S]-alpha-methyl benzylamine, [R,S]-beta-methyl phenyl amine) were used as nucleophiles, Novozyme-435 enantioselectively catalyzed amidation of poly(ethyl acrylate). Poly(vinyl formamide), P(VfAm) by acid or base-catalyzed hydrolysis leads to poly(vinylamine), P(VAm), and

  6. Stochastic amplification and signaling in enzymatic futile cycles through noise-induced bistability with oscillations

    Science.gov (United States)

    Samoilov, Michael; Plyasunov, Sergey; Arkin, Adam P.

    2005-02-01

    Stochastic effects in biomolecular systems have now been recognized as a major physiologically and evolutionarily important factor in the development and function of many living organisms. Nevertheless, they are often thought of as providing only moderate refinements to the behaviors otherwise predicted by the classical deterministic system description. In this work we show by using both analytical and numerical investigation that at least in one ubiquitous class of (bio)chemical-reaction mechanisms, enzymatic futile cycles, the external noise may induce a bistable oscillatory (dynamic switching) behavior that is both quantitatively and qualitatively different from what is predicted or possible deterministically. We further demonstrate that the noise required to produce these distinct properties can itself be caused by a set of auxiliary chemical reactions, making it feasible for biological systems of sufficient complexity to generate such behavior internally. This new stochastic dynamics then serves to confer additional functional modalities on the enzymatic futile cycle mechanism that include stochastic amplification and signaling, the characteristics of which could be controlled by both the type and parameters of the driving noise. Hence, such noise-induced phenomena may, among other roles, potentially offer a novel type of control mechanism in pathways that contain these cycles and the like units. In particular, observations of endogenous or externally driven noise-induced dynamics in regulatory networks may thus provide additional insight into their topology, structure, and kinetics. network motif | signal transduction | chemical reaction | synthetic biology | systems biology

  7. Armature reaction of permanent magnet-excited small dc motors with shell type magnets and possibilities of power increase

    Energy Technology Data Exchange (ETDEWEB)

    Gutt, H J; Tran, Q N

    1983-07-01

    Permanent magnet-excited small dc motors allow an increase of power up to 30% compared with present permanent excited motors. The calculation of immediate irreversible demagnetization of the air-gap situated shell type magnets is necessary for a good motor design. Numerical calculated field line plots show the critical zones of the irreversible demagnetization at high armature reaction and refer how to avoid the flux loss and to increase the motor power.

  8. Ecological optimization of an irreversible quantum Carnot heat engine with spin-1/2 systems

    International Nuclear Information System (INIS)

    Liu Xiaowei; Chen Lingen; Wu Feng; Sun Fengrui

    2010-01-01

    A model of a quantum heat engine with heat resistance, internal irreversibility and heat leakage and many non-interacting spin-1/2 systems is established in this paper. The quantum heat engine cycle is composed of two isothermal processes and two irreversible adiabatic processes and is referred to as a spin quantum Carnot heat engine. Based on the quantum master equation and the semi-group approach, equations of some important performance parameters, such as power output, efficiency, entropy generation rate and ecological function (a criterion representing the optimal compromise between exergy output rate and exergy loss rate), for the irreversible spin quantum Carnot heat engine are derived. The optimal ecological performance of the heat engine in the classical limit is analyzed with numerical examples. The effects of internal irreversibility and heat leakage on ecological performance are discussed in detail.

  9. Chemical interaction of disulfiram with nitrosodimethylamine after in vitro enzymatic activation

    International Nuclear Information System (INIS)

    Tacchi, A.M.; Bertram, B.; Wiessler, M.

    1984-01-01

    The in vitro reaction between disulfiram (DSF) and N-nitroso[ 14 C]dimethylamine [( 14 C]NDMA) was studied. Incubations of DSF with [ 14 C]NDMA were carried out in the presence of rat liver microsomes, control 9000 g (S9) supernatant fraction and phenobarbital-induced S9 fraction. HPLC analysis and liquid scintillation measurement provided evidence for the formation of methyldiethyldithiocarbamate (MeDDTC) as a product of the reaction between diethyldithiocarbamate (DDTC), the main active metabolite of DSF and the 'methyl-cation' released by NDMA after enzymatic activation. The amount of MeDDTC found here was consistent with the rate of oxidation of NDMA to formaldehyde. Scintillation counting confirmed that other radioactive peaks, not due to MeDDTC, were unrelated to the methylation of L-cysteine by [ 14 C]NDMA

  10. CONTINUOUS AND SEMICONTINUOUS REACTION SYSTEMS FOR HIGH-SOLIDS ENZYMATIC HYDROLYSIS OF LIGNOCELLULOSICS

    Directory of Open Access Journals (Sweden)

    A. González Quiroga

    2015-12-01

    Full Text Available Abstract An attractive operation strategy for the enzymatic hydrolysis of lignocellulosics results from dividing the process into three stages with complementary goals: continuous enzyme adsorption at low-solids loading (5% w/w with recycling of the liquid phase; continuous liquefaction at high-solids content (up to 20% w/w; and, finally, continuous or semicontinuous hydrolysis with supplementation of fresh enzymes. This paper presents a detailed modeling and simulation framework for the aforementioned operation strategies. The limiting micromixing situations of macrofluid and microfluid are used to predict conversions. The adsorption and liquefaction stages are modeled as a continuous stirred tank and a plug flow reactor, respectively. Two alternatives for the third stage are studied: a train of five cascading stirred tanks and a battery of batch reactors in parallel. Simulation results show that glucose concentrations greater than 100 g L-1 could be reached with both of the alternatives for the third stage.

  11. Profit rate performance optimization for a generalized irreversible ...

    Indian Academy of Sciences (India)

    fer law system generalized irreversible combined refrigeration cycle model with finite-rate heat ...... Chen L, Sun F, Wu C 2004b Optimum allocation of heat exchanger area for refrigeration and air conditioning plants. Appl. Energy 77(3): 339– ...

  12. Binding of Nickel to Testicular Glutamate–Ammonia Ligase Inhibits Its Enzymatic Activity

    Science.gov (United States)

    SUN, YINGBIAO; OU, YOUNG; CHENG, MIN; RUAN, YIBING; VAN DER HOORN, FRANS A.

    2016-01-01

    SUMMARY Exposure to nickel has been shown to cause damage to the testis in several animal models. It is not known if the testis expresses protein(s) that can bind nickel. To test this, we used a nickel-binding assay to isolate testicular nickel-binding proteins. We identified glutamate–ammonia ligase (GLUL) as a prominent nickel-binding protein by mass spectrometry. Protein analysis and reverse transcriptase polymerase chain reaction showed that GLUL is expressed in the testis, predominantly in interstitial cells. We determined that GLUL has a higher affinity for nickel than for its regular co-factor manganese. We produced an enzymatically active, recombinant GLUL protein. Upon binding, nickel interferes with the manganese-catalyzed enzymatic activity of recombinant GLUL protein. We also determined that GLUL activity in testes of animals exposed to nickel sulfate is reduced. Our results identify testicular GLUL as the first testicular protein shown to be affected by nickel exposure. PMID:21254280

  13. [Experiences with the enzymatic determination of sugar and sugar substitutes in dietetic cake for diabetics (author's transl)].

    Science.gov (United States)

    Klingebiel, L; Grossklaus, R; Pahlke, G

    1979-11-01

    Sorbitol and fructose were determined enzymatically in home-made and commercially produced cake for diabetics. In some commercial products, a loss of fructose depending upon the baking period was found. This loss of fructose is to be attributed to the Maillard reaction. The findings were confirmed by comparative studies will a reference cake.

  14. Effects on nuclear fusion reaction on diffusion and thermal conduction in a magnetoplasma

    International Nuclear Information System (INIS)

    Sakai, Kazuo; Aono, Osamu.

    1976-12-01

    In spite of the well spread belief in the field of irreversible thermodynamics, vectorial phenomena couple thermodynamically with the scalar phenomena. Transport coefficients concerning the diffusion and the thermal conduction across a strong magnetic field are calculated in the presence of the deuteron-triton fusion reaction on the basis of the gas kinetic theory. When the reaction takes place, the diffusion increases and the thermal conduction decreases. Effects of the reaction exceed those of the Coulomb collision as the temperature is high enough. (auth.)

  15. Process development for gelatinisation and enzymatic hydrolysis of starch at high concentrations

    OpenAIRE

    Baks, T.

    2007-01-01

    cum laude graduation (with distinction) Enzymatic hydrolysis of starch is encountered in day-to-day life for instance in the dishwasher during removal of stains with detergents or in our mouth during chewing of starch-based foods in the presence of saliva. The reaction is also important for the (food) industry, for example for the production of beer or bio-ethanol. In industry, it is usually preceded by gelatinisation to make the starch molecules available for the enzymes. Both gelatinisation...

  16. Colorimetric method for enzymatic screening assay of ATP using Fe(III)-xylenol orange complex formation.

    Science.gov (United States)

    Ishida, Akihiko; Yamada, Yasuko; Kamidate, Tamio

    2008-11-01

    In hygiene management, recently there has been a significant need for screening methods for microbial contamination by visual observation or with commonly used colorimetric apparatus. The amount of adenosine triphosphate (ATP) can serve as the index of a microorganism. This paper describes the development of a colorimetric method for the assay of ATP, using enzymatic cycling and Fe(III)-xylenol orange (XO) complex formation. The color characteristics of the Fe(III)-XO complexes, which show a distinct color change from yellow to purple, assist the visual observation in screening work. In this method, a trace amount of ATP was converted to pyruvate, which was further amplified exponentially with coupled enzymatic reactions. Eventually, pyruvate was converted to the Fe(III)-XO complexes through pyruvate oxidase reaction and Fe(II) oxidation. As the assay result, yellow or purple color was observed: A yellow color indicates that the ATP concentration is lower than the criterion of the test, and a purple color indicates that the ATP concentration is higher than the criterion. The method was applied to the assay of ATP extracted from Escherichia coli cells added to cow milk.

  17. Irreversible electroporation: state of the art

    Directory of Open Access Journals (Sweden)

    Wagstaff PGK

    2016-04-01

    Full Text Available Peter GK Wagstaff,1 Mara Buijs,1 Willemien van den Bos,1 Daniel M de Bruin,2 Patricia J Zondervan,1 Jean JMCH de la Rosette,1 M Pilar Laguna Pes1 1Department of Urology, 2Department of Biomedical Engineering and Physics, Academic Medical Center, Amsterdam, the Netherlands Abstract: The field of focal ablative therapy for the treatment of cancer is characterized by abundance of thermal ablative techniques that provide a minimally invasive treatment option in selected tumors. However, the unselective destruction inflicted by thermal ablation modalities can result in damage to vital structures in the vicinity of the tumor. Furthermore, the efficacy of thermal ablation intensity can be impaired due to thermal sink caused by large blood vessels in the proximity of the tumor. Irreversible electroporation (IRE is a novel ablation modality based on the principle of electroporation or electropermeabilization, in which electric pulses are used to create nanoscale defects in the cell membrane. In theory, IRE has the potential of overcoming the aforementioned limitations of thermal ablation techniques. This review provides a description of the principle of IRE, combined with an overview of in vivo research performed to date in the liver, pancreas, kidney, and prostate. Keywords: irreversible electroporation, IRE, tumor, ablation, focal therapy, cancer

  18. Sugar ester surfactants: enzymatic synthesis and applications in food industry.

    Science.gov (United States)

    Neta, Nair S; Teixeira, José A; Rodrigues, Lígia R

    2015-01-01

    Sugar esters are non-ionic surfactants that can be synthesized in a single enzymatic reaction step using lipases. The stability and efficiency of lipases under unusual conditions and using non-conventional media can be significantly improved through immobilization and protein engineering. Also, the development of de novo enzymes has seen a significant increase lately under the scope of the new field of synthetic biology. Depending on the esterification degree and the nature of fatty acid and/or sugar, a range of sugar esters can be synthesized. Due to their surface activity and emulsifying capacity, sugar esters are promising for applications in food industry.

  19. Enzymatic description of the anhydrofructose pathway of glycogen degradation. I

    DEFF Research Database (Denmark)

    Yu, Shukun; Refdahl, Charlotte; Lundt, Inge

    2004-01-01

    The anhydrofructose pathway describes the degradation of glycogen and starch to metabolites via 1,5-anhydro-D-fructose (1,5AnFru). The enzyme catalyzing the first reaction step of this pathway, i.e., a-1,4-glucan lyase (EC 4.2.1.13), has been purified, cloned and characterized from fungi and red...... possessed all enzymes needed for conversion of glycogen to APP, an a-1,4-glucan lyase from this fungus was isolated and partially sequenced. Based on this work, a scheme of the enzymatic description of the anhydrofructose pathway in A. melaloma was proposed. Keywords: Anhydrofructose pathway; Anthracobia...

  20. Optimization of enzymatic hydrolysis of guar gum using response surface methodology

    OpenAIRE

    Mudgil, Deepak; Barak, Sheweta; Khatkar, B. S.

    2012-01-01

    Guar gum is a polysaccharide obtained from guar seed endosperm portion. Enzymatically hydrolyzed guar gum is low in viscosity and has several health benefits as dietary fiber. In this study, response surface methodology was used to determine the optimum conditions for hydrolysis that give minimum viscosity of guar gum. Central composite was employed to investigate the effects of pH (3–7), temperature (20–60 °C), reaction time (1–5 h) and cellulase concentration (0.25–1.25 mg/g) on viscosity d...

  1. The degree of irreversibility in deterministic finite automata

    DEFF Research Database (Denmark)

    Axelsen, Holger Bock; Holzer, Markus; Kutrib, Martin

    2016-01-01

    the language, and show that the degree induces a strict infinite hierarchy of languages. We examine how the degree of irreversibility behaves under the usual language operations union, intersection, complement, concatenation, and Kleene star, showing tight bounds (some asymptotically) on the degree....

  2. Exergetic efficiency optimization for an irreversible heat pump ...

    Indian Academy of Sciences (India)

    This paper deals with the performance analysis and optimization for irreversible heat pumps working on reversed Brayton cycle with constant-temperature heat reservoirs by taking exergetic efficiency as the optimization objective combining exergy concept with finite-time thermodynamics (FTT). Exergetic efficiency is ...

  3. Monoacylglycerol synthesis via enzymatic glycerolysis using a simple and efficient reaction system

    DEFF Research Database (Denmark)

    Yang, Tiankui; MORTEN, REBSDORF; ULRIK, ENGELRUD

    2005-01-01

    TL IM and Novozym 435 were employed in a batch reaction system. Novozym 435 showed better properties in glycerolysis. The increased temperature and high glycerol/oil ratio had little effect on the yield of MAGs in such a system. The reaction in a packed bed reactor (PBR) gave lower yield of MAGs...

  4. Functional bio-based polyesters by enzymatic polymerization

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Hoffmann, Christian; Andersen, Christian

    During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting...... polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels...... based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been...

  5. Pretreatment and enzymatic hydrolysis of lignocellulosic biomass

    Science.gov (United States)

    Corredor, Deisy Y.

    The performance of soybean hulls and forage sorghum as feedstocks for ethanol production was studied. The main goal of this research was to increase fermentable sugars' yield through high-efficiency pretreatment technology. Soybean hulls are a potential feedstock for production of bio-ethanol due to their high carbohydrate content (≈50%) of nearly 37% cellulose. Soybean hulls could be the ideal feedstock for fuel ethanol production, because they are abundant and require no special harvesting and additional transportation costs as they are already in the plant. Dilute acid and modified steam-explosion were used as pretreatment technologies to increase fermentable sugars yields. Effects of reaction time, temperature, acid concentration and type of acid on hydrolysis of hemicellulose in soybean hulls and total sugar yields were studied. Optimum pretreatment parameters and enzymatic hydrolysis conditions for converting soybean hulls into fermentable sugars were identified. The combination of acid (H2SO4, 2% w/v) and steam (140°C, 30 min) efficiently solubilized the hemicellulose, giving a pentose yield of 96%. Sorghum is a tropical grass grown primarily in semiarid and dry parts of the world, especially in areas too dry for corn. The production of sorghum results in about 30 million tons of byproducts mainly composed of cellulose, hemicellulose, and lignin. Forage sorghum such as brown midrib (BMR) sorghum for ethanol production has generated much interest since this trait is characterized genetically by lower lignin concentrations in the plant compared with conventional types. Three varieties of forage sorghum and one variety of regular sorghum were characterized and evaluated as feedstock for fermentable sugar production. Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and X-Ray diffraction were used to determine changes in structure and chemical composition of forage sorghum before and after pretreatment and enzymatic hydrolysis

  6. Enzymatic carotenoid cleavage in star fruit (Averrhoa carambola).

    Science.gov (United States)

    Fleischmann, Peter; Watanabe, Naoharu; Winterhalter, Peter

    2003-05-01

    This paper presents the first description of an enzyme fraction exhibiting carotenoid cleavage activity isolated from fruit skin of Averrhoa carambola. Partial purification of the enzyme could be achieved by acetone precipitation, ultrafiltration (300 kDa, 50 kDa), isoelectric focusing (pH 3-10) and sodium dodecyl sulfate polyacrylamide gel electrophoresis (7.5%). In this way, an enzymatically active protein fraction was obtained, consisting of four proteins in the molecular weight range of between 12 and 90 kDa. Using beta-carotene as substrate, the enzyme activity was detected spectrophotometrically at 505 nm. The main reaction product, detected by GC analysis, was beta-ionone. This proves that the isolated enzymes are closely related to aroma metabolism and release of star fruit. The time constant of the reaction was 16.6 min, the Michaelis Constant K(m)=3.6 micromol 1(-1) and the maximum velocity V(max)=10.5 x 10(-3) micromol l(-1) s(-1) mg((Protein))(-1). The optimum temperature was 45 degrees C.

  7. Effects of Surfactants on the Rate of Chemical Reactions

    Directory of Open Access Journals (Sweden)

    B. Samiey

    2014-01-01

    Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.

  8. Microwave irradiation of lignocellulosic materials, 4: Enhancement of enzymatic susceptibility of microwave-irradiated softwoods

    International Nuclear Information System (INIS)

    Azuma, J.; Higashino, J.; Isaka, M.; Koshijima, T.

    1985-01-01

    Effect of microwave irradiation on the enzymatic susceptibility of various softwoods was investigated. The pH values of the reaction liquor dropped with increasing temperature to 2.9-3.3 at 230°C, consistent with increase in acidity (0.5-0.85 meq at 230-239° C). Above approximately 180°C, hemicellulose underwent acid-mediated autohydrolysis and became water-soluble yielding a mixture of oligosaccharides and monosaccharides. The composition of water-soluble portion was similar for all wood species tested. The maximum extents of saccharification below 240°C ranged between 36-62% for softwoods, while those for hardwoods were between 88-93%. The present investigation confirmed that microwave pretreatment enhanced the enzymatic susceptibility of various softwoods. However, further attempt should be needed to give higher values equal to those for hardwoods. (author)

  9. Enzymatic polymerization of aniline in the presence of different inorganic substrates

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Loyola, E. [Centro de Investigacion en Quimica Aplicada, Blvd. Enrique Reyna No. 140, CP 25100 Saltillo, Coah (Mexico); Escuela de Ciencias Biologicas, UA de C. Carr. Torreon-Matamoros Km 7.5, Ciudad Universitaria, CP 27400 Torreon, Coah. (Mexico)], E-mail: erika-flores@mail.uadec.mx; Cruz-Silva, R. [Centro de Investigacion en Ingenieria y Ciencias Aplicadas, UAEM. Av. Universidad 1001, Col. Chamilpa, CP 62210, Cuernavaca Mor. (Mexico); Romero-Garcia, J.; Angulo-Sanchez, J.L. [Centro de Investigacion en Quimica Aplicada, Blvd. Enrique Reyna No. 140, CP 25100 Saltillo, Coah (Mexico); Castillon, F.F.; Farias, M.H. [Centro de Ciencias de la Materia Condensada de la UNAM, Apdo. Postal 2681, CP 22800 Ensenada, B.C. (Mexico)

    2007-09-15

    The effect of different inorganic substrates in the structure of polyaniline synthesized by enzymatic oxidation was studied. The polymer characterization was done by electronic absorption and X-ray photoelectron spectroscopy. The substrates studied were: controlled pore glass, mordenite, zeolite Y, zeolite MCM-41, Wollastonite, silica gel, fuming silica and short glass fibers type E. Polyaniline was synthesized in the presence of the substrates under acidic aqueous conditions, using hydrogen peroxide as oxidizer and HRP or SBP enzymes as catalyst. The composition of the substrates strongly affected the degree of electronic conjugation of the synthesized polyaniline, whereas the pore size and the enzyme type apparently had no effect. The chemical structure of polyaniline enzymatically synthesized was more sensitive to the substrate composition than that chemically synthesized. Apparently substrates containing alkaline ions, such as sodium and calcium, promoted the formation of the branched, non-conductive polyaniline form. The effect of the substrates on the polyaniline structure can be explained considering the local pH effect of the templates surface on the coupling reaction of aniline radicals.

  10. Enzymatic Phorbol Esters Degradation using the Germinated Jatropha Curcas Seed Lipase as Biocatalyst: Optimization Process Conditions by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Avita Kusuma Wardhani

    2016-10-01

    Full Text Available Utilization of Jatropha curcas seed cake is limited by the presence of phorbol esters (PE, which are the main toxic compound and heat stable. The objective of this research was to optimize the reaction conditions of the enzymatic PE degradation of the defatted Jatropha curcas seed cake (DJSC using the acetone-dried lipase from the germinated Jatropha curcas seeds as a biocatalyst. Response Surface Methodology (RSM using three-factors-three-levels Box-Behnken design was used to evaluate the effects of the reaction time, the ratio of buffer volume to DJSC, and the ratio of enzyme to DJSC on PE degradation. The results showed that the optimum conditions of PE degradation were 29.33 h, 51.11 : 6 (mL/g, and 30.10 : 5 (U/g cake for the reaction time, the ratio of buffer volume to DJSC, and the ratio of enzyme to DJSC, respectively. The predicted degradation of PE was 98.96% and not significantly different with the validated data of PE degradation. PE content was 0.035 mg/g, in which it was lower than PE in non-toxic Jatropha seeds. The results indicated that enzymatic degradation of PE might be a promising method for degradation of PE.  Copyright © 2016 BCREC GROUP. All rights reserved Received: 22nd December 2015; Revised: 1st April 2016; Accepted: 14th April 2016 How to Cite: Wardhani, A.K., Hidayat, C., Hastuti, P. (2016. Enzymatic Phorbol Esters Degradation using the Germinated Jatropha Curcas Seed Lipase as Biocatalyst: Optimization Process Conditions by Response Surface Methodology. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 346-353 (doi:10.9767/bcrec.11.3.574.346-353 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.574.346-353

  11. Properties important for solid–liquid separations change during the enzymatic hydrolysis of pretreated wheat straw

    DEFF Research Database (Denmark)

    Weiss, Noah Daniel; Felby, Claus; Thygesen, Lisbeth Garbrecht

    2018-01-01

    Objectives The biochemical conversion of lignocellulosic biomass into renewable fuels and chemicals provides new challenges for industrial scale processes. One such process, which has received little attention, but is of great importance for efficient product recovery, is solid–liquid separations......, which may occur both after pretreatment and after the enzymatic hydrolysis steps. Due to the changing nature of the solid biomass during processing, the solid–liquid separation properties of the biomass can also change. The objective of this study was to show the effect of enzymatic hydrolysis...... of cellulose upon the water retention properties of pretreated biomass over the course of the hydrolysis reaction. Results Water retention value measurements, coupled with 1H NMR T2 relaxometry data, showed an increase in water retention and constraint of water by the biomass with increasing levels...

  12. DOTA-Functionalized Polylysine: A High Number of DOTA Chelates Positively Influences the Biodistribution of Enzymatic Conjugated Anti-Tumor Antibody chCE7agl.

    OpenAIRE

    Grünberg Jürgen; Jeger Simone; Sarko Dikran; Dennler Patrick; Zimmermann Kurt; Mier Walter; Schibli Roger

    2013-01-01

    Site-specific enzymatic reactions with microbial transglutaminase (mTGase) lead to a homogenous species of immunoconjugates with a defined ligand/antibody ratio. In the present study, we have investigated the influence of different numbers of 1,4,7,10-tetraazacyclododecane-N-N'-N''-N'''-tetraacetic acid (DOTA) chelats coupled to a decalysine backbone on the in vivo behavior of the chimeric monoclonal anti-L1CAM antibody chCE7agl. The enzymatic conjugation of (DOTA)1-decalysine, (DOTA)3-decaly...

  13. Irreversible denaturation of maltodextrin glucosidase studied by differential scanning calorimetry, circular dichroism, and turbidity measurements.

    Science.gov (United States)

    Goyal, Megha; Chaudhuri, Tapan K; Kuwajima, Kunihiro

    2014-01-01

    Thermal denaturation of Escherichia coli maltodextrin glucosidase was studied by differential scanning calorimetry, circular dichroism (230 nm), and UV-absorption measurements (340 nm), which were respectively used to monitor heat absorption, conformational unfolding, and the production of solution turbidity. The denaturation was irreversible, and the thermal transition recorded at scan rates of 0.5-1.5 K/min was significantly scan-rate dependent, indicating that the thermal denaturation was kinetically controlled. The absence of a protein-concentration effect on the thermal transition indicated that the denaturation was rate-limited by a mono-molecular process. From the analysis of the calorimetric thermograms, a one-step irreversible model well represented the thermal denaturation of the protein. The calorimetrically observed thermal transitions showed excellent coincidence with the turbidity transitions monitored by UV-absorption as well as with the unfolding transitions monitored by circular dichroism. The thermal denaturation of the protein was thus rate-limited by conformational unfolding, which was followed by a rapid irreversible formation of aggregates that produced the solution turbidity. It is thus important to note that the absence of the protein-concentration effect on the irreversible thermal denaturation does not necessarily means the absence of protein aggregation itself. The turbidity measurements together with differential scanning calorimetry in the irreversible thermal denaturation of the protein provided a very effective approach for understanding the mechanisms of the irreversible denaturation. The Arrhenius-equation parameters obtained from analysis of the thermal denaturation were compared with those of other proteins that have been reported to show the one-step irreversible thermal denaturation. Maltodextrin glucosidase had sufficiently high kinetic stability with a half-life of 68 days at a physiological temperature (37°C).

  14. Production of resistant starch by enzymatic debranching in legume flours.

    Science.gov (United States)

    Morales-Medina, Rocío; Del Mar Muñío, María; Guadix, Emilia M; Guadix, Antonio

    2014-01-30

    Resistant starch (RS) was produced by enzymatic hydrolysis of flours from five different legumes: lentil, chickpea, faba bean, kidney bean and red kidney bean. Each legume was firstly treated thermally, then hydrolyzed with pullulanase for 24h at 50°C and pH 5 and lyophilized. At the end of each hydrolysis reaction, the RS amount ranged from 4.7% for red kidney beans to 7.5% for chickpeas. With respect to the curves of RS against hydrolysis time, a linear increase was observed initially and a plateau was generally achieved by the end of reaction. These curves were successfully modeled by a kinetic equation including three parameters: initial RS, RS at long operation time and a kinetic constant (k). Furthermore, the relative increase in hydrolysis, calculated using the kinetic parameters, was successfully correlated to the percentage of amylose. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Anesthetic Efficacy in Irreversible Pulpitis: A Randomized Clinical Trial.

    Science.gov (United States)

    Allegretti, Carlos E; Sampaio, Roberta M; Horliana, Anna C R T; Armonia, Paschoal L; Rocha, Rodney G; Tortamano, Isabel Peixoto

    2016-01-01

    Inferior alveolar nerve block has a high failure rate in the treatment of mandibular posterior teeth with irreversible pulpitis. The aim of this study was to compare the anesthetic efficacy of 4% articaine, 2% lidocaine and 2% mepivacaine, all in combination with 1:100,000 epinephrine, in patients with irreversible pulpitis of permanent mandibular molars during a pulpectomy procedure. Sixty-six volunteers from the Emergency Center of the School of Dentistry, University of São Paulo, randomly received 3.6 mL of local anesthetic as a conventional inferior alveolar nerve block (IANB). The subjective signal of lip numbness, pulpal anesthesia and absence of pain during the pulpectomy procedure were evaluated respectively, by questioning the patient, stimulation using an electric pulp tester and a verbal analogue scale. All patients reported the subjective signal of lip numbness. Regarding pulpal anesthesia success as measured with the pulp tester, the success rate was respectively 68.2% for mepivacaine, 63.6% for articaine and 63.6% for lidocaine. Regarding patients who reported no pain or mild pain during the pulpectomy, the success rate was, respectively 72.7% for mepivacaine, 63.6% for articaine and 54.5% for lidocaine. These differences were not statistically significant. Neither of the solutions resulted in 100% anesthetic success in patients with irreversible pulpitis of mandibular molars.

  16. Bi-modified Pd/C catalyst via irreversible adsorption and its catalytic activity for ethanol oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Cai, Jindi; Huang, Yiyin; Guo, Yonglang

    2013-01-01

    Highlights: • Pd-Bi/C catalysts were easily prepared by irreversible adsorption of Bi on Pd/C surface. • The adsorption of Bi increases the oxygen-containing species obviously on Pd-Bi/C surface. • Only a little amount of Bi on Pd-Bi/C can play a significant role in ethanol oxidation reaction (EOR). • Current density of EOR on Pd-Bi/C (20:1) is 2.4 times higher than that on Pd/C. • Anti-poisoning ability and durability of Pd-Bi/C (20:1) is greatly enhanced. -- Abstract: A facile approach to promote ethanol electro-oxidation on Pd-based catalysts is presented by the modification of Bi on Pd/C catalyst via irreversible adsorption. X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) measurements show that the modification of Bi has no significant effect on the Pd morphology and particle size distribution. Bi(III) and Pd(0) are the dominant forms in Pd-Bi/C catalyst. Electrochemical tests show that the modification of the appropriate amount of Bi on Pd/C catalyst can remarkably enhance activity toward ethanol oxidation reaction (EOR) up to about 2.4 times higher compared to Pd/C catalyst. The Pd-Bi/C (20:1) catalyst exhibits excellent stability and enhances CO tolerance. The enhanced electrochemical performance of Pd-Bi/C catalyst is attributed to the electronic effect and the bifunctional mechanism. The high exchange current density and the low apparent activation energy on Pd-Bi/C (20:1) catalyst reveal its faster kinetics and higher intrinsic activity compared to Pd/C catalyst

  17. Sample size effect on the determination of the irreversibility line of high-Tc superconductors

    International Nuclear Information System (INIS)

    Li, Q.; Suenaga, M.; Li, Q.; Freltoft, T.

    1994-01-01

    The irreversibility lines of a high-J c superconducting Bi 2 Sr 2 Ca 2 Cu 3 O x /Ag tape were systematically measured upon a sequence of subdivisions of the sample. The irreversibility field H r (T) (parallel to the c axis) was found to change approximately as L 0.13 , where L is the effective dimension of the superconducting tape. Furthermore, it was found that the irreversibility line for a grain-aligned Bi 2 Sr 2 Ca 2 Cu 3 O x specimen can be approximately reproduced by the extrapolation of this relation down to a grain size of a few tens of micrometers. The observed size effect could significantly obscure the real physical meaning of the irreversibility lines. In addition, this finding surprisingly indicated that the Bi 2 Sr 2 Ca 2 Cu 2 O x /Ag tape and grain-aligned specimen may have similar flux line pinning strength

  18. Trans-methylation reactions in plants: focus on the activated methyl cycle.

    Science.gov (United States)

    Rahikainen, Moona; Alegre, Sara; Trotta, Andrea; Pascual, Jesús; Kangasjärvi, Saijaliisa

    2018-02-01

    Trans-methylation reactions are vital in basic metabolism, epigenetic regulation, RNA metabolism, and posttranslational control of protein function and therefore fundamental in determining the physiological processes in all living organisms. The plant kingdom is additionally characterized by the production of secondary metabolites that undergo specific hydroxylation, oxidation and methylation reactions to obtain a wide array of different chemical structures. Increasing research efforts have started to reveal the enzymatic pathways underlying the biosynthesis of complex metabolites in plants. Further engineering of these enzymatic machineries offers significant possibilities in the development of bio-based technologies, but necessitates deep understanding of their potential metabolic and regulatory interactions. Trans-methylation reactions are tightly coupled with the so-called activated methyl cycle (AMC), an essential metabolic circuit that maintains the trans-methylation capacity in all living cells. Tight regulation of the AMC is crucial in ensuring accurate trans-methylation reactions in different subcellular compartments, cell types, developmental stages and environmental conditions. This review addresses the organization and posttranslational regulation of the AMC and elaborates its critical role in determining metabolic regulation through modulation of methyl utilization in stress-exposed plants. © 2017 Scandinavian Plant Physiology Society.

  19. Determination of myoglobin based on its enzymatic activity by stopped-flow spectrophotometry

    Science.gov (United States)

    Zheng, Qi; Liu, Zhihong; Cai, Ruxiu

    2005-04-01

    A new method has been developed for the determination of myoglobin (Mb) based on its enzymatic activity for the oxidation of o-phenylenediamine (OPDA) with hydrogen peroxide. Stopped-flow spectrophotometry was used to study the kinetic behavior of the oxidation reaction. The catalytic activity of Mb was compared to other three kinds of catalyst. The time dependent absorbance of the reaction product, 2,3-diamimophenazine (DAPN), at a wavelength of 426 nm was recorded. The initial reaction rate obtained at 40 °C was found to be proportional to the concentration of Mb in the range of 1.0 × 10 -6 to 4.0 × 10 -9 mol L -1. The detection limit of Mb was found to be 9.93 × 10 -10 mol L -1. The relative standard deviations were within 5% for the determination of different concentrations of Mb. Excess of bovine serum albumin (BSA), Ca(II), Mg(II), Cu(II), glucose, caffeine, lactose and uric acid did not interfere.

  20. Physico-chemical, spectroscopical and thermal characterization of bio diesel obtained by enzymatic route as a tool to select the most efficient immobilized lipase

    International Nuclear Information System (INIS)

    Silva, G.A.M.; Ros, P.C.M. da; Souza, L.T.A.; Costa, A.P.O.; Castro, H.F. de

    2012-01-01

    Two microbial lipases from Burkholderia cepacia and Pseudomonas fluorescens were evaluated as catalysts for the enzymatic transesterification of beef tallow with ethanol and the most efficient lipase source was selected by taking into account the properties of the product to be used as fuel. Both lipases were immobilized on an epoxy silica-polyvinyl alcohol composite by covalent immobilization and used to perform the reactions under the following operational conditions: beef tallow-to-ethanol molar ratio of 1:9, 45 degree C and 400 units of enzymatic activity per gram of fat. Products, characterized using Fourier Transform Infrared spectroscopy (FTIR), viscosimetry, thermogravimetry and 1 H NMR spectroscopy, suggested that the bio diesel sample obtained in the reaction catalyzed by Burkholderia cepacia lipase has the best set of properties for fuel usage. (author)

  1. Physico-chemical, spectroscopical and thermal characterization of bio diesel obtained by enzymatic route as a tool to select the most efficient immobilized lipase

    Energy Technology Data Exchange (ETDEWEB)

    Silva, G.A.M.; Ros, P.C.M. da; Souza, L.T.A.; Costa, A.P.O.; Castro, H.F. de, E-mail: heizir@dequi.eel.usp.br [Engineering School of Lorena. University of Sao Paulo (EEL/USP), Lorena, SP (Brazil)

    2012-01-15

    Two microbial lipases from Burkholderia cepacia and Pseudomonas fluorescens were evaluated as catalysts for the enzymatic transesterification of beef tallow with ethanol and the most efficient lipase source was selected by taking into account the properties of the product to be used as fuel. Both lipases were immobilized on an epoxy silica-polyvinyl alcohol composite by covalent immobilization and used to perform the reactions under the following operational conditions: beef tallow-to-ethanol molar ratio of 1:9, 45 degree C and 400 units of enzymatic activity per gram of fat. Products, characterized using Fourier Transform Infrared spectroscopy (FTIR), viscosimetry, thermogravimetry and {sup 1}H NMR spectroscopy, suggested that the bio diesel sample obtained in the reaction catalyzed by Burkholderia cepacia lipase has the best set of properties for fuel usage. (author)

  2. Irreversible absorption heat-pump and its optimal performance

    International Nuclear Information System (INIS)

    Chen Lingen; Qin Xiaoyong; Sun Fengrui; Wu Chih

    2005-01-01

    On the basis of an endoreversible absorption heat-pump cycle, a generalized irreversible four-heat-reservoir absorption heat-pump cycle model is established by taking account of the heat resistances, heat leak and irreversibilities due to the internal dissipation of the working substance. The heat transfer between the heat reservoir and the working substance is assumed to obey the linear (Newtonian) heat-transfer law, and the overall heat-transfer surface area of the four heat-exchangers is assumed to be constant. The fundamental optimal relations between the coefficient of performance (COP) and the heating-load, the maximum COP and the corresponding heating-load, the maximum heating load and the corresponding COP, as well as the optimal temperatures of the working substance and the optimal heat-transfer surface areas of the four heat-exchangers are derived by using finite-time thermodynamics. Moreover, the effects of the cycle parameters on the characteristics of the cycle are studied by numerical examples

  3. Quantum mechanical irreversibility and measurement

    CERN Document Server

    Grigolini, P

    1993-01-01

    This book is intended as a tutorial approach to some of the techniques used to deal with quantum dissipation and irreversibility, with special focus on their applications to the theory of measurements. The main purpose is to provide readers without a deep expertise in quantum statistical mechanics with the basic tools to develop a critical judgement on whether the major achievements in this field have to be considered a satisfactory solution of quantum paradox, or rather this ambitious achievement has to be postponed to when a new physics, more general than quantum and classical physics, will

  4. Enzymatic interesterification of palm stearin and coconut oil by a dual lipase system

    DEFF Research Database (Denmark)

    Ibrahim, Nuzul Amri Bin; Guo, Zheng; Xu, Xuebing

    2008-01-01

    greater than 100% over the theoretical value when the reaction proceeds for 2 h. The co-immobilization action of the carrier of the immobilized lipases towards the free lipase was proposed as being one of the reasons leading to the synergistic effect and this has been experimentally verified by a reaction......Enzymatic interesterification of palm stearin with coconut oil was conducted by applying a dual lipase system in comparison with individual lipase-catalyzed reactions. The results indicated that a synergistic effect occurred for many lipase combinations, but largely depending on the lipase species...... mixed and their ratios. The combination of Lipozyme TL IM and RM IM was found to generate a positive synergistic action at all test mixing ratios. Only equivalent amount mixtures of Lipozyme TL IM with Novozym 435 or Lipozyme RM IM with Novozym 435 produced a significant synergistic effect as well...

  5. Reversing the irreversible: From limit cycles to emergent time symmetry

    Science.gov (United States)

    Cortês, Marina; Smolin, Lee

    2018-01-01

    In 1979 Penrose hypothesized that the arrows of time are explained by the hypothesis that the fundamental laws are time irreversible [R. Penrose, in General Relativity: An Einstein Centenary Survey (1979)]. That is, our reversible laws, such as the standard model and general relativity are effective, and emerge from an underlying fundamental theory which is time irreversible. In [M. Cortês and L. Smolin, Phys. Rev. D 90, 084007 (2014), 10.1103/PhysRevD.90.084007; 90, 044035 (2014), 10.1103/PhysRevD.90.044035; 93, 084039 (2016), 10.1103/PhysRevD.93.084039] we put forward a research program aiming at realizing just this. The aim is to find a fundamental description of physics above the Planck scale, based on irreversible laws, from which will emerge the apparently reversible dynamics we observe on intermediate scales. Here we continue that program and note that a class of discrete dynamical systems are known to exhibit this very property: they have an underlying discrete irreversible evolution, but in the long term exhibit the properties of a time reversible system, in the form of limit cycles. We connect this to our original model proposal in [M. Cortês and L. Smolin, Phys. Rev. D 90, 084007 (2014), 10.1103/PhysRevD.90.084007], and show that the behaviors obtained there can be explained in terms of the same phenomenon: the attraction of the system to a basin of limit cycles, where the dynamics appears to be time reversible. Further than that, we show that our original models exhibit the very same feature: the emergence of quasiparticle excitations obtained in the earlier work in the space-time description is an expression of the system's convergence to limit cycles when seen in the causal set description.

  6. Nonequilibrium and irreversibility

    CERN Document Server

    Gallavotti, Giovanni

    2014-01-01

    This book concentrates on the properties of the stationary states in chaotic systems of particles or fluids, leaving aside the theory of the way they can be reached. The stationary states of particles or of fluids (understood as probability distributions on microscopic configurations or on the fields describing continua) have received important new ideas and data from numerical simulations and reviews are needed. The starting point is to find out which time invariant distributions come into play in physics. A special feature of this book is the historical approach. To identify the problems the author analyzes the papers of the founding fathers Boltzmann, Clausius and Maxwell including translations of the relevant (parts of ) historical documents. He also establishes a close link between treatment of irreversible phenomena in statistical mechanics and the theory of chaotic systems at and beyond the onset of turbulence as developed by Sinai, Ruelle, Bowen (SRB) and others: the author gives arguments intending t...

  7. Investment Irreversibility and Precautionary Savings in General Equilibrium

    DEFF Research Database (Denmark)

    Ejarque, João

    than irreversibility effects. If shocks are idiosyncratic and affect a cross section of agents over capital, an increase in their variance may induce an increase in aggregate investment even if all agents have an incentive to invest less, because zero investment is now an active lower bound for part...

  8. Fuel starvation. Irreversible degradation mechanisms in PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Rangel, Carmen M.; Silva, R.A.; Travassos, M.A.; Paiva, T.I.; Fernandes, V.R. [LNEG, National Laboratory for Energy and Geology, Lisboa (Portugal). UPCH Fuel Cells and Hydrogen Unit

    2010-07-01

    PEM fuel cell operates under very aggressive conditions in both anode and cathode. Failure modes and mechanism in PEM fuel cells include those related to thermal, chemical or mechanical issues that may constrain stability, power and lifetime. In this work, the case of fuel starvation is examined. The anode potential may rise to levels compatible with the oxidization of water. If water is not available, oxidation of the carbon support will accelerate catalyst sintering. Diagnostics methods used for in-situ and ex-situ analysis of PEM fuel cells are selected in order to better categorize irreversible changes of the cell. Electrochemical Impedance Spectroscopy (EIS) is found instrumental in the identification of fuel cell flooding conditions and membrane dehydration associated to mass transport limitations / reactant starvation and protonic conductivity decrease, respectively. Furthermore, it indicates that water electrolysis might happen at the anode. Cross sections of the membrane catalyst and gas diffusion layers examined by scanning electron microscopy indicate electrode thickness reduction as a result of reactions taking place during hydrogen starvation. Catalyst particles are found to migrate outwards and located on carbon backings. Membrane degradation in fuel cell environment is analyzed in terms of the mechanism for fluoride release which is considered an early predictor of membrane degradation. (orig.)

  9. Filtration behavior of casein glycomacropeptide (CGMP) in an enzymatic membrane reactor: fouling control by membrane selection and threshold flux operation

    DEFF Research Database (Denmark)

    Luo, Jianquan; Morthensen, Sofie Thage; Meyer, Anne S.

    2014-01-01

    . In this study, the filtration performance and fouling behavior during ultrafiltration (UF) of CGMP for the enzymatic production of 3′-sialyllactose were investigated. A 5kDa regenerated cellulose membrane with high anti-fouling performance, could retain CGMP well, permeate 3′-sialyllactose, and was found...... to be the most suitable membrane for this application. Low pH increased CGMP retention but produced more fouling. Higher agitation and lower CGMP concentration induced larger permeate flux and higher CGMP retention. Adsorption fouling and pore blocking by CGMP in/on membranes could be controlled by selecting...... a highly hydrophilic membrane with appropriate pore size. Operating under threshold flux could minimize the concentration polarization and cake/gel/scaling layers, but might not avoid irreversible fouling caused by adsorption and pore blocking. The effects of membrane properties, pH, agitation and CGMP...

  10. Enzymatic Degradation of Poly(ethylene 2,5-furanoate Powders and Amorphous Films

    Directory of Open Access Journals (Sweden)

    Simone Weinberger

    2017-10-01

    Full Text Available Poly(ethylene 2,5-furanoate (PEF is arousing great interest as a biobased alternative to plastics like poly(ethylene terephthalate (PET due to its wide range of potential applications, such as food and beverage packaging, clothing, and in the car industry. In the present study, the hydrolysis of PEF powders of different molecular masses (Mn = 55, Mw = 104 kg/mol and Mn = 18, Mw = 29 kg/mol and various particle sizes (180 < d and 180 < d < 425 µm using cutinase 1 from Thermobifida cellulosilytica (Thc_cut1 was studied. Thereby, the effects of molecular mass, particle size and crystallinity on enzymatic hydrolysis were investigated. The results show that particles with lower molecular mass are hydrolyzed faster than those with higher masses, and that the higher the molecular mass, the lower the influence of the particle size on the hydrolysis. Furthermore, cutinases from Humicola insolens (HiC and Thc_cut1 were compared with regard to their hydrolytic activity on amorphous PEF films (measured as release of 2,5-furandicarboxylic acid (FDCA and weight loss in different reaction media (1 M KPO pH 8, 0.1 M Tris-HCl pH 7 and at different temperatures (50 °C and 65 °C. A 100% hydrolysis of the PEF films was achieved after only 72 h of incubation with a HiC in 1 M KPO pH 8 at 65 °C. Moreover, the hydrolysis reaction was monitored by LC/TOF-MS analysis of the released reaction products and by Scanning Electron Microscopy (SEM examination of the polymer surfaces. Enzymatic hydrolysis of PEF with Thc_cut1 and HiC has potential for use in surface functionalization and recycling purposes.

  11. Linear irreversible thermodynamics and Onsager reciprocity for information-driven engines

    Science.gov (United States)

    Yamamoto, Shumpei; Ito, Sosuke; Shiraishi, Naoto; Sagawa, Takahiro

    2016-11-01

    In the recent progress in nonequilibrium thermodynamics, information has been recognized as a kind of thermodynamic resource that can drive thermodynamic current without any direct energy injection. In this paper, we establish the framework of linear irreversible thermodynamics for a broad class of autonomous information processing. In particular, we prove that the Onsager reciprocity holds true with information: The linear response matrix is well-defined and is shown symmetric with both of the information affinity and the conventional thermodynamic affinity. As an application, we derive a universal bound for the efficiency at maximum power for information-driven engines in the linear regime. Our result reveals the fundamental role of information flow in linear irreversible thermodynamics.

  12. Computational study on a puzzle in the biosynthetic pathway of anthocyanin: Why is an enzymatic oxidation/ reduction process required for a simple tautomerization?

    Science.gov (United States)

    Sato, Hajime; Wang, Chao; Yamazaki, Mami; Saito, Kazuki; Uchiyama, Masanobu

    2018-01-01

    In the late stage of anthocyanin biosynthesis, dihydroflavonol reductase (DFR) and anthocyanidin synthase (ANS) mediate a formal tautomerization. However, such oxidation/reduction process requires high energy and appears to be unnecessary, as the oxidation state does not change during the transformation. Thus, a non-enzymatic pathway of tautomerization has also been proposed. To resolve the long-standing issue of whether this non-enzymatic pathway is the main contributor for the biosynthesis, we carried out density functional theory (DFT) calculations to examine this non-enzymatic pathway from dihydroflavonol to anthocyanidin. We show here that the activation barriers for the proposed non-enzymatic tautomerization are too high to enable the reaction to proceed under normal aqueous conditions in plants. The calculations also explain the experimentally observed requirement for acidic conditions during the final step of conversion of 2-flaven-3,4-diol to anthocyanidin; a thermodynamically and kinetically favorable concerted pathway can operate under these conditions.

  13. Label-free and sensitive detection of T4 polynucleotide kinase activity via coupling DNA strand displacement reaction with enzymatic-aided amplification.

    Science.gov (United States)

    Cheng, Rui; Tao, Mangjuan; Shi, Zhilu; Zhang, Xiafei; Jin, Yan; Li, Baoxin

    2015-11-15

    Several fluorescence signal amplification strategies have been developed for sensitive detection of T4 polynucleotide kinase (T4 PNK) activity, but they need fluorescence dye labeled DNA probe. We have addressed the limitation and report here a label-free strategy for sensitive detection of PNK activity by coupling DNA strand displacement reaction with enzymatic-aided amplification. A hairpin oligonucleotide (hpDNA) with blunt ends was used as the substrate for T4 PNK phosphorylation. In the presence of T4 PNK, the stem of hpDNA was phosphorylated and further degraded by lambda exonuclease (λ exo) from 5' to 3' direction to release a single-stranded DNA as a trigger of DNA strand displacement reaction (SDR). The trigger DNA can continuously displace DNA P2 from P1/P2 hybrid with the help of specific cleavage of nicking endonuclease (Nt.BbvCI). Then, DNA P2 can form G-quadruplex in the presence of potassium ions and quadruplex-selective fluorphore, N-methyl mesoporphyrin IX (NMM), resulting in a significant increase in fluorescence intensity of NMM. Thus, the accumulative release of DNA P2 led to fluorescence signal amplification for determining T4 PNK activity with a detection limit of 6.6×10(-4) U/mL, which is superior or comparative with established approaches. By ingeniously utilizing T4 PNK-triggered DNA SDR, T4 PNK activity can be specifically and facilely studied in homogeneous solution containing complex matrix without any external fluorescence labeling. Moreover, the influence of different inhibitors on the T4 PNK activity revealed that it also can be explored to screen T4 PNK inhibitors. Therefore, this label-free amplification strategy presents a facile and cost-effective approach for nucleic acid phosphorylation related research. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Oxidative degradation and non-enzymatic browning due to the interaction between oxidised lipids and primary amine groups in different marine PL emulsions

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

    2012-01-01

    investigated through the measurement of secondary volatile compounds by solid-phase microextraction (SPME) and dynamic headspace (DHS) connected to gas chromatography (GC–MS). Non-enzymatic browning reactions were investigated through the measurement of Strecker derived volatiles, colour changes and pyrrole...

  15. Mathematical models and equilibrium in irreversible microeconomics

    Directory of Open Access Journals (Sweden)

    Anatoly M. Tsirlin

    2010-07-01

    Full Text Available A set of equilibrium states in a system consisting of economic agents, economic reservoirs, and firms is considered. Methods of irreversible microeconomics are used. We show that direct sale/purchase leads to an equilibrium state which depends upon the coefficients of supply/demand functions. To reach the unique equilibrium state it is necessary to add either monetary exchange or an intermediate firm.

  16. DNA-Based Sensor for Real-Time Measurement of the Enzymatic Activity of Human Topoisomerase I

    DEFF Research Database (Denmark)

    Marcussen, Lærke Bay; Jepsen, Morten Leth; Kristoffersen, Emil Laust

    2013-01-01

    Sensors capable of quantitative real-time measurements may present the easiest and most accurate way to study enzyme activities. Here we present a novel DNA-based sensor for specific and quantitative real-time measurement of the enzymatic activity of the essential human enzyme, topoisomerase I....... The basic design of the sensor relies on two DNA strands that hybridize to form a hairpin structure with a fluorophore-quencher pair. The quencher moiety is released from the sensor upon reaction with human topoisomerase I thus enabling real-time optical measurement of enzymatic activity. The sensor....... The cytotoxic effect of camptothecins correlates directly with the intracellular topoisomerase I activity. We therefore envision that the presented sensor may find use for the prediction of cellular drug response. Moreover, inhibition of topoisomerase I by camptothecin is readily detectable using the presented...

  17. Lignocellulose pretreatment technologies affect the level of enzymatic cellulose oxidation by LPMO

    DEFF Research Database (Denmark)

    Rodríguez-Zúñiga, Ursula Fabiola; Cannella, David; de Campos Giordano, Roberto

    2015-01-01

    of the cellulose oxidizing enzyme lytic polysaccharide monooxygenase (LPMO). The highest activity of LPMO was observed for the hydrothermally pretreated biomasses, which also contained the highest level of lignin. All hydrolysis were done at high dry matter levels, using a commercial enzyme preparation containing......Sugarcane bagasse, corn stover, and wheat straw are among the most available resources for production of cellulosic ethanol. For these biomasses we study the influence of pre-treatment methods on the chemical composition, as well as on the subsequent reactions of enzymatic hydrolysis and oxidation...

  18. Improved pretreatment of lignocellulosic biomass using enzymatically-generated peracetic acid.

    Science.gov (United States)

    Yin, DeLu Tyler; Jing, Qing; AlDajani, Waleed Wafa; Duncan, Shona; Tschirner, Ulrike; Schilling, Jonathan; Kazlauskas, Romas J

    2011-04-01

    Release of sugars from lignocellulosic biomass is inefficient because lignin, an aromatic polymer, blocks access of enzymes to the sugar polymers. Pretreatments remove lignin and disrupt its structure, thereby enhancing sugar release. In previous work, enzymatically generated peracetic acid was used to pretreat aspen wood. This pretreatment removed 45% of the lignin and the subsequent saccharification released 97% of the sugars remaining after pretreatment. In this paper, the amount of enzyme needed is reduced tenfold using first, an improved enzyme variant that makes twice as much peracetic acid and second, a two-phase reaction to generate the peracetic acid, which allows enzyme reuse. In addition, the eight pretreatment cycles are reduced to only one by increasing the volume of peracetic acid solution and increasing the temperature to 60 °C and the reaction time to 6h. For the pretreatment step, the weight ratio of peracetic acid to wood determines the amount of lignin removed. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Anistropically varying conductivity in irreversible electroporation simulations.

    Science.gov (United States)

    Labarbera, Nicholas; Drapaca, Corina

    2017-11-01

    One recent area of cancer research is irreversible electroporation (IRE). Irreversible electroporation is a minimally invasive procedure where needle electrodes are inserted into the body to ablate tumor cells with electricity. The aim of this paper is to propose a mathematical model that incorporates a tissue's conductivity increasing more in the direction of the electrical field as this has been shown to occur in experiments. It was necessary to mathematically derive a valid form of the conductivity tensor such that it is dependent on the electrical field direction and can be easily implemented into numerical software. The derivation of a conductivity tensor that can take arbitrary functions for the conductivity in the directions tangent and normal to the electrical field is the main contribution of this paper. Numerical simulations were performed for isotropic-varying and anisotropic-varying conductivities to evaluate the importance of including the electrical field's direction in the formulation for conductivity. By starting from previously published experimental results, this paper derived a general formulation for an anistropic-varying tensor for implementation into irreversible electroporation modeling software. The anistropic-varying tensor formulation allows the conductivity to take into consideration both electrical field direction and magnitude, as opposed to previous published works that only took into account electrical field magnitude. The anisotropic formulation predicts roughly a five percent decrease in ablation size for the monopolar simulation and approximately a ten percent decrease in ablation size for the bipolar simulations. This is a positive result as previously reported results found the isotropic formulation to overpredict ablation size for both monopolar and bipolar simulations. Furthermore, it was also reported that the isotropic formulation overpredicts the ablation size more for the bipolar case than the monopolar case. Thus, our

  20. Ecological optimization for an irreversible magnetic Ericsson refrigeration cycle

    International Nuclear Information System (INIS)

    Wang Hao; Wu Guo-Xing

    2013-01-01

    An irreversible Ericsson refrigeration cycle model is established, in which multi-irreversibilities such as finite-rate heat transfer, regenerative loss, heat leakage, and the efficiency of the regenerator are taken into account. Expressions for several important performance parameters, such as the cooling rate, coefficient of performance (COP), power input, exergy output rate, entropy generation rate, and ecological function are derived. The influences of the heat leakage and the time of the regenerative processes on the ecological performance of the refrigerator are analyzed. The optimal regions of the ecological function, cooling rate, and COP are determined and evaluated. Furthermore, some important parameter relations of the refrigerator are revealed and discussed in detail. The results obtained here have general significance and will be helpful in gaining a deep understanding of the magnetic Ericsson refrigeration cycle. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  1. Detailed Modeling and Irreversible Transfer Process Analysis of a Multi-Element Thermoelectric Generator System

    Science.gov (United States)

    Xiao, Heng; Gou, Xiaolong; Yang, Suwen

    2011-05-01

    Thermoelectric (TE) power generation technology, due to its several advantages, is becoming a noteworthy research direction. Many researchers conduct their performance analysis and optimization of TE devices and related applications based on the generalized thermoelectric energy balance equations. These generalized TE equations involve the internal irreversibility of Joule heating inside the thermoelectric device and heat leakage through the thermoelectric couple leg. However, it is assumed that the thermoelectric generator (TEG) is thermally isolated from the surroundings except for the heat flows at the cold and hot junctions. Since the thermoelectric generator is a multi-element device in practice, being composed of many fundamental TE couple legs, the effect of heat transfer between the TE couple leg and the ambient environment is not negligible. In this paper, based on basic theories of thermoelectric power generation and thermal science, detailed modeling of a thermoelectric generator taking account of the phenomenon of energy loss from the TE couple leg is reported. The revised generalized thermoelectric energy balance equations considering the effect of heat transfer between the TE couple leg and the ambient environment have been derived. Furthermore, characteristics of a multi-element thermoelectric generator with irreversibility have been investigated on the basis of the new derived TE equations. In the present investigation, second-law-based thermodynamic analysis (exergy analysis) has been applied to the irreversible heat transfer process in particular. It is found that the existence of the irreversible heat convection process causes a large loss of heat exergy in the TEG system, and using thermoelectric generators for low-grade waste heat recovery has promising potential. The results of irreversibility analysis, especially irreversible effects on generator system performance, based on the system model established in detail have guiding significance for

  2. Structural parameter identifiability analysis for dynamic reaction networks

    DEFF Research Database (Denmark)

    Davidescu, Florin Paul; Jørgensen, Sten Bay

    2008-01-01

    method based on Lie derivatives. The proposed systematic two phase methodology is illustrated on a mass action based model for an enzymatically catalyzed reaction pathway network where only a limited set of variables is measured. The methodology clearly pinpoints the structurally identifiable parameters...... where for a given set of measured variables it is desirable to investigate which parameters may be estimated prior to spending computational effort on the actual estimation. This contribution addresses the structural parameter identifiability problem for the typical case of reaction network models....... The proposed analysis is performed in two phases. The first phase determines the structurally identifiable reaction rates based on reaction network stoichiometry. The second phase assesses the structural parameter identifiability of the specific kinetic rate expressions using a generating series expansion...

  3. Quantum chemical modeling of enzymatic reactions: the case of 4-oxalocrotonate tautomerase.

    Science.gov (United States)

    Sevastik, Robin; Himo, Fahmi

    2007-12-01

    The reaction mechanism of 4-oxalocrotonate tautomerase (4-OT) is studied using the density functional theory method B3LYP. This enzyme catalyzes the isomerisation of unconjugated alpha-keto acids to their conjugated isomers. Two different quantum chemical models of the active site are devised and the potential energy curves for the reaction are computed. The calculations support the proposed reaction mechanism in which Pro-1 acts as a base to shuttle a proton from the C3 to the C5 position of the substrate. The first step (proton transfer from C3 to proline) is shown to be the rate-limiting step. The energy of the charge-separated intermediate (protonated proline-deprotonated substrate) is calculated to be quite low, in accordance with measured pKa values. The results of the two models are used to evaluate the methodology employed in modeling enzyme active sites using quantum chemical cluster models.

  4. Transglycosylation reactions, a main mechanism of phenolics incorporation in coffee melanoidins: Inhibition by Maillard reaction.

    Science.gov (United States)

    Moreira, Ana S P; Nunes, Fernando M; Simões, Cristiana; Maciel, Elisabete; Domingues, Pedro; Domingues, M Rosário M; Coimbra, Manuel A

    2017-07-15

    Under roasting conditions, polysaccharides depolymerize and also are able to polymerize, forming new polymers through non-enzymatic transglycosylation reactions (TGRs). TGRs can also occur between carbohydrates and aglycones, such as the phenolic compounds present in daily consumed foods like coffee. In this study, glycosidically-linked phenolic compounds were quantified in coffee melanoidins, the polymeric nitrogenous brown-colored compounds formed during roasting, defined as end-products of Maillard reaction. One third of the phenolics present were in glycosidically-linked form. In addition, the roasting of solid-state mixtures mimicking coffee beans composition allowed the conclusion that proteins play a regulatory role in TGRs extension and, consequently, modulate melanoidins composition. Overall, the results obtained showed that TGRs are a main mechanism of phenolics incorporation in melanoidins and are inhibited by amino groups through Maillard reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Science.gov (United States)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  6. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Energy Technology Data Exchange (ETDEWEB)

    Fedorenko, S. G. [Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk (Russian Federation); Burshtein, A. I. [Weizmann Institute of Science, 76100, Rehovot (Israel)

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  7. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    International Nuclear Information System (INIS)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-01-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics

  8. Production of Fish Hydrolysates Protein From Waste of Fish Carp (Cyprinus Carpio by Enzymatic Hydrolysis

    Directory of Open Access Journals (Sweden)

    Dede Saputra

    2016-03-01

    Full Text Available Fish Protein Hydrolysates (FPH is the mixed products of polypeptide, dipeptides, and amino acid. It can be produced from materials that contained of protein by acid reaction, base reaction or enzymatic hydrolysis. The objectives of this study were to study the production of FPH from fish carp meat at post rigor phase and viscera by enzymatic hydrolysis, to determine the specific activity of papain enzyme, and to determine the solubility of FPH. Capacity of fish hydrolyzing can be identified by analyzing the content of dissolved total nitrogen (NTT compared with nitrogen total ingredient (NTB in order to get the value of total soluble nitrogen/total nitrogen material (NTT/NTB. The hydrolysis processes were carried out in 0,26% (w/v papain, 60 οC for 3 hours. The result showed that the specific activity of papain enzyme was about 3.28 U/mg. Solubility of FPH by comparing NTT/NTB was about 0.29% (fish meat and 0.40% (fish viscera. Proximate test of protein content of fish meat was 18.34 ± 0.04 (g/100 g; while viscera was about 0.95±0.04 (g/100 g. The result indicated that product waste of fish carp had potential as a major of source of FPH.

  9. Enzymatic hydrolysis of pretreated soybean straw

    International Nuclear Information System (INIS)

    Xu Zhong; Wang Qunhui; Jiang Zhaohua; Yang Xuexin; Ji Yongzhen

    2007-01-01

    In order to produce lactic acid, from agricultural residues such as soybean straw, which is a raw material for biodegradable plastic production, it is necessary to decompose the soybean straw into soluble sugars. Enzymatic hydrolysis is one of the methods in common use, while pretreatment is the effective way to increase the hydrolysis rate. The optimal conditions of pretreatment using ammonia and enzymatic hydrolysis of soybean straw were determined. Compared with the untreated straw, cellulose in straw pretreated by ammonia liquor (10%) soaking for 24 h at room temperature increased 70.27%, whereas hemicellulose and lignin in pretreated straw decreased to 41.45% and 30.16%, respectively. The results of infrared spectra (IR), scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis also showed that the structure and the surface of the straw were changed through pretreatment that is in favor of the following enzymatic hydrolysis. maximum enzymatic hydrolysis rate of 51.22% was achieved at a substrate concentration of 5% (w/v) at 50 deg. C and pH 4.8 using cellulase (50 fpu/g of substrate) for 36 h

  10. Assessing the reaction conditions to mediate the milkfat-soybean oil enzymatic interesterification

    Directory of Open Access Journals (Sweden)

    Ariela Veloso de Paula

    Full Text Available Summary A food grade lipase from Rhizopus oryzae immobilized on a hybrid polysiloxane-polyvinyl alcohol matrix (SiO2-PVA was used as the biocatalyst to mediate the interesterification reactions of a blend containing 65% milkfat and 35% soybean oil. All the reactions occurred in an inert nitrogen atmosphere in cylindrical glass reactors (80 mL with 40 g of the milkfat-soybean oil blend. The influence of the following variables was evaluated: biocatalyst loading (250-1500 activity units per gram of blend, biocatalyst moisture content (5-20%, temperature (45-60 °C and incubation time (2-48 h. The reactions were monitored by determining the free fatty acid content, triacylglycerol (TAGs composition in carbon species, and the consistency of the interesterified (IE products. The reaction conditions were set based on the parameters that provided a high interesterification yield and good consistency of the final product within the ideal range (200 to 800 gf cm-2. Hence the best results were obtained using a biocatalyst loading of 500 U g-1 of blend with 10% moisture content at 45 °C for 4 h. Under these conditions the consistency of the interesterified product was 539.7 ± 38 gf cm-2. The results demonstrated the potential of the immobilized lipase to alter the TAGs profile of the milkfat-soybean oil blend, allowing for the production of structured lipids.

  11. Irreversible JPEG 2000 compression of abdominal CT for primary interpretation: assessment of visually lossless threshold

    International Nuclear Information System (INIS)

    Lee, Kyoung Ho; Kim, Young Hoon; Kim, Bo Hyoung; Kim, Kil Joong; Kim, Tae Jung; Kim, Hyuk Jung; Hahn, Seokyung

    2007-01-01

    To estimate the visually lossless threshold for Joint Photographic Experts Group (JPEG) 2000 compression of contrast-enhanced abdominal computed tomography (CT) images, 100 images were compressed to four different levels: a reversible (as negative control) and irreversible 5:1, 10:1, and 15:1. By alternately displaying the original and the compressed image on the same monitor, six radiologists independently determined if the compressed image was distinguishable from the original image. For each reader, we compared the proportion of the compressed images being rated distinguishable from the original images between the reversible compression and each of the three irreversible compressions using the exact test for paired proportions. For each reader, the proportion was not significantly different between the reversible (0-1%, 0/100 to 1/100) and irreversible 5:1 compression (0-3%). However, the proportion significantly increased with the irreversible 10:1 (95-99%) and 15:1 compressions (100%) versus reversible compression in all readers (P < 0.001); 100 and 95% of the 5:1 compressed images were rated indistinguishable from the original images by at least five of the six readers and all readers, respectively. Irreversibly 5:1 compressed abdominal CT images are visually lossless and, therefore, potentially acceptable for primary interpretation. (orig.)

  12. Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

    Science.gov (United States)

    Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

    2013-01-01

    Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes. PMID:23563856

  13. Antimicrobial activity and properties of irreversible hydrocolloid impression materials incorporated with silver nanoparticles.

    Science.gov (United States)

    Ginjupalli, Kishore; Alla, Rama Krishna; Tellapragada, Chaitanya; Gupta, Lokendra; Upadhya Perampalli, Nagaraja

    2016-06-01

    Conventional spray and the immersion disinfection of irreversible hydrocolloid impression materials may lead to dimensional changes. The purpose of this in vitro study was to investigate the antimicrobial activity and properties of irreversible hydrocolloid impression materials incorporated with silver nanoparticles. The antimicrobial activity and properties of 2 commercially available irreversible hydrocolloid impression materials were evaluated after incorporating varying concentrations of silver nanoparticles. Antimicrobial activity was determined using the disk diffusion method. The gel strength, permanent deformation, flow, and gelation time were measured according to American Dental Association specification #18. Analysis of variance was used to identify the significant differences within and across the groups (α=.05). Adding silver nanoparticles to irreversible hydrocolloid impression materials resulted in superior antimicrobial activity without adversely affecting their properties. Adding silver nanoparticles to Zelgan significantly increased the gel strength compared with the control group, except at 5 wt%. However, the gel strength of Tropicalgin was unaffected except at 5 wt%. An increase in the permanent deformation was found with the incorporation of silver nanoparticles in both Zelgan and Tropicalgin. The flow of Zelgan increased with the incorporation of silver nanoparticles, whereas a decrease in the flow of Tropicalgin was observed at 1 wt% and 2 wt%. An increase in the gelation time of both Zelgan and Tropicalgin was observed with the incorporation of silver nanoparticles. Based on this in vitro study, silver nanoparticles can be incorporated into irreversible hydrocolloid impression materials as antimicrobial agents without adversely affecting their properties. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

  14. Prostaglandin E2 to diagnose between reversible and irreversible pulpitis.

    Science.gov (United States)

    Petrini, M; Ferrante, M; Ciavarelli, L; Brunetti, L; Vacca, M; Spoto, G

    2012-01-01

    The aim of this work is to verify a correlation between the grade of inflammation and the concentration of PGE2 in human dental pulp. A total of 25 human dental pulps were examined by histological analysis and radioimmunologic dosage of PGE2. The pulps used in this experiment were from healthy and symptomatic teeth; the first ones were collected from teeth destined to be extracted for orthodontic reasons. An increase was observed of PGE2 in reversible pulpitis compared with healthy pulps and with the irreversible pulpitis and the clear decrease of these when NSAIDs are taken. This study demonstrates that PGE2 level is correlated to histological analysis thus allowing to distinguish symptomatic teeth in reversible and irreversible pulpitis.

  15. Direct and irreversible inhibition of cyclooxygenase-1 by nitroaspirin (NCX 4016).

    Science.gov (United States)

    Corazzi, Teresa; Leone, Mario; Maucci, Raffaella; Corazzi, Lanfranco; Gresele, Paolo

    2005-12-01

    Benzoic acid, 2-(acetyl-oxy)-3-[(nitrooxy)methyl]phenyl ester (NCX 4016), a new drug made by an aspirin molecule linked, through a spacer, to a nitric oxide (NO)-donating moiety, is now under clinical testing for the treatment of atherothrombotic conditions. Aspirin exerts its antithrombotic activity by irreversibly inactivating platelet cyclooxygenase (COX)-1. NCX 4016 in vivo undergoes metabolism into deacetylated and/or denitrated metabolites, and it is not known whether NCX 4016 needs to liberate aspirin to inhibit COX-1, or whether it can block it as a whole molecule. The aim of our study was to evaluate the effects of NCX 4016 and its analog or metabolites on platelet COX-1 and whole blood COX-2 and on purified ovine COX (oCOX)-1 and oCOX-2. In particular, we have compared the mechanism by which NCX 4016 inhibits purified oCOX enzymes with that of aspirin using a spectrophotometric assay. All the NCX 4016 derivatives containing acetylsalicylic acid inhibited the activity of oCOX-1 and oCOX-2, whereas the deacetylated metabolites and the nitric oxide-donating moiety were inactive. Dialysis experiments showed that oCOX-1 inhibition by NCX 4016, similar to aspirin, is irreversible. Reversible COX inhibitors (indomethacin) or salicylic acid incubated with the enzyme before NCX 4016 prevent the irreversible inhibition of oCOX-1 by NCX 4016 as well as by aspirin. In conclusion, our data show that NCX 4016 acts as a direct and irreversible inhibitor of COX-1 and that the presence of a spacer and NO-donating moiety in the molecule slows the kinetics of COX-1 inhibition by NCX 4016, compared with aspirin.

  16. Enzymatic conformational fluctuations along the reaction coordinate of cytidine deaminase

    OpenAIRE

    Noonan, Ryan C.; Carter, Charles W.; Bagdassarian, Carey K.

    2002-01-01

    Analysis of the crystal structures for cytidine deaminase complexed with substrate analog 3-deazacytidine, transition-state analog zebularine 3,4-hydrate, and product uridine establishes significant changes in the magnitude of atomic-scale fluctuations along the (approximate) reaction coordinate of this enzyme. Differences in fluctuations between the substrate analog complex, transition-state analog complex, and product complex are monitored via changes in corresponding crystallographic tempe...

  17. Enzymatic hydrolysis of biomimetic bacterial cellulose-hemicellulose composites.

    Science.gov (United States)

    Penttilä, Paavo A; Imai, Tomoya; Hemming, Jarl; Willför, Stefan; Sugiyama, Junji

    2018-06-15

    The production of biofuels and other chemicals from lignocellulosic biomass is limited by the inefficiency of enzymatic hydrolysis. Here a biomimetic composite material consisting of bacterial cellulose and wood-based hemicelluloses was used to study the effects of hemicelluloses on the enzymatic hydrolysis with a commercial cellulase mixture. Bacterial cellulose synthesized in the presence of hemicelluloses, especially xylan, was found to be more susceptible to enzymatic hydrolysis than hemicellulose-free bacterial cellulose. The reason for the easier hydrolysis could be related to the nanoscale structure of the substrate, particularly the packing of cellulose microfibrils into ribbons or bundles. In addition, small-angle X-ray scattering was used to show that the average nanoscale morphology of bacterial cellulose remained unchanged during the enzymatic hydrolysis. The reported easier enzymatic hydrolysis of bacterial cellulose produced in the presence of wood-based xylan offers new insights to overcome biomass recalcitrance through genetic engineering. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Uma perspectiva computacional sobre catálise enzimática A computational perspective on enzymatic catalysis

    Directory of Open Access Journals (Sweden)

    Guilherme M. Arantes

    2008-01-01

    Full Text Available Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.

  19. Simplification of lipase design in the enzymatic kinetic resolution of amines by saturation transfer difference NMR

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Marcio S.; Pietrobom, Daniel, E-mail: s.marcio@ufabc.edu.br [Universidade Federal do ABC (CCNH/UFABC), Santo André, SP (Brazil). Centro de Ciências Naturais e Humanas

    2016-07-01

    In this work, we demonstrate a nuclear magnetic resonance (NMR) method for racemic amide and lipase interaction as a first-pass design method in the enzymatic kinetic resolution of amines. As a novel adaptation of commonly used protein-ligand screening NMR methodologies, this approach relies upon a lipase-amide interaction wherein the time-consuming is reduced drastically and new insights are produced during the development of biocatalysis reactions. (author)

  20. On the impedance of galvanic cells XXVII. The temperature-dependence of the kinetic parameters of the hydrogen electrode reaction on mercury in concentrated HI

    NARCIS (Netherlands)

    Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1969-01-01

    The impedance of a dropping mercury electrode in 57% HI (7.6 M) was measured at temperatures between −35° and +25°C. In a certain potential and temperature region, two reactions were found to be proceeding simultaneously: the reversible Hg/HgI4−2 reaction and the irreversible H+/H2(Hg) reaction.

  1. Low melting point pyridinium ionic liquid pretreatment for enhancing enzymatic saccharification of cellulosic biomass.

    Science.gov (United States)

    Uju; Nakamoto, Aya; Shoda, Yasuhiro; Goto, Masahiro; Tokuhara, Wataru; Noritake, Yoshiyuki; Katahira, Satoshi; Ishida, Nobuhiro; Ogino, Chiaki; Kamiya, Noriho

    2013-05-01

    The potential of 1-hexylpyridinium chloride ([Hpy][Cl]), to pretreat cellulosic feedstocks was investigated using microcrystalline cellulose (Avicel) and Bagasse at 80 °C or 100 °C. Short [Hpy][Cl] pretreatments, conversion of pretreated Avicel to glucose was attained after 24h enzymatic saccharification under optimal conditions, whereas regenerated Bagasse showed 1-3-fold higher conversion than untreated biomass. FT-IR analysis of both Avicel and Bagasse samples pretreated with [Hpy][Cl] or 1-ethyl-3-methyimidazolium acetate ([Emim][OAc]) revealed that these ionic liquids behaved differently during pretreatment. [Hpy][Cl] pretreatment for an extended duration (180 min) released mono- and disaccharides without using cellulase enzymes, suggesting [Hpy][Cl] has capability for direct saccharification of cellulosic feedstocks. On the basis of the results obtained, [Hpy][Cl] pretreatment enhanced initial reaction rates in enzymatic saccharification by either crystalline polymorphic alteration of cellulose or partial degradation of the crystalline cellulosic fraction in biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. On the existence of physiological age based on functional hierarchy: a formal definition related to time irreversibility.

    Science.gov (United States)

    Chauvet, Gilbert A

    2006-09-01

    The present approach of aging and time irreversibility is a consequence of the theory of functional organization that I have developed and presented over recent years (see e.g., Ref. 11). It is based on the effect of physically small and numerous perturbations known as fluctuations, of structural units on the dynamics of the biological system during its adult life. Being a highly regulated biological system, a simple realistic hypothesis, the time-optimum regulation between the levels of organization, leads to the existence of an internal age for the biological system, and time-irreversibility associated with aging. Thus, although specific genes are controlling aging, time-irreversibility of the system may be shown to be due to the degradation of physiological functions. In other words, I suggest that for a biological system, the nature of time is specific and is an expression of the highly regulated integration. An internal physiological age reflects the irreversible course of a living organism towards death because of the irreversible course of physiological functions towards dysfunction, due to the irreversible changes in the regulatory processes. Following the works of Prigogine and his colleagues in physics, and more generally in the field of non-integrable dynamical systems (theorem of Poincaré-Misra), I have stated this problem in terms of the relationship between the macroscopic irreversibility of the functional organization and the basic mechanisms of regulation at the lowest "microscopic" level, i.e., the molecular, lowest level of organization. The neuron-neuron elementary functional interaction is proposed as an illustration of the method to define aging in the nervous system.

  3. Transesterification of Waste Frying Oil and Soybean Oil by Combi-lipases Under Ultrasound-Assisted Reactions.

    Science.gov (United States)

    Poppe, Jakeline Kathiele; Matte, Carla Roberta; Fernandez-Lafuente, Roberto; Rodrigues, Rafael C; Ayub, Marco Antônio Záchia

    2018-04-21

    This work describes the use of an ultrasound system for the enzymatic transesterification of oils using combi-lipases as biocatalyst. The reactions were carried out evaluating the individual use of waste oil and fresh soybean oil, and the immobilized lipases CALB, TLL, and RML were used as biocatalysts. It was performed in a mixture design of three factors to obtain the ideal mixture of lipases according to the composition of fatty acids present in each oil, and the main reaction variables were optimized. After 18 h of reaction, ultrasound provided a biodiesel yield of about 90% when using soybean oil and 70% using the waste oil. The results showed that ultrasound technology, in combination with the application of enzyme mixtures, known as combi-lipases, and the use of waste oil, could be a promising route to reduce the overall process costs of enzymatic production of biodiesel.

  4. Enzymatic transesterification of soybean oil with ethanol using lipases immobilized on highly crystalline PVA microspheres

    International Nuclear Information System (INIS)

    Bergamasco, Juliana; Araujo, Marcelo V. de; Vasconcellos, Adriano de; Luizon Filho, Roberto A.; Hatanaka, Rafael R.; Giotto, Marcus V.; Aranda, Donato A.G.; Nery, José G.

    2013-01-01

    Polyvinyl alcohol (PVA) microspheres with different degree of crystallinity were used as solid supports for Rhizomucor miehei lipase immobilization, and the enzyme-PVA complexes were used as biocatalysts for the transesterification of soybean oil to fatty acid ethyl esters (FAEE). The amounts of immobilized enzyme on the polymeric supports were similar for both the amorphous microspheres (PVA4) and the high crystalline microspheres (PVA25). However, the enzymatic activity of the immobilized enzymes was depended on the crystallinity degree of the PVA microspheres: enzymes immobilized on the PVA4 microspheres have shown low enzymatic activity (6.13 U mg −1 ), in comparison with enzymes immobilized on the high crystalline PVA25 microspheres (149.15 U mg −1 ). A synergistic effect was observed for the enzyme-PVA25 complex during the transesterification reaction of soybean oil to FAEE: transesterification reactions with free enzyme with the equivalent amount of enzyme that were immobilized onto the PVA25 microspheres (5.4 U) have yielded only 20% of FAEE, reactions with the pure highly crystalline microsphere PVA25 have not yielded FAEE, however reactions with the enzyme-PVA25 complexes have yielded 66.3% of FAEE. This synergistic effect of an immobilized enzyme on a polymeric support has not been observed before for transesterification reaction of triacylglycerides into FAEE. Based on ATR-FTIR, 23 Na- and 13 C-NMR-MAS spectroscopic data and the interaction of the polymeric network intermolecular hydrogen bonds with the lipases residual amino acids a possible explanation for this synergistic effect is provided. Highlights: • Rhizomucor miehei lipase was immobilized on PVA microspheres (PVA4, PVA12, PVA25). • Polymer-enzyme complex was characterized by XDR, SEM, ATR-FTIR, 13 C-CPMAS-NMR, 23 Na-MAS-NMR. • Polymer-enzymes (PVA12 and PVA25) enzymes yielded considerable amount of ethyl esters. • Synergistic effect was observed for the polymer-enzyme complexes

  5. Pinning and irreversibility in superconducting bulk MgB{sub 2} with added nanodiamonds

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Anurag [Superconductivity and Cryogenics Division, National Physical Laboratory (CSIR), New Delhi-110012 (India); Narlikar, A V, E-mail: anurag@mail.nplindia.ernet.i [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore-452017, MP (India)

    2009-12-15

    Resistance, R(T), and magnetization, M(B), studies on superconducting bulk MgB{sub 2} samples containing nanodiamonds (ND) as additives (wt% of ND: x = 0%, 1%, 3%, 5%, 7% and 10%) were recently published in two articles (Vajpayee et al 2007 Supercond. Sci. Technol. 20 S155, Vajpayee et al 2008 J. Appl. Phys. 103 07C708). The main observations reported were significant improvements in the critical current density J{sub c}(B), irreversibility line B{sub irr}(T) and upper critical field B{sub c2}(T) with ND addition. However, a closer look shows that as regards the potential of this technologically important material at higher magnetic fields and temperatures, there is still a lot of room for improvement. With that in mind we revisit the R(T) and M(B) data and analyze them, in the present work. We show that, despite ND addition, J{sub c} depends strongly on B in the high field region and tends to vanish at irreversibility lines that lie deep, i.e. at around 0.3 B{sub c2}(T), in the B-T phase diagram. The irreversibility lines, determined by R(T){yields}0 in the presence of B, are found to lie at around 0.5 B{sub c2}(T) in the phase diagram. These results for pinning and irreversibility lines are discussed in the light of various models such as those of surface sheath superconductivity, magnetically introduced percolation in polycrystalline MgB{sub 2}, thermally assisted flux motion (TAFM) and a modified flux line shear mechanism. Our analysis hints at TAFM and weak pinning channels with distributed superconducting properties percolating in our samples determining the irreversibility and pinning properties.

  6. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  7. Antibacterial efficacy and effect of chlorhexidine mixed with irreversible hydrocolloid for dental impressions: a randomized controlled trial.

    Science.gov (United States)

    Cubas, Glória; Valentini, Fernanda; Camacho, Guilherme Brião; Leite, Fábio; Cenci, Maximiliano Sérgio; Pereira-Cenci, Tatiana

    2014-01-01

    This study aimed to evaluate whether chlorhexidine mixed with irreversible hydrocolloid powder decreases microbial contamination during impression taking without affecting the resulting casts. Twenty volunteers were randomly divided into two groups (n = 10) according to the liquid used for impression taking in conjunction with irreversible hydrocolloid: 0.12% chlorhexidine or water. Surface roughness and dimensional stability of the casts were evaluated. Chlorhexidine mixed with irreversible hydrocolloid decreased the percentage of microorganisms when compared with water (P impression quality.

  8. Noncanonical substrate preference of lambda exonuclease for 5'-nonphosphate-ended dsDNA and a mismatch-induced acceleration effect on the enzymatic reaction.

    Science.gov (United States)

    Wu, Tongbo; Yang, Yufei; Chen, Wei; Wang, Jiayu; Yang, Ziyu; Wang, Shenlin; Xiao, Xianjin; Li, Mengyuan; Zhao, Meiping

    2018-04-06

    Lambda exonuclease (λ exo) plays an important role in the resection of DNA ends for DNA repair. Currently, it is also a widely used enzymatic tool in genetic engineering, DNA-binding protein mapping, nanopore sequencing and biosensing. Herein, we disclose two noncanonical properties of this enzyme and suggest a previously undescribed hydrophobic interaction model between λ exo and DNA substrates. We demonstrate that the length of the free portion of the substrate strand in the dsDNA plays an essential role in the initiation of digestion reactions by λ exo. A dsDNA with a 5' non-phosphorylated, two-nucleotide-protruding end can be digested by λ exo with very high efficiency. Moreover, we show that when a conjugated structure is covalently attached to an internal base of the dsDNA, the presence of a single mismatched base pair at the 5' side of the modified base may significantly accelerate the process of digestion by λ exo. A detailed comparison study revealed additional π-π stacking interactions between the attached label and the amino acid residues of the enzyme. These new findings not only broaden our knowledge of the enzyme but will also be very useful for research on DNA repair and in vitro processing of nucleic acids.

  9. Lignin from hydrothermally pretreated grass biomass retards enzymatic cellulose degradation by acting as a physical barrier rather than by inducing nonproductive adsorption of enzymes.

    Science.gov (United States)

    Djajadi, Demi T; Jensen, Mads M; Oliveira, Marlene; Jensen, Anders; Thygesen, Lisbeth G; Pinelo, Manuel; Glasius, Marianne; Jørgensen, Henning; Meyer, Anne S

    2018-01-01

    Lignin is known to hinder efficient enzymatic conversion of lignocellulose in biorefining processes. In particular, nonproductive adsorption of cellulases onto lignin is considered a key mechanism to explain how lignin retards enzymatic cellulose conversion in extended reactions. Lignin-rich residues (LRRs) were prepared via extensive enzymatic cellulose degradation of corn stover ( Zea mays subsp. mays L.), Miscanthus  ×  giganteus stalks (MS) and wheat straw ( Triticum aestivum L.) (WS) samples that each had been hydrothermally pretreated at three severity factors (log R 0 ) of 3.65, 3.83 and 3.97. The LRRs had different residual carbohydrate levels-the highest in MS; the lowest in WS. The residual carbohydrate was not traceable at the surface of the LRRs particles by ATR-FTIR analysis. The chemical properties of the lignin in the LRRs varied across the three types of biomass, but monolignols composition was not affected by the severity factor. When pure cellulose was added to a mixture of LRRs and a commercial cellulolytic enzyme preparation, the rate and extent of glucose release were unaffected by the presence of LRRs regardless of biomass type and severity factor, despite adsorption of the enzymes to the LRRs. Since the surface of the LRRs particles were covered by lignin, the data suggest that the retardation of enzymatic cellulose degradation during extended reaction on lignocellulosic substrates is due to physical blockage of the access of enzymes to the cellulose caused by the gradual accumulation of lignin at the surface of the biomass particles rather than by nonproductive enzyme adsorption. The study suggests that lignin from hydrothermally pretreated grass biomass retards enzymatic cellulose degradation by acting as a physical barrier blocking the access of enzymes to cellulose rather than by inducing retardation through nonproductive adsorption of enzymes.

  10. Inhibition of tyrosinase-mediated enzymatic browning by sulfite and natural alternatives

    NARCIS (Netherlands)

    Kuijpers, T.F.M.; Vincken, J.P.

    2013-01-01

    Although sulfite is widely used to counteract enzymatic browning, its mechanism has remained largely unknown. We describe a double inhibitory mechanism of sulfite on enzymatic browning, affecting both the enzymatic oxidation of phenols into o‑quinones, as well as the non‑enzymatic

  11. Enzymatic Synthesis of Esculin Ester in Ionic Liquids Buffered with Organic Solvents

    DEFF Research Database (Denmark)

    Hu, Yifan; Guo, Zheng; Lue, Bena-Marie

    2009-01-01

    The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model...... in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf2N](-) > [PF6](-) > [BF4](-) > [CF3SO3](-) > [C4F9SO3](-) > [TAF...

  12. Intracellular Microreactors as Artificial Organelles to Conduct Multiple Enzymatic Reactions Simultaneously

    DEFF Research Database (Denmark)

    Gallardo, Maria Godoy; Labay, Cédric Pierre; Jansman, Michelle M. T.

    2017-01-01

    The creation of artificial organelles is a new paradigm in medical therapy that aims to substitute for missing cellular function by replenishing a specific cellular task. Artificial organelles tackle the challenge of mimicking metabolism, which is the set of chemical reactions that occur within a...

  13. Inequalities for trace anomalies, length of the RG flow, distance between the fixed points and irreversibility

    International Nuclear Information System (INIS)

    Anselmi, Damiano

    2004-01-01

    I discuss several issues about the irreversibility of the RG flow and the trace anomalies c, a and a'. First I argue that in quantum field theory: (i) the scheme-invariant area Δ a' of the graph of the effective beta function between the fixed points defines the length of the RG flow; (ii) the minimum of Δ a' in the space of flows connecting the same UV and IR fixed points defines the (oriented) distance between the fixed points and (iii) in even dimensions, the distance between the fixed points is equal to Δ a = a UV - a IR . In even dimensions, these statements imply the inequalities 0 ≤ Δ a ≤ Δ a' and therefore the irreversibility of the RG flow. Another consequence is the inequality a ≤ c for free scalars and fermions (but not vectors), which can be checked explicitly. Secondly, I elaborate a more general axiomatic set-up where irreversibility is defined as the statement that there exist no pairs of non-trivial flows connecting interchanged UV and IR fixed points. The axioms, based on the notions of length of the flow, oriented distance between the fixed points and certain 'oriented-triangle inequalities', imply the irreversibility of the RG flow without a global a function. I conjecture that the RG flow is also irreversible in odd dimensions (without a global a function). In support of this, I check the axioms of irreversibility in a class of d = 3 theories where the RG flow is integrable at each order of the large N expansion

  14. Irreversible thermodynamics, parabolic law and self-similar state in grain growth

    International Nuclear Information System (INIS)

    Rios, P.R.

    2004-01-01

    The formalism of the thermodynamic theory of irreversible processes is applied to grain growth to investigate the nature of the self-similar state and its corresponding parabolic law. Grain growth does not reach a steady state in the sense that the entropy production remains constant. However, the entropy production can be written as a product of two factors: a scale factor that tends to zero for long times and a scaled entropy production. It is suggested that the parabolic law and the self-similar state may be associated with the minimum of this scaled entropy production. This result implies that the parabolic law and the self-similar state have a sound irreversible thermodynamical basis

  15. Bioelectrocatalytic NAD+/NADH inter-conversion: transformation of an enzymatic fuel cell into an enzymatic redox flow battery.

    Science.gov (United States)

    Quah, Timothy; Milton, Ross D; Abdellaoui, Sofiene; Minteer, Shelley D

    2017-07-25

    Diaphorase and a benzylpropylviologen redox polymer were combined to create a bioelectrode that can both oxidize NADH and reduce NAD + . We demonstrate how bioelectrocatalytic NAD + /NADH inter-conversion can transform a glucose/O 2 enzymatic fuel cell (EFC) with an open circuit potential (OCP) of 1.1 V into an enzymatic redox flow battery (ERFB), which can be rapidly recharged by operation as an EFC.

  16. Monitoring the enzymatic conversion of urea to ammonium by conventional or microchip capillary electrophoresis with contactless conductivity detection.

    Science.gov (United States)

    Schuchert-Shi, Aiping; Hauser, Peter C

    2008-05-15

    Capillary electrophoresis with contactless conductivity detection was used to directly quantify the ammonium produced in the enzymatic conversion of urea with urease. This allowed the characterization of the reaction without having to use more elaborate indirect optical methods for quantification. The maximum rate of reaction, V(max), was determined as 5.1 mmol x mL(-1) x min(-1), and the Michaelis-Menten constant, K(m), was determined as 16 mM. Furthermore, the method was successfully applied to the determination of urea in clinical samples of human blood by using a conventional capillary and a microchip device.

  17. The universal power and efficiency characteristics for irreversible reciprocating heat engine cycles

    CERN Document Server

    Qin Xiao Yong; Sun Feng Rui; Wu Chih

    2003-01-01

    The performance of irreversible reciprocating heat engine cycles with heat transfer loss and friction-like term loss is analysed using finite-time thermodynamics. The universal relations between the power output and the compression ratio, between the thermal efficiency and the compression ratio, and the optimal relation between power output and the efficiency of the cycles are derived. Moreover, analysis and optimization of the model were carried out in order to investigate the effect of cycle processes on the performance of the cycle using numerical examples. The results obtained herein include the performance characteristics of irreversible reciprocating Diesel, Otto, Atkinson and Brayton cycles.

  18. A general nonlinear evolution equation for irreversible conservative approach to stable equilibrium

    International Nuclear Information System (INIS)

    Beretta, G.P.

    1986-01-01

    This paper addresses a mathematical problem relevant to the question of nonequilibrium and irreversibility, namely, that of ''designing'' a general evolution equation capable of describing irreversible but conservative relaxtion towards equilibrium. The objective is to present an interesting mathematical solution to this design problem, namely, a new nonlinear evolution equation that satisfies a set of very stringent relevant requirements. Three different frameworks are defined from which the new equation could be adopted, with entirely different interpretations. Some useful well-known mathematics involving Gram determinants are presented and a nonlinear evolution equation is given which meets the stringent design specifications

  19. Half-of-the-sites reactivity of outer-membrane phospholipase A against an active-site-directed inhibitor.

    Science.gov (United States)

    Ubarretxena-Belandia, I; Cox, R C; Dijkman, R; Egmond, M R; Verheij, H M; Dekker, N

    1999-03-01

    The reaction of a novel active-site-directed phospholipase A1 inhibitor with the outer-membrane phospholipase A (OMPLA) was investigated. The inhibitor 1-p-nitrophenyl-octylphosphonate-2-tridecylcarbamoyl-3-et hanesulfonyl -amino-3-deoxy-sn-glycerol irreversibly inactivated OMPLA. The inhibition reaction did not require the cofactor calcium or an unprotonated active-site His142. The inhibition of the enzyme solubilized in hexadecylphosphocholine micelles was characterized by a rapid (t1/2 = 20 min) and complete loss of enzymatic activity, concurrent with the covalent modification of 50% of the active-site serines, as judged from the amount of p-nitrophenolate (PNP) released. Modification of the remaining 50% occurred at a much lower rate, indicative of half-of-the-sites reactivity against the inhibitor of this dimeric enzyme. Inhibition of monomeric OMPLA solubilized in hexadecyl-N,N-dimethyl-1-ammonio-3-propanesulfonate resulted in an equimolar monophasic release of PNP, concurrent with the loss of enzymatic activity (t1/2 = 14 min). The half-of-the-sites reactivity is discussed in view of the dimeric nature of this enzyme.

  20. Improved enzymatic production of phenolated glycerides through alkyl phenolate intermediate

    DEFF Research Database (Denmark)

    Yang, Zhiyong; Feddern, Vivian; Glasius, Marianne

    2011-01-01

    This work reported a novel approach for synthesis of dihydrocaffoylated glycerides, consisting of 2 steps: enzymatic synthesis of octyl dihydrocaffeate (as a synthetic intermediate) from octanol and dihydrocaffeic acid (DHCA), and enzymatic interesterification of triglycerides with octyl dihydroc......This work reported a novel approach for synthesis of dihydrocaffoylated glycerides, consisting of 2 steps: enzymatic synthesis of octyl dihydrocaffeate (as a synthetic intermediate) from octanol and dihydrocaffeic acid (DHCA), and enzymatic interesterification of triglycerides with octyl...

  1. Irreversibility analysis for gravity driven non-Newtonian liquid film along an inclined isothermal plate

    International Nuclear Information System (INIS)

    Makinde, O.D.

    2005-10-01

    In this paper, the first and second law of thermodynamics are employed in order to study the inherent irreversibility for a gravity driven non-Newtonian Ostwald-de Waele power law liquid film along an inclined isothermal plate. Based on some simplified assumptions, the governing equations are obtained and solved analytically. Expressions for fluid velocity, temperature, volumetric entropy generation numbers, irreversibility distribution ratio and the Bejan number are also determined. (author)

  2. Influence of enzymatic reactions on the electrochemical behavior of EN X2CrNiMo17-11-2 (AISI 316L) stainless steel in bio-corrosion: role of interfacial processes on the modification of the passive layer; Influence des reactions enzymatiques sur le comportement electrochimique de l'acier inoxydable ENX2CrNiMo17-11-2 (AISI 316L) en biocorrosion: role des processus interfaciaux sur la modification du film passif

    Energy Technology Data Exchange (ETDEWEB)

    Landoulsi, J

    2008-01-15

    The outstanding corrosion behavior of stainless steels (SS) results from the presence of thin oxide layer (some nanometers). In non sterile aqueous media, stainless steels may exhibit a non stable behavior resulting from interactions between microbial species and passive film. In fact, microorganisms can be deeply involved in the corrosion processes usually reported as Microbial Influenced Corrosion (MIC). They can induce the initiation or the acceleration of this phenomenon and they do so when organized in bio-films. From the electrochemical point of view, stainless steels showed an increase of the free corrosion potential (Ecorr) attributed to the bio-film settlement. The Eco' ennoblement was broadly reported in seawater and seems to be confirmed in fresh water according to recent findings. A considerable progress in the comprehension of MIC processes was related to the role of extracellular species, essentially enzymes. Many enzymatic reactions occurring in bio-films consist on using oxygen as electron acceptor to generate hydrogen peroxide and related species. The aim of this work is to understand the mechanisms involved in the electrochemical behavior of stainless steel according to an enzymatic approach in medium simulating fresh water. To this end, glucose oxidase was chosen to globalize aerobic activities of bio-films. Electrochemical measurements in situ and surface analysis allow the comprehension of the role and the nature of interfacial processes. Surface characterization was performed with the help of a new quantitative utilization of XPS analysis and AFM. Results show a significant evolution in term of morphology (surface organization), (ii) chemical composition (passive layer, adsorbed organic species) and (iii) chemical reaction (oxidation, dissolution, effect of enzyme). Finally, a new enzymatic system is proposed to mimic specific physicochemical conditions at the SS / bio-film interface, in particular enzymatic generation of oxidant species

  3. Enhanced Enzymatic Synthesis of a Cephalosporin, Cefadroclor, in the Presence of Organic Co-solvents.

    Science.gov (United States)

    Liu, Kun; Li, Sha; Pang, Xiao; Xu, Zheng; Li, Dengchao; Xu, Hong

    2017-05-01

    In this study, we investigated the enzymatic synthesis of a semi-synthetic cephalosporin, cefadroclor, from 7-aminodesacetoxymethyl-3-chlorocephalosporanic acid (7-ACCA) and p-OH-phenylglycine methyl ester (D-HPGM) using immobilized penicillin G acylase (IPA) in organic co-solvents. Ethylene glycol (EG) was employed as a component of the reaction mixture to improve the yield of cefadroclor. EG was found to increase the yield of cefadroclor by 15-45%. An investigation of altered reaction parameters including type and concentration of organic solvents, pH of reaction media, reaction temperature, molar ratio of substrates, enzyme loading, and IPA recycling was carried out in the buffer mixture. The best result was a 76.5% conversion of 7-ACCA, which was obtained from the reaction containing 20% EG (v/v), D-HPGM to 7-ACCA molar ratio of 4:1 and pH 6.2, catalyzed by 16 IU mL -1 IPA at 20 °C for 10 h. Under the optimum conditions, no significant loss of IPA activity was found after seven repeated reaction cycles. In addition, cefadroclor exhibited strong inhibitory activity against yeast, Bacillus subtilis NX-2, and Escherichia coli and weaker activity against Staphylococcus aureus and Pseudomonas aeruginosa. Cefadroclor is a potential antibiotic with activity against common pathogenic microorganisms.

  4. A coupled CFD and two-phase substrate kinetic model for enzymatic hydrolysis of lignocellulose

    Science.gov (United States)

    Danes, Nicholas; Sitaraman, Hariswaran; Stickel, Jonathan; Sprague, Michael

    2017-11-01

    Cost-effective production of fuels from lignocellulosic biomass is an important subject of research in order to meet the world's current and future energy demands. Enzymatic hydrolysis is one of the several steps in the biochemical conversion of biomass into fuels. This process involves the interplay of non-Newtonian fluid dynamics that happen over tens of seconds coupled with chemical reactions that happen over several hours. In this work, we present a coupled CFD-reaction model for conversion of cellulose to sugars in a benchtop mixer reactor. A subcycling approach is used to circumvent the large time scale disparity between fluid dynamics and reactions. We will present a validation study of our simulations with experiments for well-mixed and stratified reactor scenarios along with predictions for conversion rates and product concentrations at varying impeller speeds and in scaled-up reactors. This work is funded by the Bioenergy Technology Office of DOE and the NSF's Enriched Doctoral Training program (DMS-1551229).

  5. Treatise on irreversible and statistical thermodynamics an introduction to nonclassical thermodynamics

    CERN Document Server

    Yourgrau, Wolfgang; Raw, Gough

    2002-01-01

    Extensively revised edition of a much-respected work examines thermodynamics of irreversible processes, general principles of statistical thermodynamics, assemblies of noninteracting structureless particles, and statistical theory. 1966 edition.

  6. Influence of delayed pouring on irreversible hydrocolloid properties

    Directory of Open Access Journals (Sweden)

    Stéfani Becker Rodrigues

    2012-10-01

    Full Text Available The aim of this study was to evaluate the physical properties of irreversible hydrocolloid materials poured immediately and after different storage periods. Four alginates were tested: Color Change (Cavex; Hydrogum (Zhermack; Hydrogum 5 (Zhermack; and Hydro Print Premium (Coltene. Their physical properties, including the recovery from deformation (n = 3, compressive strength (n = 3, and detail reproduction and gypsum compatibility (n = 3, were analyzed according to ANSI/ADA specification no. 18. Specimens were stored at 23ºC and humidity and were then poured with gypsum immediately and after 1, 2, 3, 4, and 5 days. The data were analyzed by two-way analysis of variance (ANOVA and Tukey's test at p < 0.05. All of the alginate impression materials tested exhibited detail reproduction and gypsum compatibility at all times. Hydro Print Premium and Hydrogum 5 showed recovery from deformation, as established by ANSI/ADA specification no. 18, after 5 days of storage. As the storage time increased, the compressive strength values also increased. Considering the properties of compounds' recovery from deformation, compressive strength, and detail reproduction and gypsum compatibility, irreversible hydrocolloids should be poured immediately.

  7. Irreversible entropy model for damage diagnosis in resistors

    Energy Technology Data Exchange (ETDEWEB)

    Cuadras, Angel, E-mail: angel.cuadras@upc.edu; Crisóstomo, Javier; Ovejas, Victoria J.; Quilez, Marcos [Instrumentation, Sensor and Interfaces Group, Electronic Engineering Department, Escola d' Enginyeria de Telecomunicació i Aeronàutica de Castelldefels EETAC, Universitat Politècnica de Catalunya, Barcelona Tech (UPC), Castelldefels-Barcelona (Spain)

    2015-10-28

    We propose a method to characterize electrical resistor damage based on entropy measurements. Irreversible entropy and the rate at which it is generated are more convenient parameters than resistance for describing damage because they are essentially positive in virtue of the second law of thermodynamics, whereas resistance may increase or decrease depending on the degradation mechanism. Commercial resistors were tested in order to characterize the damage induced by power surges. Resistors were biased with constant and pulsed voltage signals, leading to power dissipation in the range of 4–8 W, which is well above the 0.25 W nominal power to initiate failure. Entropy was inferred from the added power and temperature evolution. A model is proposed to understand the relationship among resistance, entropy, and damage. The power surge dissipates into heat (Joule effect) and damages the resistor. The results show a correlation between entropy generation rate and resistor failure. We conclude that damage can be conveniently assessed from irreversible entropy generation. Our results for resistors can be easily extrapolated to other systems or machines that can be modeled based on their resistance.

  8. Irreversible entropy model for damage diagnosis in resistors

    International Nuclear Information System (INIS)

    Cuadras, Angel; Crisóstomo, Javier; Ovejas, Victoria J.; Quilez, Marcos

    2015-01-01

    We propose a method to characterize electrical resistor damage based on entropy measurements. Irreversible entropy and the rate at which it is generated are more convenient parameters than resistance for describing damage because they are essentially positive in virtue of the second law of thermodynamics, whereas resistance may increase or decrease depending on the degradation mechanism. Commercial resistors were tested in order to characterize the damage induced by power surges. Resistors were biased with constant and pulsed voltage signals, leading to power dissipation in the range of 4–8 W, which is well above the 0.25 W nominal power to initiate failure. Entropy was inferred from the added power and temperature evolution. A model is proposed to understand the relationship among resistance, entropy, and damage. The power surge dissipates into heat (Joule effect) and damages the resistor. The results show a correlation between entropy generation rate and resistor failure. We conclude that damage can be conveniently assessed from irreversible entropy generation. Our results for resistors can be easily extrapolated to other systems or machines that can be modeled based on their resistance

  9. Effects of thermo-chemical pretreatment plus microbial fermentation and enzymatic hydrolysis on saccharification and lignocellulose degradation of corn straw.

    Science.gov (United States)

    Wang, Ping; Chang, Juan; Yin, Qingqiang; Wang, Erzhu; Zhu, Qun; Song, Andong; Lu, Fushan

    2015-10-01

    In order to increase corn straw degradation, the straw was kept in the combined solution of 15% (w/w) lime supernatant and 2% (w/w) sodium hydroxide with liquid-to-solid ratio of 13:1 (mL/g) at 83.92°C for 6h; and then added with 3% (v/v) H2O2 for reaction at 50°C for 2h; finally cellulase (32.3 FPU/g dry matter) and xylanase (550 U/g dry matter) was added to keep at 50°C for 48 h. The maximal reducing sugars yield (348.77 mg/g) was increased by 126.42% (Pcellulose, hemicellulose and lignin in pretreated corn straw with enzymatic hydrolysis were increased by 40.08%, 45.71% and 52.01%, compared with the native corn straw with enzymatic hydrolysis (P<0.05). The following study indicated that the combined microbial fermentation and enzymatic hydrolysis could further increase straw degradation and reducing sugar yield (442.85 mg/g, P<0.05). Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Computing molecular fluctuations in biochemical reaction systems based on a mechanistic, statistical theory of irreversible processes.

    Science.gov (United States)

    Kulasiri, Don

    2011-01-01

    We discuss the quantification of molecular fluctuations in the biochemical reaction systems within the context of intracellular processes associated with gene expression. We take the molecular reactions pertaining to circadian rhythms to develop models of molecular fluctuations in this chapter. There are a significant number of studies on stochastic fluctuations in intracellular genetic regulatory networks based on single cell-level experiments. In order to understand the fluctuations associated with the gene expression in circadian rhythm networks, it is important to model the interactions of transcriptional factors with the E-boxes in the promoter regions of some of the genes. The pertinent aspects of a near-equilibrium theory that would integrate the thermodynamical and particle dynamic characteristics of intracellular molecular fluctuations would be discussed, and the theory is extended by using the theory of stochastic differential equations. We then model the fluctuations associated with the promoter regions using general mathematical settings. We implemented ubiquitous Gillespie's algorithms, which are used to simulate stochasticity in biochemical networks, for each of the motifs. Both the theory and the Gillespie's algorithms gave the same results in terms of the time evolution of means and variances of molecular numbers. As biochemical reactions occur far away from equilibrium-hence the use of the Gillespie algorithm-these results suggest that the near-equilibrium theory should be a good approximation for some of the biochemical reactions. © 2011 Elsevier Inc. All rights reserved.

  11. Potentialities of a Membrane Reactor with Laccase Grafted Membranes for the Enzymatic Degradation of Phenolic Compounds in Water

    Directory of Open Access Journals (Sweden)

    Vorleak Chea

    2014-10-01

    Full Text Available This paper describes the degradation of phenolic compounds by laccases from Trametes versicolor in an enzymatic membrane reactor (EMR. The enzymatic membranes were prepared by grafting laccase on a gelatine layer previously deposited onto α-alumina tubular membranes. The 2,6-dimethoxyphenol (DMP was selected  from among the three different phenolic compounds tested (guaiacol, 4-chlorophenol and DMP to study the performance of the EMR in dead end configuration. At the lowest feed substrate concentration tested (100 mg·L−1, consumption increased with flux (up to 7.9 × 103 mg·h−1·m−2 at 128 L·h−1·m−2, whereas at the highest substrate concentration (500 mg·L−1, it was shown that the reaction was limited by the oxygen content.

  12. Solvent-free enzymatic synthesis of feruloylated structured lipids by the transesterification of ethyl ferulate with castor oil.

    Science.gov (United States)

    Sun, Shangde; Zhu, Sha; Bi, Yanlan

    2014-09-01

    A novel enzymatic route of feruloylated structured lipids synthesis by the transesterification of ethyl ferulate (EF) with castor oil, in solvent-free system, was investigated. The transesterification reactions were catalysed by Novozym 435, Lipozyme RMIM, and Lipozyme TLIM, among which Novozym 435 showed the best catalysis performance. Effects of feruloyl donors, reaction variables, and ethanol removal on the transesterification were also studied. High EF conversion (∼100%) was obtained under the following conditions: enzyme load 20% (w/w, relative to the weight of substrates), reaction temperature 90 °C, substrate molar ratio 1:1 (EF/castor oil), 72 h, vacuum pressure 10 mmHg, and 200 rpm. Under these conditions, the transesterification product consisted of 62.6% lipophilic feruloylated structured lipids and 37.3% hydrophilic feruloylated lipids. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Enzymatic desulfurization of coal

    Energy Technology Data Exchange (ETDEWEB)

    Boyer, Y.N.; Crooker, S.C.; Kitchell, J.P.; Nochur, S.V.

    1991-05-16

    The overall objective of this program was to investigate the feasibility of an enzymatic desulfurization process specifically intended for organic sulfur removal from coal. Toward that end, a series of specific objectives were defined: (1) establish the feasibility of (bio)oxidative pretreatment followed by biochemical sulfate cleavage for representative sulfur-containing model compounds and coals using commercially-available enzymes; (2) investigate the potential for the isolation and selective use of enzyme preparations from coal-utilizing microbial systems for desulfurization of sulfur-containing model compounds and coals; and (3) develop a conceptual design and economic analysis of a process for enzymatic removal of organic sulfur from coal. Within the scope of this program, it was proposed to carry out a portion of each of these efforts concurrently. (VC)

  14. High-performance liquid chromatography analysis methods developed for quantifying enzymatic esterification of flavonoids in ionic liquids.

    Science.gov (United States)

    Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

    2008-07-11

    Methods using reversed-phase high-performance liquid chromatography (RP-HPLC) with ELSD were investigated to quantify enzymatic reactions of flavonoids with fatty acids in the presence of diverse room temperature ionic liquids (RTILs). A buffered salt (preferably triethylamine-acetate) was found essential for separation of flavonoids from strongly polar RTILs, whereby RTILs were generally visible as two major peaks identified based on an ion-pairing/exchanging hypothesis. C8 and C12 stationary phases were optimal while mobile phase pH (3-7) had only a minor influence on separation. The method developed was successfully applied for primary screening of RTILs (>20), with in depth evaluation of substrates in 10 RTILs, for their evaluation as reaction media.

  15. The influence of Fe2+ on growth and development of cells enzymatically isolated from Porphyra yezoensis blades

    Science.gov (United States)

    Songdong, Shen; Jixun, Dai

    2005-03-01

    Fe2+ acted as an accessorial factor for many cellular enzymatic reactions is very important for seaweed growth and development, but the Fe2+ requirement in nori had not been seen, Porphyra yezoensis cells were separated enzymatically and cultured in a series of sterilized seawater media containing various concentrations of Fe2+. The growth development and cell were investigated in this work. Through this experiment, two biologically-meant concentration scales were found, one is low concentrations, 12.1-102.1 μg/L, 10-100 times than that in seawater, favoring the development of isolated cells of Porphyra and the other was high concentrations, more than 10mg/L inhibiting the cell growth, leading to the deformity and shrinkage of the cells. At the concentration of 50 mg/L, the cells stopped growing and died eventually.

  16. Enzymatic Browning: a practical class

    Directory of Open Access Journals (Sweden)

    Maria Teresa Pedrosa Silva Clerici

    2014-10-01

    Full Text Available This paper presents a practical class about the enzymes polyphenol oxidases, which have been shown to be responsible for the enzymatic browning of fruits and vegetables. Vegetables samples were submitted to enzymatic inactivation process with chemical reagents, as well as by bleaching methods of applying heat by conventional oven and microwave oven. Process efficiency was assessed qualitatively by both observing the guaiacol peroxidase activity and after the storage period under refrigeration or freezing. The practical results obtained in this class allow exploring multidisciplinary knowledge in food science, with practical applications in everyday life.

  17. Microbiome of Deep Dentinal Caries Lesions in Teeth with Symptomatic Irreversible Pulpitis.

    Science.gov (United States)

    Rôças, Isabela N; Alves, Flávio R F; Rachid, Caio T C C; Lima, Kenio C; Assunção, Isauremi V; Gomes, Patrícia N; Siqueira, José F

    2016-01-01

    This study used a next-generation sequencing approach to identify the bacterial taxa occurring in the advanced front of caries biofilms associated with pulp exposure and irreversible pulpitis. Samples were taken from the deepest layer of dentinal caries lesions associated with pulp exposure in 10 teeth diagnosed with symptomatic irreversible pulpitis. DNA was extracted and the microbiome was characterized on the basis of the V4 hypervariable region of the 16S rRNA gene by using paired-end sequencing on Illumina MiSeq device. Bacterial taxa were mapped to 14 phyla and 101 genera composed by 706 different OTUs. Three phyla accounted for approximately 98% of the sequences: Firmicutes, Actinobacteria and Proteobacteria. These phyla were also the ones with most representatives at the species level. Firmicutes was the most abundant phylum in 9/10 samples. As for genera, Lactobacillus accounted for 42.3% of the sequences, followed by Olsenella (13.7%), Pseudoramibacter (10.7%) and Streptococcus (5.5%). Half of the samples were heavily dominated by Lactobacillus, while in the other half lactobacilli were in very low abundance and the most dominant genera were Pseudoramibacter, Olsenella, Streptococcus, and Stenotrophomonas. High bacterial diversity occurred in deep dentinal caries lesions associated with symptomatic irreversible pulpitis. The microbiome could be classified according to the relative abundance of Lactobacillus. Except for Lactobacillus species, most of the highly prevalent and abundant bacterial taxa identified in this study have been commonly detected in infected root canals. The detected taxa can be regarded as candidate pathogens for irreversible pulpitis and possibly the pioneers in pulp invasion to initiate endodontic infection.

  18. Microbiome of Deep Dentinal Caries Lesions in Teeth with Symptomatic Irreversible Pulpitis.

    Directory of Open Access Journals (Sweden)

    Isabela N Rôças

    Full Text Available This study used a next-generation sequencing approach to identify the bacterial taxa occurring in the advanced front of caries biofilms associated with pulp exposure and irreversible pulpitis. Samples were taken from the deepest layer of dentinal caries lesions associated with pulp exposure in 10 teeth diagnosed with symptomatic irreversible pulpitis. DNA was extracted and the microbiome was characterized on the basis of the V4 hypervariable region of the 16S rRNA gene by using paired-end sequencing on Illumina MiSeq device. Bacterial taxa were mapped to 14 phyla and 101 genera composed by 706 different OTUs. Three phyla accounted for approximately 98% of the sequences: Firmicutes, Actinobacteria and Proteobacteria. These phyla were also the ones with most representatives at the species level. Firmicutes was the most abundant phylum in 9/10 samples. As for genera, Lactobacillus accounted for 42.3% of the sequences, followed by Olsenella (13.7%, Pseudoramibacter (10.7% and Streptococcus (5.5%. Half of the samples were heavily dominated by Lactobacillus, while in the other half lactobacilli were in very low abundance and the most dominant genera were Pseudoramibacter, Olsenella, Streptococcus, and Stenotrophomonas. High bacterial diversity occurred in deep dentinal caries lesions associated with symptomatic irreversible pulpitis. The microbiome could be classified according to the relative abundance of Lactobacillus. Except for Lactobacillus species, most of the highly prevalent and abundant bacterial taxa identified in this study have been commonly detected in infected root canals. The detected taxa can be regarded as candidate pathogens for irreversible pulpitis and possibly the pioneers in pulp invasion to initiate endodontic infection.

  19. Fed batch enzymatic saccharification of food waste improves the sugar concentration in the hydrolysates and eventually the ethanol fermentation by Saccharomyces cerevisiae H058

    Directory of Open Access Journals (Sweden)

    Shoubao Yan

    2012-04-01

    Full Text Available The enzymatic hydrolysis of food waste by commercially available enzymes and the subsequent ethanol fermentation of the hydrolysates by Saccharomyces cerecisiae H058 were studied in this work. The optimum batch enzymatic conditions were found to be saccharification pH of 4.5, temperature of 55!, glucoamylase concentration of 120 u/g, α-amylase concentration of 10 u/g, solid-liquid ratio of 1: 0.75 (w/w. Fed batch hydrolysis process was started with a solid-liquid ratio of 1: 1 (w/w, with solid food waste added at time lapse of 2 h to get a final solid-liquid ratio of 1: 0.5 (w/w. After 4 h of reaction, the reducing sugar concentration reached 194.43 g/L with a enzymatic digestibility of 93.12%. Further fermentation of the batch and fed batch enzymatic hydrolysates, which contained reducing sugar concentration of 131.41 and 194.43 g/L respectively, was performed using Saccharomyces cerevisiae H058, 62.93 and 90.72 g/L ethanol was obtained within 48 h.

  20. Effects of oxymorphazone in frogs: long lasting antinociception in vivo, and apparently irreversible binding in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Benyhe, S.; Hoffman, G.; Varga, E.; Hosztafi, S.; Toth, G.; Borsodi, A.; Wollemann, M.

    1989-01-01

    Oxymorphazone was found to be a relatively weak antinociceptive drug in intact frog (Rana esculenta) when acetic acid was used as pain stimulus. Frogs remained analgesic for at least 48 hrs following oxymorphazone administration. The ligand increased the latency of wiping reflex in spinal frogs too. There effects were blocked by naloxone. In equilibrium binding studies (/sup 3/H)oxymorphazone had high affinity to the opioid receptors of frog brain and spinal cord as well. Kinetic experiments show that only 25% of the bound (/sup 3/H)oxymorphazone is readily dissociable. Preincubation of the membranes with labeled oxymorphazone results in a washing resistant inhibition of the opioid binding sites. At least 70% of the (/sup 3/H)oxymorphazone specific binding is apparently irreversible after reaction at 5 nM ligand concentration, and this can be enhanced by a higher concentration of tritiated ligand.

  1. Enzymatic biodiesel production: Technical and economical considerations

    DEFF Research Database (Denmark)

    Munk Nielsen, Per; Brask, Jesper; Fjerbæk, Lene

    2008-01-01

    It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial-scale biodiesel production. This is mainly due to non-optimized process design...... and a lack of available costeffective enzymes. The technology to re-use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates...... that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy....

  2. Extended irreversible thermodynamics and the Jeffreys type constitutive equations

    International Nuclear Information System (INIS)

    Serdyukov, S.I.

    2003-01-01

    A postulate of extended irreversible thermodynamics is considered, according to which the entropy density is a function of the internal energy, the specific volume, and their material time derivatives. On the basis of this postulate, entropy balance equations and phenomenological equations are obtained, which directly lead to the Jeffreys type constitutive equations

  3. Enzymatic and free radical formation of cis- and trans- epoxyeicosatrienoic acids in vitro and in vivo.

    Science.gov (United States)

    Aliwarga, Theresa; Raccor, Brianne S; Lemaitre, Rozenn N; Sotoodehnia, Nona; Gharib, Sina A; Xu, Libin; Totah, Rheem A

    2017-11-01

    Epoxyeicosatrienoic acids (EETs) are metabolites of arachidonic acid (AA) oxidation that have important cardioprotective and signaling properties. AA is an ω-6 polyunsaturated fatty acid (PUFA) that is prone to autoxidation. Although hydroperoxides and isoprostanes are major autoxidation products of AA, EETs are also formed from the largely overlooked peroxyl radical addition mechanism. While autoxidation yields both cis- and trans-EETs, cytochrome P450 (CYP) epoxygenases have been shown to exclusively catalyze the formation of all regioisomer cis-EETs, on each of the double bonds. In plasma and red blood cell (RBC) membranes, cis- and trans-EETs have been observed, and both have multiple physiological functions. We developed a sensitive ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) assay that separates cis- and trans- isomers of EETs and applied it to determine the relative distribution of cis- vs. trans-EETs in reaction mixtures of AA subjected to free radical oxidation in benzene and liposomes in vitro. We also determined the in vivo distribution of EETs in several tissues, including human and mouse heart, and RBC membranes. We then measured EET levels in heart and RBC of young mice compared to old. Formation of EETs in free radical reactions of AA in benzene and in liposomes exhibited time- and AA concentration-dependent increase and trans-EET levels were higher than cis-EETs under both conditions. In contrast, cis-EET levels were overall higher in biological samples. In general, trans-EETs increased with mouse age more than cis-EETs. We propose a mechanism for the non-enzymatic formation of cis- and trans-EETs involving addition of the peroxyl radical to one of AA's double bonds followed by bond rotation and intramolecular homolytic substitution (S H i). Enzymatic formation of cis-EETs by cytochrome P450 most likely occurs via a one-step concerted mechanism that does not allow bond rotation. The ability to accurately measure

  4. Anticancer system created by acrolein and hydroxyl radical generated in enzymatic oxidation of spermine and other biochemical reactions.

    Science.gov (United States)

    Alarcon, R A

    2012-10-01

    A hypothesis suggesting the existence of a ubiquitous physiological anticancer system created by two highly reactive oxidative stress inducers with anticancer properties, acrolein and hydroxyl radical, is reported in this communication. Both components can originate separately or together in several biochemical interactions, among them, the enzymatic oxidation of the polyamine spermine, which appear to be their main source. The foundations of this hypothesis encompass our initial search for growth-inhibitors or anticancer compounds in biological material leading to the isolation of spermine, a polyamine that became highly cytotoxic through the generation of acrolein, when enzymatically oxidized. Findings complemented with pertinent literature data by other workers and observed anticancer activities by sources capable of producing acrolein and hydroxyl radical. This hypothesis obvious implication: spermine enzymatic oxidations or other biochemical interactions that would co-generate acrolein and hydroxyl radical, the anticancer system components, should be tried as treatments for any given cancer. The biochemical generation of acrolein observed was totally unexpected, since this aldehyde was known; as a very toxic and highly reactive xenobiotic chemical produced in the pyrolysis of fats and other organic material, found as an atmospheric pollutant, in tobacco smoke and car emissions, and mainly used as a pesticide or aquatic herbicide. Numerous studies on acrolein, considered after our work a biological product, as well, followed. In them, acrolein widespread presence, its effects on diverse cellular proteins, such as, growth factors, and its anticancer activities, were additionally reported. Regarding hydroxyl radical, the second component of the proposed anticancer system, and another cytotoxic product in normal cell metabolism, it co-generates with acrolein in several biochemical interactions, occurrences suggesting that these products might jointly fulfill some

  5. Effects of irreversibility and economics on the performance of a heat engine

    International Nuclear Information System (INIS)

    Ibrahim, O.M.; Klein, S.A.; Mitchell, J.W.

    1992-01-01

    In this paper, optimization of the power output of an internally irreversible heat engine is considered for finite capacitance rates of the external fluid streams. The method of Lagrange multipliers is used to solve for working fluid temperatures which yield maximum power. Analytical expressions for the maximum power and the cycle efficiency at miximum power are obtained. The effects of irreversibility and economics on the performance of a heat engine are investigated. A relationship between the maximum power point and economically optimum design is identified. It is demonstrated that, with certain reasonable economic assumptions, the maximum power point of a heat engine corresponds to a point of minimum life-cycle costs

  6. Ethacrynic acid improves the antitumor effects of irreversible epidermal growth factor receptor tyrosine kinase inhibitors in breast cancer.

    Science.gov (United States)

    Liu, Bing; Huang, XinPing; Hu, YunLong; Chen, TingTing; Peng, BoYa; Gao, NingNing; Jin, ZhenChao; Jia, TieLiu; Zhang, Na; Wang, ZhuLin; Jin, GuangYi

    2016-09-06

    Prolonged treatment of breast cancer with epidermal growth factor receptor (EGFR) tyrosine kinase inhibitors (TKIs) often results in acquired resistance and a narrow therapeutic index. One strategy to improve the therapeutic effects of EGFR TKIs is to combine them with drugs used for other clinical indications. Ethacrynic acid (EA) is an FDA approved drug that may have antitumor effects and may enhance the cytotoxicity of chemotherapeutic agents by binding to glutathione and inhibiting WNT signaling. While the α,β-unsaturated-keto structure of EA is similar to that of irreversible TKIs, the mechanism of action of EA when combined with irreversible EGFR TKIs in breast cancer remains unknown. We therefore investigated the combination of irreversible EGFR TKIs and EA. We found that irreversible EGFR TKIs and EA synergistically inhibit breast cancer both in vitro and in vivo. The combination of EGFR TKIs and EA induces necrosis and cell cycle arrest and represses WNT/β-catenin signaling as well as MAPK-ERK1/2 signaling. We conclude that EA synergistically enhances the antitumor effects of irreversible EGFR TKIs in breast cancer.

  7. Positive Feedback of NDT80 Expression Ensures Irreversible Meiotic Commitment in Budding Yeast

    Science.gov (United States)

    Tsuchiya, Dai; Yang, Yang; Lacefield, Soni

    2014-01-01

    In budding yeast, meiotic commitment is the irreversible continuation of the developmental path of meiosis. After reaching meiotic commitment, cells finish meiosis and gametogenesis, even in the absence of the meiosis-inducing signal. In contrast, if the meiosis-inducing signal is removed and the mitosis-inducing signal is provided prior to reaching meiotic commitment, cells exit meiosis and return to mitosis. Previous work has shown that cells commit to meiosis after prophase I but before entering the meiotic divisions. Since the Ndt80 transcription factor induces expression of middle meiosis genes necessary for the meiotic divisions, we examined the role of the NDT80 transcriptional network in meiotic commitment. Using a microfluidic approach to analyze single cells, we found that cells commit to meiosis in prometaphase I, after the induction of the Ndt80-dependent genes. Our results showed that high-level expression of NDT80 is important for the timing and irreversibility of meiotic commitment. A modest reduction in NDT80 levels delayed meiotic commitment based on meiotic stages, although the timing of each meiotic stage was similar to that of wildtype cells. A further reduction of NDT80 resulted in the surprising finding of inappropriately uncommitted cells: withdrawal of the meiosis-inducing signal and addition of the mitosis-inducing signal to cells at stages beyond metaphase I caused return to mitosis, leading to multi-nucleate cells. Since Ndt80 enhances its own transcription through positive feedback, we tested whether positive feedback ensured the irreversibility of meiotic commitment. Ablating positive feedback in NDT80 expression resulted in a complete loss of meiotic commitment. These findings suggest that irreversibility of meiotic commitment is a consequence of the NDT80 transcriptional positive feedback loop, which provides the high-level of Ndt80 required for the developmental switch of meiotic commitment. These results also illustrate the

  8. Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

    DEFF Research Database (Denmark)

    Li, Deng; Xu, Xuebing; Gudmundur G, Haraldsson

    2005-01-01

    This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary...... in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RM IM, and Lipase PS-C. Many...

  9. Carbon dioxide/methanol conversion cycle based on cascade enzymatic reactions supported on superparamagnetic nanoparticles

    Directory of Open Access Journals (Sweden)

    CATERINA G.C. MARQUES NETTO

    2017-10-01

    Full Text Available ABSTRACT The conversion of carbon dioxide into important industrial feedstock is a subject of growing interest in modern society. A possible way to achieve this goal is by carrying out the CO2/methanol cascade reaction, allowing the recycle of CO2 using either chemical catalysts or enzymes. Efficient and selective reactions can be performed by enzymes; however, due to their low stability, immobilization protocols are required to improve their performance. The cascade reaction to reduce carbon dioxide into methanol has been explored by the authors, using, sequentially, alcohol dehydrogenase (ADH, formaldehyde dehydrogenase (FalDH, and formate dehydrogenase (FDH, powered by NAD+/NADH and glutamate dehydrogenase (GDH as the co-enzyme regenerating system. All the enzymes have been immobilized on functionalized magnetite nanoparticles, and their reactions investigated separately in order to establish the best performance conditions. Although the stepwise scheme led to only 2.3% yield of methanol per NADH; in a batch system under CO2 pressure, the combination of the four immobilized enzymes increased the methanol yield by 64 fold. The studies indicated a successful regeneration of NADH in situ, envisaging a real possibility of using immobilized enzymes to perform the cascade CO2-methanol reaction.

  10. Dimensional Stability of Color-Changing Irreversible Hydrocolloids after Disinfection

    Directory of Open Access Journals (Sweden)

    Khaledi AAR

    2015-03-01

    Full Text Available Statement of Problem: Disinfection of dental impressions is a weak point in the dental hygiene chain. In addition, dental office personnel and dental technicians are endangered by cross-contamination. Objectives: This study aimed to investigate the dimensional stability of two color-changing irreversible hydrocolloid materials (IH after disinfection with glutaraldehyde. Materials and Methods: In this in vitro study, impressions were made of a master maxillary arch containing three reference inserts on the occlucal surface of the left and right maxillary second molars and in the incisal surface of the maxillary central incisors. Two types of color-changing irreversible hydrocolloid (tetrachrom, cavex were used. Glutaraldehyde 2% was used in two methods of spraying and immersion to disinfect the impressions. The control group was not disinfected. Casts were made of type IV gypsum. The linear dimensional change of the stone casts was measured with a profile projector. For statistical analysis, Kruskall-Wallis and Mann-Witney tests were used (α=0.05. Results: By immersion method, the casts fabricated from tetrachrom were 0.36% larger in the anteroposterior (AP and 0.05% smaller in cross arch (CA dimensions; however, the casts prepared after spraying of tetrachrom were 0.44% larger in the AP and 0.10% smaller in CA dimensions. The casts made from Cavex were 0.05% smaller in the AP and 0.02% smaller in CA dimensions after spraying and 0.01% smaller in the AP and 0.003% smaller in CA dimensions after immersion. Generally there were not significant differences in AP and CA dimensions of the experimental groups compared to the control (p > 0.05. Conclusions: Disinfection of the tested color-changing irreversible hydrocolloids by glutaraldahyde 2% did not compromise the accuracy of the obtained casts.

  11. Noncanonical substrate preference of lambda exonuclease for 5′-nonphosphate-ended dsDNA and a mismatch-induced acceleration effect on the enzymatic reaction

    Science.gov (United States)

    Yang, Yufei; Chen, Wei; Wang, Jiayu; Yang, Ziyu; Wang, Shenlin; Xiao, Xianjin; Li, Mengyuan

    2018-01-01

    Abstract Lambda exonuclease (λ exo) plays an important role in the resection of DNA ends for DNA repair. Currently, it is also a widely used enzymatic tool in genetic engineering, DNA-binding protein mapping, nanopore sequencing and biosensing. Herein, we disclose two noncanonical properties of this enzyme and suggest a previously undescribed hydrophobic interaction model between λ exo and DNA substrates. We demonstrate that the length of the free portion of the substrate strand in the dsDNA plays an essential role in the initiation of digestion reactions by λ exo. A dsDNA with a 5′ non-phosphorylated, two-nucleotide-protruding end can be digested by λ exo with very high efficiency. Moreover, we show that when a conjugated structure is covalently attached to an internal base of the dsDNA, the presence of a single mismatched base pair at the 5′ side of the modified base may significantly accelerate the process of digestion by λ exo. A detailed comparison study revealed additional π–π stacking interactions between the attached label and the amino acid residues of the enzyme. These new findings not only broaden our knowledge of the enzyme but will also be very useful for research on DNA repair and in vitro processing of nucleic acids. PMID:29490081

  12. Magnetic irreversibility in granular superconductors: ac susceptibility study

    International Nuclear Information System (INIS)

    Perez, F.; Obradors, X.; Fontcuberta, J.; Vallet, M.; Gonzalez-Calbet, J.

    1991-01-01

    Ac susceptibility measurements of a ceramic weak-coupled superconductor in very low ac fields (2mG, 111Hz) are reported. We present evidence for the observation of the magnetic irreversibility following a ZFC-FC thermal cycling by means of ac susceptibilty measurements. It is shown that this technique also reflect local magnetic field effects in granular superconductors, as previously suggested in microwave surface resistance and I-V characteristics. (orig.)

  13. Chemical Synthesis of Proanthocyanidins in Vitro and Their Reactions in Aging Wines

    Directory of Open Access Journals (Sweden)

    Qiu-Hong Pan

    2008-12-01

    Full Text Available Proanthocyanidins are present in many fruits and plant products like grapes and wine, and contribute to their taste and health benefits. In the past decades of years, substantial progresses has been achieved in the identification of composition and structure of proanthocyanidins, but the debate concerning the existence of an enzymatic or nonenzymatic mechanism for proanthocyanidin condensation still goes on. Substantial attention has been paid to elucidating the potential mechanism of formation by means of biomimetic and chemical synthesis in vitro. The present paper aims at summarizing the research status on chemical synthesis of proanthocyanidins, including non-enzymatic synthesis of proanthocyanidin precursors, chemical synthesis of proanthocyanidins with direct condensation of flavanols and stereoselective synthesis of proanthocyanidins. Proanthocyanidin-involved reactions in aging wines are also reviewed such as direct and indirect reactions among proanthocyanidins, flavanols and anthocyanins. Topics for future research in this field are also put forward in this paper.

  14. Irreversible dilation of NaCl contaminated lime-cement mortar due to crystallization cycles

    International Nuclear Information System (INIS)

    Lubelli, B.; Hees, R.P.J. van; Huinink, H.P.; Groot, C.J.W.P.

    2006-01-01

    The mechanism of damage occurring in NaCl contaminated materials has not been clarified yet. Apart from crystallization pressure, other hypotheses have been proposed to explain the cause of decay. Irreversible dilation has been observed in a few cases but has never been studied in a more systematic way. The aim of the research is to contribute to the modeling of this phenomenon. In the present paper the effect of NaCl on the hydric and hygric behavior of a lime-cement mortar is extensively studied. The results indicate that NaCl influences the hydric and hygric dilation behavior of the material. The material contaminated with NaCl shrinks during dissolution and dilates during crystallization of the salt. This dilation is irreversible and sufficient to damage the material after few dissolution/crystallization cycles. This behavior is not restricted to NaCl, but is observed in the presence of other salts as well (NaNO 3 and KCl). Outcomes of electron microscopy studies suggest that salts causing irreversible dilation tend to crystallize as layers on the pore wall

  15. Unifying principles of irreversibility minimization for efficiency maximization in steady-flow chemically-reactive engines

    International Nuclear Information System (INIS)

    Ramakrishnan, Sankaran; Edwards, Christopher F.

    2014-01-01

    Systems research has led to the conception and development of various steady-flow, chemically-reactive, engine cycles for stationary power generation and propulsion. However, the question that remains unanswered is: What is the maximum-efficiency steady-flow chemically-reactive engine architecture permitted by physics? On the one hand the search for higher-efficiency cycles continues, often involving newer processes and devices (fuel cells, carbon separation, etc.); on the other hand the design parameters for existing cycles are continually optimized in response to improvements in device engineering. In this paper we establish that any variation in engine architecture—parametric change or process-sequence change—contributes to an efficiency increase via one of only two possible ways to minimize total irreversibility. These two principles help us unify our understanding from a large number of parametric analyses and cycle-optimization studies for any steady-flow chemically-reactive engine, and set a framework to systematically identify maximum-efficiency engine architectures. - Highlights: • A unified thermodynamic model to study chemically-reactive engine architectures is developed. • All parametric analyses of efficiency are unified by two irreversibility-minimization principles. • Variations in internal energy transfers yield a net work increase that is greater than engine irreversibility reduced. • Variations in external energy transfers yield a net work increase that is lesser than engine irreversibility reduced

  16. Enhanced sugar production from pretreated barley straw by additive xylanase and surfactants in enzymatic hydrolysis for acetone-butanol-ethanol fermentation.

    Science.gov (United States)

    Yang, Ming; Zhang, Junhua; Kuittinen, Suvi; Vepsäläinen, Jouko; Soininen, Pasi; Keinänen, Markku; Pappinen, Ari

    2015-01-01

    This study aims to improve enzymatic sugar production from dilute sulfuric acid-pretreated barley straw for acetone-butanol-ethanol (ABE) fermentation. The effects of additive xylanase and surfactants (polyethylene glycol [PEG] and Tween) in an enzymatic reaction system on straw hydrolysis yields were investigated. By combined application of 2g/100g dry-matter (DM) xylanase and PEG 4000, the glucose yield was increased from 53.2% to 86.9% and the xylose yield was increased from 36.2% to 70.2%, which were considerably higher than results obtained with xylanase or surfactant alone. The ABE fermentation of enzymatic hydrolysate produced 10.8 g/L ABE, in which 7.9 g/L was butanol. The enhanced sugar production increased the ABE yield from 93.8 to 135.0 g/kg pretreated straw. The combined application of xylanase and surfactants has a large potential to improve sugar production from barley straw pretreated with a mild acid and that the hydrolysate showed good fermentability in ABE production. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Enzymatic Processes in Marine Biotechnology.

    Science.gov (United States)

    Trincone, Antonio

    2017-03-25

    In previous review articles the attention of the biocatalytically oriented scientific community towards the marine environment as a source of biocatalysts focused on the habitat-related properties of marine enzymes. Updates have already appeared in the literature, including marine examples of oxidoreductases, hydrolases, transferases, isomerases, ligases, and lyases ready for food and pharmaceutical applications. Here a new approach for searching the literature and presenting a more refined analysis is adopted with respect to previous surveys, centering the attention on the enzymatic process rather than on a single novel activity. Fields of applications are easily individuated: (i) the biorefinery value-chain, where the provision of biomass is one of the most important aspects, with aquaculture as the prominent sector; (ii) the food industry, where the interest in the marine domain is similarly developed to deal with the enzymatic procedures adopted in food manipulation; (iii) the selective and easy extraction/modification of structurally complex marine molecules, where enzymatic treatments are a recognized tool to improve efficiency and selectivity; and (iv) marine biomarkers and derived applications (bioremediation) in pollution monitoring are also included in that these studies could be of high significance for the appreciation of marine bioprocesses.

  18. Computer investigations on the asymptotic behavior of the rate coefficient for the annihilation reaction A + A → product and the trapping reaction in three dimensions.

    Science.gov (United States)

    Litniewski, Marek; Gorecki, Jerzy

    2011-06-28

    We have performed intensive computer simulations of the irreversible annihilation reaction: A + A → C + C and of the trapping reaction: A + B → C + B for a variety of three-dimensional fluids composed of identical spherical particles. We have found a significant difference in the asymptotic behavior of the rate coefficients for these reactions. Both the rate coefficients converge to the same value with time t going to infinity but the convergence rate is different: the O(t(-1/2)) term for the annihilation reaction is higher than the corresponding term for the trapping reaction. The simulation results suggest that ratio of the terms is a universal quantity with the value equal to 2 or slightly above. A model for the annihilation reaction based on the superposition approximation predicts the difference in the O(t(-1/2)) terms, but overestimates the value for the annihilation reaction by about 30%. We have also performed simulations for the dimerization process: A + A → E, where E stands for a dimer. The dimerization decreases the reaction rate due to the decrease in the diffusion constant for A. The effect is successfully predicted by a simple model.

  19. Antibacterial efficacy and effect of Morinda citrifolia L. mixed with irreversible hydrocolloid for dental impressions: A randomized controlled trial.

    Science.gov (United States)

    Ahmed, A Shafath; Charles, P David; Cholan, R; Russia, M; Surya, R; Jailance, L

    2015-08-01

    This study aimed to evaluate whether the extract of Morinda citrifolia L. mixed with irreversible hydrocolloid powder decreases microbial contamination during impression making without affecting the resulting casts. Twenty volunteers were randomly divided into two groups (n = 10). Group A 30 ml extract of M. citrifolia L diluted in 30 ml of water was mixed to make the impression with irreversible hydrocolloid material. Group B 30 ml deionized water was mixed with irreversible hydrocolloid material to make the impressions following which the surface roughness and dimensional stability of casts were evaluated. Extract of M. citrifolia L. mixed with irreversible hydrocolloid decreased the percentage of microorganisms when compared with water (P impression quality.

  20. Next-Generation Catalysis for Renewables: Combining Enzymatic with Inorganic Heterogeneous Catalysis for Bulk Chemical Production

    DEFF Research Database (Denmark)

    Vennestrøm, Peter Nicolai Ravnborg; Christensen, C.H.; Pedersen, S.

    2010-01-01

    chemical platform under different conditions than those conventionally employed. Indeed, new process and catalyst concepts need to be established. Both enzymatic catalysis (biocatalysis) and heterogeneous inorganic catalysis are likely to play a major role and, potentially, be combined. One type...... of combination involves one-pot cascade catalysis with active sites from bio- and inorganic catalysts. In this article the emphasis is placed specifically on oxidase systems involving the coproduction of hydrogen peroxide, which can be used to create new in situ collaborative oxidation reactions for bulk...

  1. Phase control of light amplification with dynamically irreversible pathways of population transfer in a Λ system

    International Nuclear Information System (INIS)

    Yuan Shi; Wu Jinhui; Gao Jinyue; Pan Chunliu

    2002-01-01

    We use the relative phase of two coherent fields for the control of light amplification with dynamically irreversible pathways of population transfer in a Λ system. The population inversion and gain with dynamically irreversible pathways of population transfer are shown as the relative phase is varied. We support our results by numerical calculation and analytical explanation

  2. Logic reversibility and thermodynamic irreversibility demonstrated by DNAzyme-based Toffoli and Fredkin logic gates.

    Science.gov (United States)

    Orbach, Ron; Remacle, Françoise; Levine, R D; Willner, Itamar

    2012-12-26

    The Toffoli and Fredkin gates were suggested as a means to exhibit logic reversibility and thereby reduce energy dissipation associated with logic operations in dense computing circuits. We present a construction of the logically reversible Toffoli and Fredkin gates by implementing a library of predesigned Mg(2+)-dependent DNAzymes and their respective substrates. Although the logical reversibility, for which each set of inputs uniquely correlates to a set of outputs, is demonstrated, the systems manifest thermodynamic irreversibility originating from two quite distinct and nonrelated phenomena. (i) The physical readout of the gates is by fluorescence that depletes the population of the final state of the machine. This irreversible, heat-releasing process is needed for the generation of the output. (ii) The DNAzyme-powered logic gates are made to operate at a finite rate by invoking downhill energy-releasing processes. Even though the three bits of Toffoli's and Fredkin's logically reversible gates manifest thermodynamic irreversibility, we suggest that these gates could have important practical implication in future nanomedicine.

  3. Application of photocatalytic cadmium sulfide nanoparticles to detection of enzymatic activities of glucose oxidase and glutathione reductase using oxidation of 3,3′,5,5′-tetramethylbenzidine

    Energy Technology Data Exchange (ETDEWEB)

    Grinyte, Ruta; Garai-Ibabe, Gaizka; Saa, Laura; Pavlov, Valeri, E-mail: vpavlov@cicbiomagune.es

    2015-06-30

    Highlights: • The light-powered nanosensor fabricated by enzymatic reactions was reported. • The sensor use energy of photons for oxidation of chromogenic enzymatic substrates. • Enzymatic assays for glucose oxidase and glutathione reductase were developed. - Abstract: It was found out that semiconductor CdS nanoparticles (NPs) are able to catalyze photooxidation of the well known chromogenic enzymatic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) by oxygen. The photocatalytical oxidation of TMB does not require hydrogen peroxide and its rate is directly proportional to the quantity of CdS NPs produced in situ through the interaction of Cd{sup 2+} and S{sup 2−} ions in an aqueous medium. This phenomenon was applied to development of colorimetric sensitive assays for glucose oxidase and glutathione reductase based on enzymatic generation of CdS NPs acting as light-powered catalysts. Sensitivity of the developed chromogenic assays was of the same order of magnitude or even better than that of relevant fluorogenic assays. The present approach opens the possibility for the design of simple and sensitive colorimetric assays for a number of enzymes using inexpensive and available TMB as a universal chromogenic compound.

  4. Extended irreversible thermodynamics and non-equilibrium temperature

    Directory of Open Access Journals (Sweden)

    Casas-Vazquez, Jose'

    2008-02-01

    Full Text Available We briefly review the concept of non-equilibrium temperature from the perspectives of extended irreversible thermodynamics, fluctuation theory, and statistical mechanics. The relations between different proposals are explicitly examined in two especially simple systems: an ideal gas in steady shear flow and a forced harmonic oscillator in a thermal bath. We examine with special detail temperatures related to the average molecular kinetic energy along different spatial directions, to the average configurational energy, to the derivative of the entropy with respect to internal energy, to fluctuation-dissipation relation and discuss their measurement.

  5. Statistical mechanics out of equilibrium the irreversibility

    International Nuclear Information System (INIS)

    Alvarez Estrada, R. F.

    2001-01-01

    A Round Table about the issue of Irreversibility and related matters has taken place during the last (20th) Statistical Mechanics Conference, held in Paris (July 1998). This article tries to provide a view (necessarily limited, and hence, uncompleted) of some approaches to the subject: the one based upon deterministic chaos (which is currently giving rise to a very active research) and the classical interpretation due to Boltzmann. An attempt has been made to write this article in a self-contained way, and to avoid a technical presentation wherever possible. (Author) 29 refs

  6. Transition from reversible to irreversible magnetic exchange-spring processes in antiferromagnetically exchange-coupled hard/soft/hard trilayer structures

    International Nuclear Information System (INIS)

    Wang Xiguang; Guo Guanghua; Zhang Guangfu

    2011-01-01

    The demagnetization processes of antiferromagnetically exchange-coupled hard/soft/hard trilayer structures have been studied based on the discrete one-dimensional atomic chain model and the linear partial domain-wall model. It is found that, when the magnetic anisotropy of soft layer is taken into account, the changes of the soft layer thickness and the interfacial exchange coupling strength may lead a transition of demagnetization process in soft layer from the reversible to the irreversible magnetic exchange-spring process. For the trilayer structures with very thin soft layer, the demagnetization process exhibits typical reversible exchange-spring behavior. However, as the thickness of soft layer is increased, there is a crossover point t c , after which the process becomes irreversible. Similarly, there is also a critical interfacial exchange coupling constant A sh c , above which the exchange-spring process is reversible. When A sh sh c , the irreversible exchange-spring process is achieved. The phase diagram of reversible and irreversible exchange-spring processes is mapped in the plane of the interfacial exchange coupling A sh and soft layer thickness N s . - Research highlights: → A differing magnetic exchange-spring process is found in antiferromagnetically exchange-coupled hard/soft/hard trilayers if the magnetic anisotropy of the soft layers is taken into account. → The change of the soft layer thickness may lead to a transition of demagnetization process in soft layer from the reversible to the irreversible exchange-spring process. → The change of the soft-hard interfacial exchange coupling strength may lead a transition of demagnetization process in soft layer from the reversible to the irreversible exchange-spring process. → The phase diagram of reversible and irreversible exchange-spring processes is mapped in the plane of the interfacial exchange coupling and soft layer thickness.

  7. Understanding Irreversible Degradation of Nb3Sn Wires with Fundamental Fracture Mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Yuhu [PPPL; Calzolaio, Ciro [Univ of Geneva; Senatore, Carmine [Univ of Geneva

    2014-08-01

    Irreversible performance degradation of advanced Nb3Sn superconducting wires subjected to transverse or axial mechanical loading is a critical issue for the design of large-scale fusion and accelerator magnets such as ITER and LHC. Recent SULTAN tests indicate that most cable-in-conduit conductors for ITER coils made of Nb3Sn wires processed by various fabrication techniques show similar performance degradation under cyclic loading. The irreversible degradation due to filament fracture and local strain accumulation in Nb3Sn wires cannot be described by the existing strand scaling law. Fracture mechanic modeling combined with X-ray diffraction imaging of filament micro-crack formation inside the wires under mechanical loading may reveal exciting insights to the wire degradation mechanisms. We apply fundamental fracture mechanics with a singularity approach to study influence of wire filament microstructure of initial void size and distribution to local stress concentration and potential crack propagation. We report impact of the scale and density of the void structure on stress concentration in the composite wire materials for crack initiation. These initial defects result in an irreversible degradation of the critical current beyond certain applied stress. We also discuss options to minimize stress concentration in the design of the material microstructure for enhanced wire performance for future applications.

  8. Capillary gel electrophoresis-coupled aptamer enzymatic cleavage protection strategy for the simultaneous detection of multiple small analytes.

    Science.gov (United States)

    Perrier, Sandrine; Zhu, Zhenyu; Fiore, Emmanuelle; Ravelet, Corinne; Guieu, Valérie; Peyrin, Eric

    2014-05-06

    This novel, multi small-analyte sensing strategy is the result of combining the target-induced aptamer enzymatic protection approach with the CGE-LIF (capillary gel electrophoresis with laser-induced fluorescence) technique. The implemented assay principle is based on an analysis of the phosphodiesterase I (PDE I)-mediated size variation of a fluorescein-labeled aptamer (FApt), the enzyme catalyzing the removal of nucleotides from DNA in the 3' to 5' direction. In the absence of the target, the unfolded aptamer was enzymatically cleaved into short DNA fragments. Upon target binding, the DNA substrate was partially protected against enzymatic hydrolysis. The amount of bound aptamer remaining after the exonuclease reaction was proportional to the concentration of the target. The CGE technique, which was used to determine the separation of FApt species from DNA digested products, permitted the quantification of adenosine (A), ochratoxin A (O), and tyrosinamide (T) under the same optimized enzymatic conditions. This assay strategy was subsequently applied to the simultaneous detection of A, O, and T in a single capillary under buffered conditions using corresponding FApt probes of different lengths (23, 36, and 49 nucleotides, respectively). Additionally, the detection of these three small molecules was successfully achieved in a complex medium (diluted, heat-treated human serum) showing a good recovery. It is worth noting that the multiplexed analysis was accomplished for targets with different charge states by using aptamers possessing various structural features. This sensing platform constitutes a rationalized and reliable approach with an expanded potential for a high-throughput determination of small analytes in a single capillary.

  9. Operation and Control of Enzymatic Biodiesel Production

    DEFF Research Database (Denmark)

    Price, Jason Anthony; Huusom, Jakob Kjøbsted; Nordblad, Mathias

    This work explores the control of biodiesel production via an enzymatic catalyst. The process involves the transesterification of oils/fats with an alcohol (usually methanol or ethanol), using enzymatic catalysts to generate mono-alkyl esters (the basis of biodiesel) and glycerol as by......-product. Current literature indicates that enzymatic processing of oils and fats to produce biodiesel is technically feasible and developments in immobilization technology indicate that enzyme catalysts can become cost effective compared to chemical processing. However, with very few exceptions, enzyme technology...... is not currently used in commercial-scale biodiesel production. This is mainly due to non-optimized process designs, which do not use the full potential of the catalysts in a cost-efficient way. Furthermore is it unclear what process variables need to be monitored and controlled to ensure optimal economics...

  10. ENZYMATIC PRODUCTION OF ETHYL OLEATE ESTER USING A LIPASE FROM CANDIDA ANTARCTICA B

    Directory of Open Access Journals (Sweden)

    N. Sampaio Neta

    2012-05-01

    Full Text Available Lipases are biocatalysts of great importance in different areas, being able to catalyze reactions in aqueous or organic media. Furthermore, these enzymes are capable of using several substrates being stable in a wide range of pH and temperatures. Lipases promote the esterification between fatty acids and ethanol producing oleate esters. The aim of this work is to produce ethyl oleate ester by enzymatic esterification of oleic acid with ethanol. A lipase from Candida antarctica type B was used at a temperature of 55 °C. The reaction was conducted using oleic acid, sodium sulfate anhydrous, lipase and ethanol, with a ratio of oleic acid (0.03 mol or 10 ml, lipase (0.1 mol or 0.01 g, sodium sulfate anhydrous (5 g and ethanol 99 % (100 ml. Several reaction times were studied, namely 48, 72, 96 and 120 hours. Nuclear Magnetic Resonance (1H and 13C and Infrared spectra confirmed the production of ethyl oleate ester for the studied conditions. The highest ethyl oleate production yield was obtained for 96 hours reaction time. Ethyl oleate esters have been reported to possess interesting applications in several industrial fields, such as food, aromatics, cosmetics, detergents, flavors and pharmaceuticals.

  11. Determining the complex modulus of alginate irreversible hydrocolloid dental material.

    Science.gov (United States)

    King, Shalinie; See, Howard; Thomas, Graham; Swain, Michael

    2008-11-01

    The aim of the study is to investigate the visco-elastic response of an alginate irreversible hydrocolloid dental impression material during setting. A novel squeeze film Micro-Fourier Rheometer (MFR, GBC Scientific Equipment, Australia) was used to determine the complex modulus of an alginate irreversible hydrocolloid dental impression material (Algident, ISO 1563 Class A Type 1, Dentalfarm Australia Pty. Ltd.) during setting after mixing. Data was collected every 30s for 10 min in one study and every 10 min for a total of 60 min in another study. A high level of repeatability was observed. The results indicate that the MFR is capable of recording the complex shear modulus of alginate irreversible hydrocolloid for 60 min from the start of mixing and to simultaneously report the changing visco-elastic parameters at all frequencies between 1 Hz and 100 Hz. The storage modulus shows a dramatic increase to 370% of its starting value after 6 min and then reduces to 55% after 60 min. The loss modulus increases to a maximum of 175% of its starting value after 10 min and then reduces to 94% after 60 min. The MFR enables the changes in the complex modulus through the complete setting process to be followed. It is anticipated this approach may provide a better method to compare the visco-elastic properties of impression materials and assist with identification of optimum types for different clinical requirements. The high stiffness of the instrument and the use of band-limited pseudo-random noise as the input signal are the main advantages of this technique over conventional rheometers for determining the changes in alginate visco-elasticity.

  12. Enzymatic hydrolysis of plant extracts containing inulin

    Energy Technology Data Exchange (ETDEWEB)

    Guiraud, J.P.; Galzy, P.

    1981-10-01

    Inulin-rich extracts of chicory and Jerusalem artichoke are a good potential source of fructose. Total enzymatic hydrolysis of these extracts can be effected by yeast inulinases (EC 3.2.1.7). Chemical prehydrolysis is unfavourable. Enzymatic hydrolysis has advantages over chemical hydrolysis: it does not produce a dark-coloured fraction or secondary substances. It is possible to envisage the preparation of high fructose syrups using this process. (Refs. 42).

  13. Effects of process parameters of various pretreatments on enzymatic hydrolysability of Ceiba pentandra (L.) Gaertn. (Kapok) fibre: A response surface methodology study

    International Nuclear Information System (INIS)

    Tye, Ying Ying; Lee, Keat Teong; Wan Abdullah, Wan Nadiah; Leh, Cheu Peng

    2015-01-01

    Kapok fibre is a promising raw material to produce sugar by enzymatic hydrolysis. In this work, effects of water, acid and alkaline pretreatments on the enzymatic sugar yield were studied through response surface methodology (RSM) and supported by the analysis of chemical compositions and physical structure of the fibre. For water pretreatment, reaction temperature and time were the independent variables while chemical concentration was also used as the third independent variable for acid and alkaline pretreatments. For all pretreatments, the enzymatic hydrolysis conditions were kept constant. The structure of pretreated fibre was also examined using scanning electron microscope (SEM). Results showed that water and acid pretreatments effectively dissolved hemicellulose of the fibre with the latter unveiled better results. The alkaline pretreatment resulted in the highest total glucose yield (g/kg of untreated fibre) as compared to water and acid pretreatments. SEM analysis illustrated that water and acid pretreatments led severe destruction of fibre structure; however, both of these pretreatments exhibited lower enhancement of enzymatic hydrolysability of kapok fibre as compared to that observed in alkaline pretreatment. - Highlights: • Effect of pretreatments on sugar yield was studied by response surface methodology. • Glucose yield was highly related to the chemical compositions of pretreated fibers. • Pretreatments altered the physical structure of kapok fibers. • Enzymatic hydrolysability of fibre was improved the most by alkaline treatment. • Over 94% cellulose of the pretreated fibres was converted to glucose

  14. Irreversibility analysis for optimization design of plate fin heat exchangers using a multi-objective cuckoo search algorithm

    International Nuclear Information System (INIS)

    Wang, Zhe; Li, Yanzhong

    2015-01-01

    Highlights: • The first application of IMOCS for plate-fin heat exchanger design. • Irreversibility degrees of heat transfer and fluid friction are minimized. • Trade-off of efficiency, total cost and pumping power is achieved. • Both EGM and EDM methods have been compared in the optimization of PFHE. • This study has superiority over other single-objective optimization design. - Abstract: This paper introduces and applies an improved multi-objective cuckoo search (IMOCS) algorithm, a novel met-heuristic optimization algorithm based on cuckoo breeding behavior, for the multi-objective optimization design of plate-fin heat exchangers (PFHEs). A modified irreversibility degree of the PFHE is separated into heat transfer and fluid friction irreversibility degrees which are adopted as two initial objective functions to be minimized simultaneously for narrowing the search scope of the design. The maximization efficiency, minimization of pumping power, and total annual cost are considered final objective functions. Results obtained from a two dimensional normalized Pareto-optimal frontier clearly demonstrate the trade-off between heat transfer and fluid friction irreversibility. Moreover, a three dimensional Pareto-optimal frontier reveals a relationship between efficiency, total annual cost, and pumping power in the PFHE design. Three examples presented here further demonstrate that the presented method is able to obtain optimum solutions with higher accuracy, lower irreversibility, and fewer iterations as compared to the previous methods and single-objective design approaches

  15. Anesthetic efficacy of articaine for inferior alveolar nerve blocks in patients with symptomatic versus asymptomatic irreversible pulpitis.

    Science.gov (United States)

    Argueta-Figueroa, Liliana; Arzate-Sosa, Gabriel; Mendieta-Zeron, Hugo

    2012-01-01

    This study sought to determine the anesthetic efficacy of 4% articaine with 1:100,000 epinephrine in patients with symptomatic and asymptomatic irreversible pulpitis in mandibular posterior teeth and if individual patient factors, pulpal disease characteristics, and previous medication are correlated to local anesthetic success. A second objective was to determine the specificity and sensibility of a cold test for prediction of anesthetic success prior to endodontic treatment. Seventy patients diagnosed with irreversible pulpitis in mandibular posterior teeth received 1.6 mL of 4% articaine with 1:100,000 epinephrine for an inferior alveolar nerve block (IANB) using a metal guide. The anesthetic solution was injected with a computer-preprogrammed delivery system for local anesthesia. Endodontic access was begun 15 minutes after solution deposition; later, patients rated their discomfort using the visual analog scale (VAS). The success rate for the IA NB using articaine was 64.2% in patients with symptomatic irreversible pulpitis and 86.9% in patients with asymptomatic irreversible pulpitis. Cold test prior to root canal treatment had a specificity and sensibility of 12.5% and 87.1%, respectively. The anesthetic efficacy of articaine in irreversible pulpitis is moderately acceptable, and anesthetic success increases when the patient has been premedicated with NSAIDs. The cold test appears to be a favorable indicator for predicting anesthetic success.

  16. Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics.

    Science.gov (United States)

    Glavatskiy, K S

    2015-05-28

    We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such that there exists an "integral of evolution" which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium.

  17. Electrochemical non-enzymatic glucose sensors

    International Nuclear Information System (INIS)

    Park, Sejin; Boo, Hankil; Chung, Taek Dong

    2006-01-01

    The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in 'nanoera'. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials

  18. Environmentally evaluated HPLC-ELSD method to monitor enzymatic synthesis of a non-ionic surfactant.

    Science.gov (United States)

    Gaber, Yasser; Akerman, Cecilia Orellana; Hatti-Kaul, Rajni

    2014-01-01

    N-Lauroyl-N-methylglucamide is a biodegradable surfactant derived from renewable resources. In an earlier study, we presented an enzymatic solvent-free method for synthesis of this compound. In the present report, the HPLC method developed to follow the reaction between lauric acid/methyl laurate and N-methyl glucamine (MEG) and its environmental assessment are described. Use of ultraviolet (UV) absorption or refractive index (RI) detectors did not allow the detection of N-methyl glucamine (MEG). With Evaporative light scattering detector ELSD, it was possible to apply a gradient elution, and detect MEG with a limit of detection, LOD = 0.12 μg. A good separation of the peaks: MEG, lauric acid, product (amide) and by-product (amide-ester) was achieved with the gradient program with a run time of 40 min. The setting of ELSD detector was optimized using methyl laurate as the analyte. LC-MS/MS was used to confirm the amide and amide-ester peaks. We evaluated the greenness of the developed method using the freely available software HPLC-Environmental Assessment Tool (HPLC-EAT) and the method got a scoring of 73 HPLC-EAT units, implying that the analytical procedure was more environmentally benign compared to some other methods reported in literature whose HPLC-EAT values scored up to 182. Use of ELSD detector allowed the detection and quantification of the substrates and the reaction products of enzymatic synthesis of the surfactant, N-lauroyl-N-methylglucamide. The developed HPLC method has acceptable environmental profile based on HPLC-EAT evaluation.

  19. The analysis of irreversibility, uncertainty and dynamic technical inefficiency on the investment decision in the Spanish olive sector

    NARCIS (Netherlands)

    Lambarraa, Fatima; Stefanou, Spiro; Gil, José M.

    2016-01-01

    This study addresses irreversible investment decision-making in the context of uncertainty when allowing for inefficiency to be transmitted over time. Both irreversibility and persistence in technical inefficiency can lead to sluggish adjustment of quasi-fixed factors of production. The context

  20. Biocatalysis for Biobased Chemicals

    Science.gov (United States)

    de Regil, Rubén; Sandoval, Georgina

    2013-01-01

    The design and development of greener processes that are safe and friendly is an irreversible trend that is driven by sustainable and economic issues. The use of Biocatalysis as part of a manufacturing process fits well in this trend as enzymes are themselves biodegradable, require mild conditions to work and are highly specific and well suited to carry out complex reactions in a simple way. The growth of computational capabilities in the last decades has allowed Biocatalysis to develop sophisticated tools to understand better enzymatic phenomena and to have the power to control not only process conditions but also the enzyme’s own nature. Nowadays, Biocatalysis is behind some important products in the pharmaceutical, cosmetic, food and bulk chemicals industry. In this review we want to present some of the most representative examples of industrial chemicals produced in vitro through enzymatic catalysis. PMID:24970192