Brief Report: Severe Inflammation Following Vaccination Against Streptococcus pneumoniae in Patients With Cryopyrin-Associated Periodic Syndromes.

PubMed

Walker, Ulrich A; Hoffman, Hal M; Williams, Rene; Kuemmerle-Deschner, Jasmin; Hawkins, Philip N

2016-02-01

Pneumococcal vaccination is recommended for patients receiving immunosuppressive drugs. We describe unusually severe adverse reactions to pneumococcal vaccination in each of 7 consecutive patients with cryopyrin-associated periodic syndromes (CAPS). Seven consecutive patients with CAPS were vaccinated with pneumococcal polysaccharide or conjugate vaccines. Clinical information was collected retrospectively. Within a few hours after the vaccination, all 7 patients developed severe local reactions at the injection site. Two patients had to be hospitalized for systemic reactions including fever. All symptoms resolved in a period of 3-17 days. Our findings indicate that pneumococcal vaccines can trigger a severe local and systemic inflammatory reaction in patients with CAPS and possibly patients with other autoinflammatory diseases. Careful consideration is warranted when implementing current European League Against Rheumatism immunization guidelines in this patient population. © 2015, American College of Rheumatology.

A cis-prenyltransferase from Methanosarcina acetivorans catalyzes both head-to-tail and nonhead-to-tail prenyl condensation.

PubMed

Ogawa, Takuya; Emi, Koh-Ichi; Koga, Kazushi; Yoshimura, Tohru; Hemmi, Hisashi

2016-06-01

Cis-prenyltransferase usually consecutively catalyzes the head-to-tail condensation reactions of isopentenyl diphosphate to allylic prenyl diphosphate in the production of (E,Z-mixed) polyprenyl diphosphate, which is the precursor of glycosyl carrier lipids. Some recently discovered homologs of the enzyme, however, catalyze the nonhead-to-tail condensation reactions between allylic prenyl diphosphates. In this study, we characterize a cis-prenyltransferase homolog from a methanogenic archaeon, Methanosarcina acetivorans, to obtain information on the biosynthesis of the glycosyl carrier lipids within it. This enzyme catalyzes both head-to-tail and nonhead-to-tail condensation reactions. The kinetic analysis shows that the main reaction of the enzyme is consecutive head-to-tail prenyl condensation reactions yielding polyprenyl diphosphates, while the chain lengths of the major products seem shorter than expected for the precursor of glycosyl carrier lipids. On the other hand, a subsidiary reaction of the enzyme, i.e., nonhead-to-tail condensation between dimethylallyl diphosphate and farnesyl diphosphate, gives a novel diterpenoid compound, geranyllavandulyl diphosphate. © 2016 Federation of European Biochemical Societies.

Organosolv delignification of Eucalyptus globulus: Kinetic study of autocatalyzed ethanol pulping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oliet, M.; Rodriguez, F.; Santos, A.

2000-01-01

The autocatalyzed delignification of Eucalyptus globulus in 50% ethanol (w/w) was modeled as the irreversible and consecutive dissolution of initial, bulk, and residual lignin. Their respective contributions to total lignin was estimated as 9, 75, and 16%. Isothermal pulping experiments were carried out to evaluate an empirical kinetic model among eight proposals corresponding to different reaction schemes. The calculated activation energy was found to be 96.5, 98.5, and 40.8 kJ/mol for initial, bulk, and residual delignification, respectively. The influence of hydrogen ion concentration was expressed by a power-law function model. The kinetic model developed here was validated using data frommore » nonisothermal pulping runs.« less

Pyrolysis of reinforced polymer composites: Parameterizing a model for multiple compositions

NASA Astrophysics Data System (ADS)

Martin, Geraldine E.

A single set of material properties was developed to describe the pyrolysis of fiberglass reinforced polyester composites at multiple composition ratios. Milligram-scale testing was performed on the unsaturated polyester (UP) resin using thermogravimetric analysis (TGA) coupled with differential scanning calorimetry (DSC) to establish and characterize an effective semi-global reaction mechanism, of three consecutive first-order reactions. Radiation-driven gasification experiments were conducted on UP resin and the fiberglass composites at compositions ranging from 41 to 54 wt% resin at external heat fluxes from 30 to 70 kW m -2. The back surface temperature was recorded with an infrared camera and used as the target for inverse analysis to determine the thermal conductivity of the systematically isolated constituent species. Manual iterations were performed in a comprehensive pyrolysis model, ThermaKin. The complete set of properties was validated for the ability to reproduce the mass loss rate during gasification testing.

Kinetic model for astaxanthin aggregation in water-methanol mixtures

NASA Astrophysics Data System (ADS)

Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo

2009-07-01

The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

PubMed

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Two Distinct Episodes Of Whooping Cough Caused By Consecutive Bordetella Pertussis And Bordetella Parapertussis Infections In A Fully Immunized Healthy Boy.

PubMed

Heininger, Ulrich; Schlassa, Detlef

2016-11-01

We describe a 5-year-old, fully immunized boy with polymerase chain reaction-proven consecutive Bordetella pertussis and Bordetella parapertussis infections causing typical whooping cough at the age of 2 and 5 years, respectively. Neither pertussis immunization nor disease provides reliable immunity against further episodes of whooping cough.

Stereodivergent Synthesis of Chromanones and Flavanones via Intramolecular Benzoin Reaction.

PubMed

Wen, Genfa; Su, Yingpeng; Zhang, Guoxiang; Lin, Qiqiao; Zhu, Yujin; Zhang, Qianqian; Fang, Xinqiang

2016-08-19

The strategy of stereodivergent reactions on racemic mixtures (stereodivergent RRM) was employed for the first time in intramolecular benzoin reactions and led to the rapid access of chromanones/flavanones with two consecutive stereocenters. The easily separable stereoisomers of the products were obtained with moderate to excellent enantioselectivities in a single step. Catechol type additives proved crucial in achieving the desired diastereo- and enantioselectivities.

Development of D-allose sensor on the basis of three strategic enzyme reactions.

PubMed

Miyanishi, Nobumitsu; Nakakita, Shin-Ichi; Sumiyoshi, Wataru; Okuma, Hirokazu; Izumori, Ken; Hirabayashi, Jun

2010-09-15

Rare sugars are defined as monosaccharides and their derivatives that rarely exist in nature, according to the International Society of Rare Sugars. D-Allose (3-epi d-glucose) is one of the rare sugars, for which various physiological activities have recently been found, with increasing attention to its applications to bio-industry. Until now, however, there is no convenient method of measuring these sugars in a specific manner. For detecting D-allose, three consecutive enzyme reactions were devised by fabricating of a reaction batch chamber packed with L-rhamnose isomerase (LRI), D-tagatose 3-epimerase (DTE) and a screen-printed electrode, on which D-fructose dehydrogenase (DFDH) was immobilized. To obtain a substantial sensing system, extensive experimental parameters were optimized. These included the concentration of photo-crosslinkable poly (vinyl alcohol) bearing stilbazolium groups (PVA-SbQ), reaction ratios, and temperature of the batch chamber. By adopting the three consecutive enzyme reactions, an undesirable reverse reaction was minimized. As a result, the developed sensor system exhibited a good linear response on D-allose in the range from 0.1 to 50 mM (r(2)=0.998). The system has an apparent advantage over the previous chromatography approach in terms of simplicity and inexpensiveness. Copyright 2010 Elsevier B.V. All rights reserved.

Contact allergy to oxidized geraniol among Swedish dermatitis patients-A multicentre study by the Swedish Contact Dermatitis Research Group.

PubMed

Hagvall, Lina; Bruze, Magnus; Engfeldt, Malin; Isaksson, Marléne; Lindberg, Magnus; Ryberg, Kristina; Stenberg, Berndt; Svedman, Cecilia; Karlberg, Ann-Therese; Bråred Christensson, Johanna

2018-06-21

Geraniol is a widely used fragrance terpene, and is included in fragrance mix I. Geraniol is prone to autoxidation, forming the skin sensitizers geranial, neral, and geraniol-7-hydroperoxide. Oxidized geraniol has previously been patch tested in 1 clinic, giving 1% to 4.6% positive reactions in consecutive patients when tested at 2% to 11%. To compare test reactions to pure and oxidized geraniol, to compare 2 different test concentrations of oxidized geraniol and to investigate the pattern of concomitant reactions to fragrance markers of the baseline series in a multicentre setting. One thousand four hundred and seventy-six consecutive patients referred for patch testing were patch tested with geraniol 6% pet. and oxidized geraniol 6% and 11% pet. Pure geraniol 6% pet., oxidized geraniol 6% pet. and oxidized geraniol 11% pet. gave 1%, 3% and 8% positive patch test reactions and 0.7%, 3% and 5% doubtful reactions, respectively. Approximately 50% of the patients with doubtful reactions to oxidized geraniol 6% pet. had positive reactions to oxidized geraniol 11% pet. Oxidized geraniol 11% pet. provides better detection than oxidized geraniol 6% pet. As most patients reacted only to oxidized geraniol, it is important to explore further whether oxidized geraniol should be included in a baseline patch test series. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Novel guanosine-cytidine dinucleoside that self-assembles into a trimeric supramolecule.

PubMed

Sessler, Jonathan L; Jayawickramarajah, Janarthanan; Sathiosatham, Muhunthan; Sherman, Courtney L; Brodbelt, Jennifer S

2003-07-24

[reaction: see text] Synthesis and assembly studies of a guanosine-cytidine dinucleoside 1 that self-assembles into a trimeric supramolecule (I) are presented. Dinucleoside 1 was obtained by utilizing two consecutive palladium-catalyzed cross-coupling reactions. Ensemble I was analyzed by ESI-MS, NMR spectroscopies, size exclusion chromatography (SEC), and vapor pressure osmometry (VPO).

On the Meaning of Cross-Cultural Differences in Simple Cognitive Measures

ERIC Educational Resources Information Center

van de Vijver, Fons J. R.

2008-01-01

A set of 5 reaction time tests of increasing cognitive complexity were administered to 35 secondary school pupils in Zimbabwe and The Netherlands at 4 consecutive school days in order to explore the existence and nature of cross-cultural differences on reaction time tests measuring basic cognitive operations. No cross-cultural differences were…

Contact allergy to air-exposed geraniol: clinical observations and report of 14 cases.

PubMed

Hagvall, Lina; Karlberg, Ann-Therese; Christensson, Johanna Bråred

2012-07-01

The fragrance terpene geraniol forms sensitizing compounds via autoxidation and skin metabolism. Geranial and neral, the two isomers of citral, are the major haptens formed in both of these activation pathways. To investigate whether testing with oxidized geraniol detects more cases of contact allergy than testing with pure geraniol. The pattern of reactions to pure and oxidized geraniol, and metabolites/autoxidation products, was studied to investigate the importance of autoxidation or cutaneous metabolism in contact allergy to geraniol. Pure and oxidized geraniol were tested at 2.0% petrolatum in 2227 and 2179 consecutive patients, respectively. In parallel, geranial, neral and citral were tested in 2152, 1626 and 1055 consecutive patients, respectively. Pure and oxidized geraniol gave positive patch test reactions in 0.13% and 0.55% of the patients, respectively. Eight of 11 patients with positive patch test reactions to oxidized geraniol also reacted to citral or its components. Relevance for the positive patch test reactions in relation to the patients' dermatitis was found in 11 of 14 cases. Testing with oxidized geraniol could detect more cases of contact allergy to geraniol. The reaction pattern of the 14 cases presented indicates that both autoxidation and metabolism could be important in sensitization to geraniol. © 2012 John Wiley & Sons A/S.

Dual photon effects in nitrogen dioxide photolysis

NASA Technical Reports Server (NTRS)

Hakala, D.; Harteck, P.; Reeves, R. R.

1974-01-01

A previous study demonstrated two-photon consecutive absorption as being the most probable mechanism for the photodissociation of NO2 using a pulsed ruby laser at 6943 A. Additional data discussed here confirmed this and also examined an associated phenomenon, that of multiphoton induced fluorescence. The dissociation of NO2 by ON-O bond cleavage requires 3.4 eV, while the laser energy corresponds to 1.785 eV. The pooling of the energy of two photons would give more than enough energy to dissociate the NO2 into NO + O. Several mechanisms including (1) simultaneous absorption of two photons; (2) reaction of two singly excited NO2; (3) reaction of a singly excited NO2 with a ground state NO2; and (4) consecutive absorption of two photons were examined.

Parameters for the Evaluation of the Fate, Transport, and Environmental Impacts of Chemical Agents in Marine Environments

DTIC Science & Technology

2007-07-01

result, estimation of the lifetime of hydrogen cyanide in deeper ocean waters is likely to be difficult. 2.4 Sulfur Mustard (HS) The principle active ...single first-order reaction rather than consecutive first-order reactions.159 A recent study determined the activation energy of 18.5 kcal mole-1for...on the chloride ion activity . Despite the relative rapidity of the hydrolysis reaction, 1,1’-thiobis[2-chloroethane] has been found to persist in

Improving the Effectiveness of Penicillin Allergy De-labeling.

PubMed

Bourke, Jack; Pavlos, Rebecca; James, Ian; Phillips, Elizabeth

2015-01-01

Approximately 10-20% of hospitalized patients are labeled as penicillin allergic, and this is associated with significant health and economic costs. We looked at the effectiveness of penicillin allergy de-labeling in clinical practice with the aim of deriving risk stratification models to guide testing strategies. Consecutive patients aged 15 years or more, referred to a Western Australian public hospital drug allergy service between 2008 and 2013 for beta-lactam allergy, were included. Follow-up surveys were conducted. Results of skin prick testing and intradermal testing (SPT/IDT) and oral challenge (OC), and follow-up of post testing antibiotic usage were the main outcomes. SPT/IDT was performed in 401 consecutive patients with immediate (IMM) (≤ 1 hour) (n = 151) and nonimmediate (NIM) (>1 hour) (n = 250) reactions. Of 341 patients, 42 (12.3%) were SPT/IDT+ to ≥ 1 penicillin reagents, including 35/114 (30.4%) in the IMM group and 7/227 (3.1%) in the NIM group (P < .0001). Of 355 SPT/IDT patients, 3 (0.8%), all in the IMM group, had nonserious positive OC reactions to single dose penicillin VK (SPT/IDT negative predictive value [NPV] 99.2%). Selective or unrestricted beta-lactam was recommended in almost 90% overall, including 238/250 (95.2%) in the NIM group and 126/151 (83.4%) in the IMM group (P = .0001). Of 182 patients, 137 (75.3%) were following the allergy label modifications (ALM) at the time of follow-up. Penicillin SPT/IDT/OC safely de-labels penicillin-allergic patients and identifies selective beta-lactam allergies; however, incomplete adherence to ALM recommendations impairs effectiveness. Infrequent SPT/IDT+ and absent OC reactions in patients with NIM reactions suggest OC alone to be a safe and cost-effective de-labeling strategy that could improve the coverage of penicillin allergy de-labeling in lower risk populations. Copyright © 2015 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Car-Parrinello molecular dynamics study of the thermal decomposition of sodium fulminate.

PubMed

Damianos, Konstantina; Frank, Irmgard

2010-07-19

Depending on the metal cation, metal fulminates exhibit a characteristic sensitivity with respect to heat and mechanical stress. In the present paper we study the high-temperature reactions of bulk sodium fulminate using Car-Parrinello molecular dynamics simulations. We find that the initiating reaction is the formation of the fulminate dimer, while in earlier studies an electron transfer was assumed to be the first reaction step. The initial carbon--carbon bond formation is followed by fast consecutive reactions leading to polymerisation. The resulting species remain charged on the timescale of the simulations.

An agent-based approach to modelling the effects of extreme events on global food prices

NASA Astrophysics Data System (ADS)

Schewe, Jacob; Otto, Christian; Frieler, Katja

2015-04-01

Extreme climate events such as droughts or heat waves affect agricultural production in major food producing regions and therefore can influence the price of staple foods on the world market. There is evidence that recent dramatic spikes in grain prices were at least partly triggered by actual and/or expected supply shortages. The reaction of the market to supply changes is however highly nonlinear and depends on complex and interlinked processes such as warehousing, speculation, and export restrictions. Here we present for the first time an agent-based modelling framework that accounts, in simplified terms, for these processes and allows to estimate the reaction of world food prices to supply shocks on a short (monthly) timescale. We test the basic model using observed historical supply, demand, and price data of wheat as a major food grain. Further, we illustrate how the model can be used in conjunction with biophysical crop models to assess the effect of future changes in extreme event regimes on the volatility of food prices. In particular, the explicit representation of storage dynamics makes it possible to investigate the potentially nonlinear interaction between simultaneous extreme events in different food producing regions, or between several consecutive events in the same region, which may both occur more frequently under future global warming.

Limonene hydroperoxide analogues show specific patch test reactions.

PubMed

Christensson, Johanna Bråred; Hellsén, Staffan; Börje, Anna; Karlberg, Ann-Therese

2014-05-01

The fragrance terpene R-limonene is a very weak sensitizer, but forms allergenic oxidation products upon contact with air. The primary oxidation products of oxidized limonene, the hydroperoxides, have an important impact on the sensitizing potency of the oxidation mixture. One analogue, limonene-1-hydroperoxide, was experimentally shown to be a significantly more potent sensitizer than limonene-2-hydroperoxide in the local lymph node assay with non-pooled lymph nodes. To investigate the pattern of reactivity among consecutive dermatitis patients to two structurally closely related limonene hydroperoxides, limonene-1-hydroperoxide and limonene-2-hydroperoxide. Limonene-1-hydroperoxide, limonene-2-hydroperoxide, at 0.5% in petrolatum, and oxidized limonene 3.0% pet. were tested in 763 consecutive dermatitis patients. Of the tested materials, limonene-1-hydroperoxide gave most reactions, with 2.4% of the patients showing positive patch test reactions. Limonene-2-hydroperoxide and oxidized R-limonene gave 1.7% and 1.2% positive patch test reactions, respectively. Concomitant positive patch test reactions to other fragrance markers in the baseline series were frequently noted. The results are in accordance with the experimental studies, as limonene-1-hydroperoxide gave more positive patch test reactions in the tested patients than limonene-2-hydroperoxide. Furthermore, the results support the specificity of the allergenic activity of the limonene hydroperoxide analogues and the importance of oxidized limonene as a cause of contact allergy. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Oxidized limonene and oxidized linalool - concomitant contact allergy to common fragrance terpenes.

PubMed

Bråred Christensson, Johanna; Karlberg, Ann-Therese; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Giménez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

2016-05-01

Limonene and linalool are common fragrance terpenes. Both oxidized R-limonene and oxidized linalool have recently been patch tested in an international setting, showing contact allergy in 5.2% and 6.9% of dermatitis patients, respectively. To investigate concomitant reactions between oxidized R-limonene and oxidized linalool in consecutive dermatitis patients. Oxidized R-limonene 3.0% (containing limonene hydroperoxides 0.33%) and oxidized linalool 6% (linalool hydroperoxides 1%) in petrolatum were tested in 2900 consecutive dermatitis patients in Australia, Denmark, Singapore, Spain, Sweden, and the United Kingdom. A total of 281 patients reacted to either oxidized R-limonene or oxidized linalool. Of these, 25% had concomitant reactions to both compounds, whereas 29% reacted only to oxidized R-limonene and 46% only to oxidized linalool. Of the 152 patients reacting to oxidized R-limonene, 46% reacted to oxidized linalool, whereas 35% of the 200 patients reacting to oxidized linalool also reacted to oxidized R-limonene. The majority of the patients (75%) reacted to only one of the oxidation mixtures, thus supporting the specificity of the reactions. The concomitant reactions to the two fragrance allergens suggest multiple sensitizations, which most likely reflect the exposure to the different fragrance materials in various types of consumer products. This is in accordance with what is generally seen for patch test reactions to fragrance materials. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Future Power Production by LENR with Thin-Film Electrodes

NASA Astrophysics Data System (ADS)

Miley, George H.; Hora, Heinz; Lipson, Andrei; Luo, Nie; Shrestha, P. Joshi

2007-03-01

PdD cluster reaction theory was recently proposed to explain a wide range of Low energy Nuclear Reaction (LENR) experiments. If understood and optimized, cluster reactions could lead to a revolutionary new power source of nuclear energy. The route is two-fold. First, the excess heat must be obtained reproducibly and over extended run times. Second, the percentage of excess must be significantly (order of magnitude or more) higher than the 20-50% typically today. The thin film methods described here have proven to be quite reproducible, e.g. providing excess heat of 20-30% in nine consecutive runs of several weeks each. However, mechanical separation of the films occurs over long runs due to the severe mechanical stresses created.. Techniques to overcome these problems are possible using graded bonding techniques similar to that used in high temperature solid oxide fuel cells. Thus the remaining key issue is to increase the excess heat. The cluster model provides import insight into this. G. H. Miley, H. Hora, et al., 233rd Amer Chem Soc Meeting, Chicago, IL, March 25-29, 2007.

Nonenzymatic template-directed synthesis on hairpin oligonucleotides. 3. Incorporation of adenosine and uridine residues

NASA Technical Reports Server (NTRS)

Wu, T.; Orgel, L. E.

1992-01-01

We have used [32P]-labeled hairpin oligonucleotides to study template-directed synthesis on templates containing one or more A or T residues within a run of C residues. When nucleoside-5'-phosphoro(2-methyl)imidazolides are used as substrates, isolated A and T residues function efficiently in facilitating the incorporation of U and A, respectively. The reactions are regiospecific, producing mainly 3'-5'-phosphodiester bonds. Pairs of consecutive non-C residues are copied much less efficiently. Limited synthesis of CA and AC sequences on templates containing TG and GT sequences was observed along with some synthesis of the AA sequences on templates containing TT sequences. The other dimer sequences investigated, AA, AG, GA, TA, and AT, could not be copied. If A is absent from the reaction mixture, misincorporation of G residues is a significant reaction on templates containing an isolated T residue or two consecutive T residues. However, if both A and G are present, A is incorporated to a much greater extent than G. We believe that wobble-pairing between T and G is responsible for misincorporation when only G is present.

Functionalized alkoxy arene diazonium salts from paracetamol.

PubMed

Schmidt, Bernd; Berger, René; Hölter, Frank

2010-03-21

Arene diazonium tetrafluoroborates can be synthesized from aromatic acetamides via a sequence of deacetylation, diazotation and precipitation, induced by anion exchange. The reaction is conducted as a convenient one-flask transformation with consecutive addition of the appropriate reagents. Exchange of solvents or removal of byproducts prior to isolation of the product is not required. The arene diazonium salts are isolated from the reaction mixture by simple filtration. Two complementary protocols are presented, and the utility of the reaction is exemplified for a synthesis of the diarylheptanoid natural product de-O-methyl centrolobine.

Highly efficient preparation of selectively isotope cluster-labeled long chain fatty acids via two consecutive C(sp3)-C(sp3) cross-coupling reactions.

PubMed

Lethu, Sébastien; Matsuoka, Shigeru; Murata, Michio

2014-02-07

An efficient synthesis involving two copper-catalyzed alkyl-alkyl coupling reactions has been designed to easily access doubly isotope-labeled fatty acids. Such NMR- and IR-active compounds were obtained in excellent overall yields and will be further used for determining the conformation of an alkyl chain of lipidic biomolecules upon interaction with proteins.

The effect of repetitive ankle perturbations on muscle reaction time and muscle activity.

PubMed

Thain, Peter Kevin; Hughes, Gerwyn Trefor Gareth; Mitchell, Andrew Charles Stephen

2016-10-01

The use of a tilt platform to simulate a lateral ankle sprain and record muscle reaction time is a well-established procedure. However, a potential caveat is that repetitive ankle perturbation may cause a natural attenuation of the reflex latency and amplitude. This is an important area to investigate as many researchers examine the effect of an intervention on muscle reaction time. Muscle reaction time, peak and average amplitude of the peroneus longus and tibialis anterior in response to a simulated lateral ankle sprain (combined inversion and plantar flexion movement) were calculated in twenty-two physically active participants. The 40 perturbations were divided into 4 even groups of 10 dominant limb perturbations. Within-participants repeated measures analysis of variance (ANOVA) tests were conducted to assess the effect of habituation over time for each variable. There was a significant reduction in the peroneus longus average amplitude between the aggregated first and last 10 consecutive ankle perturbations (F2.15,45.09=3.90, P=0.03, ɳp(2)=0.16). Authors should implement no more than a maximum of 30 consecutive ankle perturbations (inclusive of practice perturbations) in future protocols simulating a lateral ankle sprain in an effort to avoid significant attenuation of muscle activity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Isomerization of glucose into fructose by environmentally friendly Fe/β zeolite catalysts.

PubMed

Xu, Siquan; Zhang, Lei; Xiao, Kehao; Xia, Haian

2017-06-29

Herein, the environmentally friendly Fe/β zeolite for glucose isomerization to fructose in aqueous media was reported for the first time. The effects of various reaction conditions including reaction temperature, reaction time, catalyst dosage, etc. on the isomerization reaction over Fe/β zeolite were studied in detail. Under the optimized conditions, yield of fructose higher than 20% were obtained. Moreover, the Fe/β zeolite catalysts were stable and remained constant catalytic activity after five consecutive runs. The possible active Fe species for isomerization of glucose in Fe/β zeolite is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Capillary sample introduction of polymerase chain reaction (PCR) products separated in ultrathin slab gels.

PubMed

Bullard, K M; Hietpas, P B; Ewing, A G

1998-01-01

Polymerase chain reaction (PCR) amplified short tandem repeat (STR) samples from the HUMVWF locus have been analyzed using a unique sample introduction and separation technique. A single capillary is used to transfer samples onto an ultrathin slab gel (57 microm thin). This ultrathin nondenaturing polyacrylamide gel is used to separate the amplified fragments, and laser-induced fluorescence with ethidium bromide is used for detection. The feasibility of performing STR analysis using this system has been investigated by examining the reproducibility for repeated samples. Reproducibility is examined by comparing the migration of the 14 and 17 HUMVWF alleles on three consecutive separations on the ultrathin slab gel. Using one locus, separations match in migration time with the two alleles 42 s apart for each of the three consecutive separations. This technique shows potential to increase sample throughput in STR analysis techniques although separation resolution still needs to be improved.

Effect of working consecutive night shifts on sleep time, prior wakefulness, perceived levels of fatigue and performance on a psychometric test in emergency registrars.

PubMed

Haire, Julia Christine Lydia; Ferguson, Sally Anne; Tilleard, James D; Negus, Paul; Dorrian, Jillian; Thomas, Matthew Jw

2012-06-01

To evaluate the effect of working consecutive night shifts on sleep time, prior wakefulness, perceived levels of fatigue and psychomotor performance in a group of Australian emergency registrars. A prospective observational study with a repeated within-subjects component was conducted. Sleep time was determined using sleep diaries and activity monitors. Subjective fatigue levels and reciprocal reaction times were evaluated before and after day and night shifts. A total of 11 registrars participated in the study with 120 shifts analysed. Sleep time was found to be similar during consecutive night and day shifts. The mean number of hours spent awake before the end of a night shift was 14.33. Subjective fatigue scores were worst at the end of a night shift. There was no difference in reciprocal reaction time between the end of night shift and the start of day shift. Registrars sleep a similar amount of time surrounding night and day shifts. Despite reporting the highest levels of fatigue at the end of a night shift, there is no significant difference in reaction times at the end of night shift compared with the beginning of day shift. This correlates with the finding that at the end of night shift the registrars have been awake for less than 16 h, which is the point at which psychomotor performance is expected to decline. © 2012 The Authors. EMA © 2012 Australasian College for Emergency Medicine and Australasian Society for Emergency Medicine.

A designed beta-hairpin forming peptide undergoes a consecutive stepwise process for self-assembly into nanofibrils.

PubMed

Wang, Chong; Sha, Yinlin

2010-04-01

We used a de novo designed, beta-hairpin forming T1 peptide as a model to investigate the kinetics of peptide fibrogenesis by a combination of light scattering (LS), circular dichroism (CD), fluorescence, and atomic force microscopy (AFM). The results demonstrate that the T1 fibrogenesis undergoes a consecutive stepwise process, with a high degree of cooperation, presenting sigmoidal time-courses of the peptide aggregation, the subsequent conformational conversion of the backbone, and the peptide sidechains' rearrangement. We suggest that the conformational conversion was initiated after the peptide aggregates reach a dimensional size threshold, which could be a key step in the formation of beta-structural nuclei that catalyze the subsequent reactions. Furthermore, besides triggering the peptide aggregation, the interactions between the peptide sidechains predominately facilitate the regular alignment of the peptide molecules and the formation of a well-defined suprastructure. This work provides an insight of the hierarchical self-assembly of beta-hairpin forming peptides. It is helpful for designing beta-structural peptides for self-assembly into nanowires, which would have potential applications in the construction of nano-materials.

Reactogenicity of tetanus, diphtheria, 5-component acellular pertussis vaccine administered as a sixth consecutive acellular pertussis vaccine dose to adolescents.

PubMed

Liese, Johannes G; Rieber, Nikolaus; Malzer, Thomas; Ocak, Marion; Johnson, David R; Decker, Michael D

2010-12-01

Safety of a sixth consecutive dose of acellular pertussis vaccine in adolescents was assessed in a 2-armed, randomized study. Adolescents who had received 5 doses of acellular pertussis vaccine combined with diphtheria and tetanus toxoids (6-dose group) received 1 dose of reduced 5-component acellular pertussis vaccine combined with tetanus toxoid and reduced diphtheria toxoid (Tdap). Adolescents who had received a primary series of 3 doses of whole-cell pertussis and 1 acellular or whole-cell pertussis booster received 1 dose of Tdap vaccine (5-dose group). Of 214 participants, 176 (82%) reported an injection-site reaction with pain (80%), erythema (22%), and swelling (19%) most frequently reported. A systemic reaction was reported by 169 of 214 (79%) with myalgia (66%), headache (42%), malaise (39%), and fever (9%) most frequently reported. The overall rate of solicited reactions was lower in the 6-dose group than in the 5-dose group (for injection-site reactions: 76.1% vs. 89.7%; for systemic reactions 72.6% vs. 86.6%). Significant differences were observed for injection-site pain, erythema, and for grade 1 or grade 2 increases in arm circumference. Fever, myalgia, and headache were reported at a significantly lower rate in the 6-dose group. Swelling >10 cm was observed in 5 patients (2%), 4 in the 5-dose group. Tdap vaccine was safe when given to adolescents who had received 5 prior doses of acellular pertussis vaccine.

Exploring the use of multiple analogical models when teaching and learning chemical equilibrium

NASA Astrophysics Data System (ADS)

Harrison, Allan G.; de Jong, Onno

2005-12-01

This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the observation of three consecutive Grade 12 lessons on chemical equilibrium, pre- and post-lesson interviews, and delayed student interviews. The key analogical models used in teaching were: the school dance; the sugar in a teacup; the pot of curry; and the busy highway. The lesson and interview data were subject to multiple, independent analyses and yielded the following outcomes: The teacher planned to use the students' prior knowledge wherever possible and he responded to student questions with stories and extended and enriched analogies. He planned to discuss where each analogy broke down but did not. The students enjoyed the teaching but built variable mental models of equilibrium and some of their analogical mappings were unreliable. A female student disliked masculine analogies, other students tended to see elements of the multiple models in isolation, and some did not recognize all the analogical mappings embedded in the teaching plan. Most students learned that equilibrium reactions are dynamic, occur in closed systems, and the forward and reverse reactions are balanced. We recommend the use of multiple analogies like these and insist that teachers always show where the analogy breaks down and carefully negotiate the conceptual outcomes.

The action of the bacterial toxin microcin B17. Insight into the cleavage-religation reaction of DNA gyrase.

PubMed

Pierrat, Olivier A; Maxwell, Anthony

2003-09-12

We have examined the effects of the bacterial toxin microcin B17 (MccB17) on the reactions of Escherichia coli DNA gyrase. MccB17 slows down but does not completely inhibit the DNA supercoiling and relaxation reactions of gyrase. A kinetic analysis of the cleavage-religation equilibrium of gyrase was performed to determine the effect of the toxin on the forward (cleavage) and reverse (religation) reactions. A simple mechanism of two consecutive reversible reactions with a nicked DNA intermediate was used to simulate the kinetics of cleavage and religation. The action of MccB17 on the kinetics of cleavage and religation was compared with that of the quinolones ciprofloxacin and oxolinic acid. With relaxed DNA as substrate, only a small amount of gyrase cleavage complex is observed with MccB17 in the absence of ATP, whereas the presence of the nucleotide significantly enhances the effect of the toxin on both the cleavage and religation reactions. In contrast, ciprofloxacin, oxolinic acid, and Ca2+ show lesser dependence on ATP to stabilize the cleavage complex. MccB17 enhances the overall rate of DNA cleavage by increasing the forward rate constant (k2) of the second equilibrium. In contrast, ciprofloxacin increases the amount of cleaved DNA by a combined effect on the forward and reverse rate constants of both equilibria. Based on these results and on the observations that MccB17 only slowly inhibits the supercoiling and relaxation reactions, we suggest a model of the interaction of MccB17 with gyrase.

Nitric Oxide Reduction to Ammonia by TiO 2 Electrons in Colloid Solution via Consecutive One-Electron Transfer Steps

DOE PAGES

Goldstein, Sara; Behar, David; Rajh, Tijana; ...

2015-03-02

The reaction mechanism of nitric oxide (NO) reduction by excess electrons on TiO 2 nanoparticles (e TiO2–) has been studied under anaerobic conditions. TiO 2 was loaded with 10–130 electrons per particle using γ-irradiation of acidic TiO 2 colloid solutions containing 2-propanol. The study is based on time-resolved kinetics and reactants and products analysis. The reduction of NO by e TiO2– is interpreted in terms of competition between a reaction path leading to formation of NH 3 and a path leading to N 2O and N 2. The proposed mechanism involves consecutive one-electron transfers of NO, and its reduction intermediatesmore » HNO, NH 2O•, and NH 2OH. The results show that e TiO2– does not reduce N 2O and N 2. Second-order rate constants of e TiO2– reactions with NO (740 ± 30 M –1 s –1) and NH 2OH (270 ± 30 M –1 s –1) have been determined employing the rapid-mixing stopped-flow technique and that with HNO (>1.3 × 10 6 M –1 s –1) was derived from fitting the kinetic traces to the suggested reaction mechanism, which is discussed in detail.« less

Tetrahydrofuran Calpha-tetrasubstituted amino acids: two consecutive beta-turns in a crystalline linear tripeptide.

PubMed

Maity, Prantik; Zabel, Manfred; König, Burkhard

2007-10-12

The synthesis of tetrahydrofuran Calpha-tetrasubstituted amino acids (TAAs) and their effect on the conformation in small peptides are reported. The synthesis starts from the protein amino acid methionine, which is protected at the C and N terminus and converted into the corresponding sulfonium salt by alkylation. Simple base treatment in the presence of an aryl aldehyde leads to the formation of tetrahydrofuran tetrasubstituted Calpha-amino acids in a highly diastereoselective (trans/cis ratio up to 97:3) reaction with moderate to good yields (35-78%) depending on the aldehyde used. Palladium-catalyzed coupling reactions allow a subsequent further functionalization of the TAA. The R,S,S-TAA-Ala dipeptide amide adopts a beta-turn type I conformation, whereas its S,R,S isomer does not. The R,S,S-Gly-TAA-Ala tripeptide amide shows in the solid state and in solution a conformation of two consecutive beta-turn type III structures, stabilized by i+3-->i intramolecular hydrogen bonds.

Transesterification of palm oil using sodium silicate base catalyst from geothermal sludge

NASA Astrophysics Data System (ADS)

Perdana, I.; Nugrahanti, N.; Sofiyah; Bendiyasa, I. M.

2016-11-01

The use of solid base catalysts in biodiesel synthesis is becoming more preferable because of their superiority over homogeneous catalysts. In the present work, a strong base catalyst of sodium silicate synthesized from silica-rich geothermal sludge was used in a transesterification of palm oil with methanol. The catalyst was calcined at 400°C for three hours with a temperature ramp of 20°C/min. The transesterification was carried out at varying temperature in the range of 50 - 70°C for 60 minutes with a methanol-palm oil molar ratio of 8.8:1. The catalyst-palm oil ratio was varied in the range of 1 - 5% (w/w). In order to investigate kinetics of reaction, at a certain interval of time samples were taken consecutively during the reaction. Experimental results showed that the sodium silicate was very active in the transesterification of palm oil with methanol. Reaction temperature at 60°C was sufficient to reach a conversion level as high as 93% in a relatively short reaction period. Meanwhile, the high conversion was still achievable with the use of 1 % (w/w) catalyst. In addition, a lumped model of reaction kinetics was adequate to approach the experimental data with a calculated activation energy of 15.73 kcal/mole. Results of the present work suggested that sodium silicate synthesized from local resources of geothermal sludge would become potential solid base catalyst in biodiesel synthesis.

Study of the techniques feasible for food synthesis aboard a spacecraft

NASA Technical Reports Server (NTRS)

Weiss, A. H.

1972-01-01

Synthesis of sugars by Ca(OH)2 catalyzed formaldehyde condensation (the formose reaction) has produced branched carbohydrates that do not occur in nature. The kinetics and mechanisms of the homogeneously catalyzed autocatalytic condensation were studied and analogies between homogeneous and heterogeneous rate laws have been found. Aldol condensations proceed simultaneously with Cannizzaro and crossed-Cannizzaro reactions and Lobry de Bruyn-Van Eckenstein rearrangements. The separate steps as well as the interactions of this highly complex reaction system were elucidated. The system exhibits instabilities, competitive catalytic, mass action, and equilibrium phenomena, complexing, and parallel and consecutive reactions. Specific finding that have been made on the problem will be of interest for synthesizing sugars, both for sustained space flight and for large scale food manufacture. A contribution to methodology for studying complex catalyzed reactions and to understanding control of reaction selectivity was a broad goal of the project.

Acoustic deterrence of bighead carp (Hypophthalmichthys nobilis) to a broadband sound stimulus

USGS Publications Warehouse

Vetter, Brooke J.; Murchy, Kelsie; Cupp, Aaron R.; Amberg, Jon J.; Gaikowski, Mark P.; Mensinger, Allen F.

2017-01-01

Recent studies have shown the potential of acoustic deterrents against invasive silver carp (Hypophthalmichthys molitrix). This study examined the phonotaxic response of the bighead carp (H. nobilis) to pure tones (500–2000 Hz) and playbacks of broadband sound from an underwater recording of a 100 hp outboard motor (0.06–10 kHz) in an outdoor concrete pond (10 × 5 × 1.2 m) at the U.S. Geological Survey Upper Midwest Environmental Science Center in La Crosse, WI. The number of consecutive times the fish reacted to sound from alternating locations at each end of the pond was assessed. Bighead carp were relatively indifferent to the pure tones with median consecutive responses ranging from 0 to 2 reactions away from the sound source. However, fish consistently exhibited significantly (P < 0.001) greater negative phonotaxis to the broadband sound (outboard motor recording) with an overall median response of 20 consecutive reactions during the 10 min trials. In over 50% of broadband sound tests, carp were still reacting to the stimulus at the end of the trial, implying that fish were not habituating to the sound. This study suggests that broadband sound may be an effective deterrent to bighead carp and provides a basis for conducting studies with wild fish.

Fragrance allergy in patients with hand eczema - a clinical study.

PubMed

Heydorn, Siri; Johansen, Jeanne Duus; Andersen, Klaus E; Bruze, Magnus; Svedman, Cecilia; White, Ian R; Basketter, David A; Menné, Torkil

2003-06-01

Fragrance allergy and hand eczema are both common among dermatological patients. Fragrance mix (FM) and its constituents have a recognized relevance to exposure to fine fragrances and cosmetic products. Based on extensive chemical analysis and database search, a new selection of fragrances was established, including 14 known fragrance allergens present in products to which hand exposure would occur. A non-irritating patch-test concentration for some fragrances was established in 212 consecutive patients. 658 consecutive patients presenting with hand eczema were patch tested with the European standard series and the developed selection of fragrances. 67 (10.2%) of the 658 patients had a positive reaction to 1 or more of our selection of fragrance chemicals present in the new selection. The most common reactions to fragrances not included in the FM were to citral, Lyral (hydroxyisohexyl-3-cyclohexene carboxaldehyde) and oxidized l-limonene. A concomitant reaction to the FM identified potential fragrance allergy in less than (1/2) of these patients. Exposure assessment and a statistically significant association between a positive patch test to our selected fragrances and patients' history support the relevance of this selection of fragrances. Those with a positive reaction to our selected fragrances were significantly more likely to have 1 or more positive patch tests in the standard series. This observation is the basis for the hypothesis concerning cross-reactivity and the effect of simultaneous exposure. The study found that fragrance allergy could be a common problem in patients with eczema on the hands.

Kinetics of non-catalyzed hydrolysis of tannin in high temperature liquid water*

PubMed Central

Lu, Li-li; Lu, Xiu-yang; Ma, Nan

2008-01-01

High temperature liquid water (HTLW) has drawn increasing attention as an environmentally benign medium for organic chemical reactions, especially acid-/base-catalyzed reactions. Non-catalyzed hydrolyses of gallotannin and tara tannin in HTLW for the simultaneous preparation of gallic acid (GA) and pyrogallol (PY) are under investigation in our laboratory. In this study, the hydrolysis kinetics of gallotannin and tara tannin were determined. The reaction is indicated to be a typical consecutive first-order one in which GA has formed as a main intermediate and PY as the final product. Selective decomposition of tannin in HTLW was proved to be possible by adjusting reaction temperature and time. The present results provide an important basic data and reference for the green preparation of GA and PY. PMID:18500780

Rhodium(i)-catalyzed asymmetric [4 + 2] cycloaddition reactions of 2-alkylenecyclobutanols with cyclic enones through C–C bond cleavage: efficient access to trans-bicyclic compounds† †Electronic supplementary information (ESI) available. CCDC 1575240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04784c

PubMed Central

Zheng, Xinxin; Guo, Rui

2018-01-01

We report a rhodium-catalyzed asymmetric formal intermolecular [4 + 2] cycloaddition reaction of 2-alkylenecyclobutanols with α,β-unsaturated cyclic ketones leading to synthetically useful trans-bicyclic molecules. Three consecutive stereogenic centers are formed in a highly enantio- and diastereoselective manner. Stepwise C–C bond cleavage and annulation are likely involved in the reaction pathway. Here, iPr-Duphos is the viable chiral ligand that promotes excellent enantio-control. PMID:29675233

Reaction mechanisms of methylene-blue degradation in three-dimensionally integrated micro-solution plasma

NASA Astrophysics Data System (ADS)

Shirafuji, Tatsuru; Ishida, Yodai; Nomura, Ayano; Hayashi, Yui; Goto, Motonobu

2017-06-01

We have performed matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) on methylene-blue aqueous solutions treated with three-dimensionally integrated micro-solution plasma, in which we have acquired the time evolution of mass spectra as a function of treatment time. The time evolution of mass spectral peak intensities for major detected species has clearly indicated that the parent methylene-blue molecules are degraded through consecutive reactions. The primary reaction is the oxidation of the parent molecules. The oxidized species still have two benzene rings in the parent molecules. The secondary reactions are the separation of the oxidized species and the formation of compounds with one benzene ring. We have also performed the numerical fitting of the time evolution of the mass spectral peak intensities, the results of which have indicated that we must assume additional primary reactions before the primary oxidation for better agreement with experimental results.

Enantioselective aldol reactions with masked fluoroacetates

NASA Astrophysics Data System (ADS)

Saadi, Jakub; Wennemers, Helma

2016-03-01

Despite the growing importance of organofluorines as pharmaceuticals and agrochemicals, the stereoselective introduction of fluorine into many prominent classes of natural products and chemotherapeutic agents is difficult. One long-standing unsolved challenge is the enantioselective aldol reaction of fluoroacetate to enable access to fluorinated analogues of medicinally relevant acetate-derived compounds, such as polyketides and statins. Herein we present fluoromalonic acid halfthioesters as biomimetic surrogates of fluoroacetate and demonstrate their use in highly stereoselective aldol reactions that proceed under mild organocatalytic conditions. We also show that the methodology can be extended to formal aldol reactions with fluoroacetaldehyde and consecutive aldol reactions. The synthetic utility of the fluorinated aldol products is illustrated by the synthesis of a fluorinated derivative of the top-selling drug atorvastatin. The results show the prospects of the method for the enantioselective introduction of fluoroacetate to access a wide variety of highly functionalized fluorinated compounds.

The fragrance mix and its constituents: a 14-year material.

PubMed

Johansen, J D; Menné, T

1995-01-01

Results from 14 years of patch testing with the fragrance mix and its constituents are reviewed. From 1979-1992, 8215 consecutive patients were patch tested with the fragrance mix and 449 (5.5%) had a positive reaction. An increase in the frequency of reactions to fragrance mix was seen from the first 5-year period to the last. Only 54.4% of the patients tested in the last 5-year period with the individual constituents of the mix had at least 1 positive reaction. The results of testing with the constituents are the basis for a discussion of methodological problems. A significant decrease in the frequency of reaction to cinnamic aldehyde was registered, at the same time as the test concentration was reduced from 2% to 1% pet. However, no significant variations in the frequency of reactions to oak moss were seen, notwithstanding a similar reduction in test concentration.

Kinetics of Eucalyptus globulus delignification in a methanol-water medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilarranz, M.A.; Rodriguez, F.; Santos, A.

1999-09-01

The kinetics of Eucalyptus Globulus delignification in methanol-water pulping has been studied. A total of 17 isothermal runs at a liquor-to-wood ratio of 50 L/kg were carried out to develop the kinetic model describing the system. In a first series of experiments, eight models were considered to study the influence of temperature on the delignification rate. The most suitable model, which was discriminated according to statistical criteria, describes delignification as the consecutive dissolution of three lignin species: initial, bulk, and residual lignin, their content in wood being 10, 69, and 21%, respectively. Initial and residual delignification were considered as irreversiblemore » reactions and bulk delignification as reversible. The influence of hydrogen ion concentration was taken into account by means of a general power-law expression. The model proposed was taken into account by means of a general power-law expression. The model proposed was validated by reproducing the experimental data from four runs carried out under nonisothermal conditions and a liquor-to-wood ratio of 7 L/kg, which are closer to industrial operating conditions.« less

Kinetic modelling of ascorbic and dehydroascorbic acids concentrations in a model solution at different temperatures and oxygen contents.

PubMed

Gómez Ruiz, Braulio; Roux, Stéphanie; Courtois, Francis; Bonazzi, Catherine

2018-04-01

The degradation kinetics of vitamin C (ascorbic and dehydroascorbic acids, AA and DHA) were determined under controlled conditions of temperature (50-90 °C) and oxygen concentrations in the gas phase (10-30% mol/mol) using a specific reactor. The degradation of vitamin C in malate buffer (20 mM, pH 3.8), mimetic of an apple puree, was assessed by sampling at regular intervals and spectrophotometric quantification of AA and DHA levels at 243 nm. The results showed that AA degradation increased with temperature and oxygen concentration, while DHA exhibited the behaviour of an intermediate species, appearing then disappearing. A kinetic model was successfully developed to simulate the experimental data by two first order consecutive reactions. The first one represented AA degradation as a function of temperature and concentration in dissolved oxygen, and the second reflected DHA degradation as a function of temperature only, both adequately following Arrhenius' law. Copyright © 2018 Elsevier Ltd. All rights reserved.

A two-stage predictive model to simultaneous control of trihalomethanes in water treatment plants and distribution systems: adaptability to treatment processes.

PubMed

Domínguez-Tello, Antonio; Arias-Borrego, Ana; García-Barrera, Tamara; Gómez-Ariza, José Luis

2017-10-01

The trihalomethanes (TTHMs) and others disinfection by-products (DBPs) are formed in drinking water by the reaction of chlorine with organic precursors contained in the source water, in two consecutive and linked stages, that starts at the treatment plant and continues in second stage along the distribution system (DS) by reaction of residual chlorine with organic precursors not removed. Following this approach, this study aimed at developing a two-stage empirical model for predicting the formation of TTHMs in the water treatment plant and subsequently their evolution along the water distribution system (WDS). The aim of the two-stage model was to improve the predictive capability for a wide range of scenarios of water treatments and distribution systems. The two-stage model was developed using multiple regression analysis from a database (January 2007 to July 2012) using three different treatment processes (conventional and advanced) in the water supply system of Aljaraque area (southwest of Spain). Then, the new model was validated using a recent database from the same water supply system (January 2011 to May 2015). The validation results indicated no significant difference in the predictive and observed values of TTHM (R 2 0.874, analytical variance <17%). The new model was applied to three different supply systems with different treatment processes and different characteristics. Acceptable predictions were obtained in the three distribution systems studied, proving the adaptability of the new model to the boundary conditions. Finally the predictive capability of the new model was compared with 17 other models selected from the literature, showing satisfactory results prediction and excellent adaptability to treatment processes.

Live cell imaging combined with high-energy single-ion microbeam

NASA Astrophysics Data System (ADS)

Guo, Na; Du, Guanghua; Liu, Wenjing; Guo, Jinlong; Wu, Ruqun; Chen, Hao; Wei, Junzhe

2016-03-01

DNA strand breaks can lead to cell carcinogenesis or cell death if not repaired rapidly and efficiently. An online live cell imaging system was established at the high energy microbeam facility at the Institute of Modern Physics to study early and fast cellular response to DNA damage after high linear energy transfer ion radiation. The HT1080 cells expressing XRCC1-RFP were irradiated with single high energy nickel ions, and time-lapse images of the irradiated cells were obtained online. The live cell imaging analysis shows that strand-break repair protein XRCC1 was recruited to the ion hit position within 20 s in the cells and formed bright foci in the cell nucleus. The fast recruitment of XRCC1 at the ion hits reached a maximum at about 200 s post-irradiation and then was followed by a slower release into the nucleoplasm. The measured dual-exponential kinetics of XRCC1 protein are consistent with the proposed consecutive reaction model, and the measurements obtained that the reaction rate constant of the XRCC1 recruitment to DNA strand break is 1.2 × 10-3 s-1 and the reaction rate constant of the XRCC1 release from the break-XRCC1 complex is 1.2 × 10-2 s-1.

Mirror me: Imitative responses in adults with autism.

PubMed

Schunke, Odette; Schöttle, Daniel; Vettorazzi, Eik; Brandt, Valerie; Kahl, Ursula; Bäumer, Tobias; Ganos, Christos; David, Nicole; Peiker, Ina; Engel, Andreas K; Brass, Marcel; Münchau, Alexander

2016-02-01

Dysfunctions of the human mirror neuron system have been postulated to underlie some deficits in autism spectrum disorders including poor imitative performance and impaired social skills. Using three reaction time experiments addressing mirror neuron system functions under simple and complex conditions, we examined 20 adult autism spectrum disorder participants and 20 healthy controls matched for age, gender and education. Participants performed simple finger-lifting movements in response to (1) biological finger and non-biological dot movement stimuli, (2) acoustic stimuli and (3) combined visual-acoustic stimuli with different contextual (compatible/incompatible) and temporal (simultaneous/asynchronous) relation. Mixed model analyses revealed slower reaction times in autism spectrum disorder. Both groups responded faster to biological compared to non-biological stimuli (Experiment 1) implying intact processing advantage for biological stimuli in autism spectrum disorder. In Experiment 3, both groups had similar 'interference effects' when stimuli were presented simultaneously. However, autism spectrum disorder participants had abnormally slow responses particularly when incompatible stimuli were presented consecutively. Our results suggest imitative control deficits rather than global imitative system impairments. © The Author(s) 2015.

Cutaneous reactions to proton pump inhibitors: a case-control study.

PubMed

Chularojanamontri, Leena; Jiamton, Sukhum; Manapajon, Araya; Suvanasuthi, Saroj; Kulthanan, Kanokvalai; Dhana, Naruemon; Jongjarearnprasert, Kowit

2012-10-01

Even though proton pump inhibitors (PPIs) are commonly used in clinical practice, a limited number of studies are available about cutaneous adverse reactions from PPIs, and most of these are case reports. To demonstrate the pattern of cutaneous reactions related to PPI usage and to evaluate the risk of developing PPI drug eruptions among adult patients. We reviewed the spontaneous reports of any adverse events associated with PPI use, as reported from January 2005 through May 2010 to the Adverse Drug Reaction Center at Siriraj Hospital in Thailand. Each control was sampled from 15 patients who had consecutive hospital numbers from each study case. The prevalence of cutaneous reactions to PPIs varied, ranging from three to 20 per 100,000 of the treated population. Sixty-four patients with a history of reaction to PPIs, and 65 controls were enrolled. Most cutaneous reactions were attributed to omeprazole (n=50; 78.1%), and the most frequently observed cutaneous reaction was maculopapular rash (43.8%). None of the patients experienced a cross-reaction between individual PPIs. Cutaneous adverse reactions to PPIs range from minor drug rashes to a severe, life-threatening reaction. Individuals with a history of adverse drug reaction have an increased risk of cutaneous reaction to PPIs.

Pre-recombination quenching of the radiation induced fluorescence as the approach to study kinetics of ion-molecular reactions

NASA Astrophysics Data System (ADS)

Borovkov, V. I.; Ivanishko, I. S.

2011-04-01

This study deals with the geminate ion recombination in the presence of bulk scavengers, that is the so-called scavenger problem, as well as with the effect of the scavenging reaction on the radiation-induced recombination fluorescence. Borovkov and Velizhanin (2004) have proposed a method to determine the rate constant of the bulk reaction between neutral scavengers and one of the geminate ions if the ion-molecular reaction prevented the formation of electronically excited states upon recombination involving a newly formed ion. If such pre-recombination quenching of the radiation-induced fluorescence took place, it manifested itself as a progressive decrease in the decay of the fluorescence intensity. The relative change in the fluorescence decay as caused by the scavengers was believed to be closely related to the kinetics of the scavenging reaction. The goal of the present study is to support this method, both computationally and experimentally because there are two factors, which cast doubt on the intuitively obvious approach to the scavenger problem: spatial correlations between the particles involved and the drift of the charged reagent in the electric field of its geminate partner. Computer simulation of geminate ions recombination with an explicit modeling of the motion trajectories of scavengers has been performed for media of low dielectric permittivity, i.e. for the maximal Coulomb interaction between the ions. The simulation has shown that upon continuous diffusion of the particles involved, the joint effect of the two above factors can be considered as insignificant with a high accuracy. Besides, it is concluded then that the method of pre-recombination quenching could be applied to study parallel and consecutive reactions where the yields of excited states in the reaction pathways are different with the use of very simple analytical relations of the formal chemical kinetics. The conclusion has been confirmed experimentally by the example of the reactions of electron transfer from the diphenylacetylene radical anion to dibromoethane and hexafluorobenzene in n-dodecane solutions.

Comparing the Effectiveness of Two Models of Initial Teacher Education Programmes in Israel: Concurrent vs. Consecutive

ERIC Educational Resources Information Center

Zuzovsky, Ruth; Donitsa-Schmidt, Smadar

2017-01-01

The purpose of the present study was to examine the effectiveness of two common models of initial teacher education programmes that are prevalent in many countries, including Israel. The two are: the concurrent model, in which disciplinary studies and pedagogical studies are integrated and taught at the same time; and the consecutive model, which…

Cross-reactions among parabens, para-phenylenediamine, and benzocaine: a retrospective analysis of patch testing.

PubMed

Turchin, Irina; Moreau, Linda; Warshaw, Erin; Sasseville, Denis

2006-12-01

Parabens are alkyl ester derivatives of para-hydroxybenzoic acid and are the most commonly used preservatives in the cosmetic industry. Cross-reactions with para-amino compounds, namely, benzocaine and para-phenylenediamine (PPD), have been reported but are thought to be extremely rare. To evaluate the rate of cross-reactivity between parabens, PPD, and benzocaine in a population of patients patch-tested in a hospital-based contact dermatitis clinic. A retrospective analysis of 4,368 patients consecutively patch-tested between July 1989 and June 2005. Our study demonstrated that the rate of cross-reactions to parabens in PPD- and benzocaine-positive patients combined is 2%. This cross-reaction rate is significant in the tested population but still falls within the previously reported rates of sensitivity to parabens in the general population (0 to 3.5%).

Bringing functions together with fusion enzymes--from nature's inventions to biotechnological applications.

PubMed

Elleuche, Skander

2015-02-01

It is a mammoth task to develop a modular protein toolbox enabling the production of posttranslational organized multifunctional enzymes that catalyze reactions in complex pathways. However, nature has always guided scientists to mimic evolutionary inventions in the laboratory and, nowadays, versatile methods have been established to experimentally connect enzymatic activities with multiple advantages. Among the oldest known natural examples is the linkage of two or more juxtaposed proteins catalyzing consecutive, non-consecutive, or opposing reactions by a native peptide bond. There are multiple reasons for the artificial construction of such fusion enzymes including improved catalytic activities, enabled substrate channelling by proximity of biocatalysts, higher stabilities, and cheaper production processes. To produce fused proteins, it is either possible to genetically fuse coding open reading frames or to connect proteins in a posttranslational process. Molecular biology techniques that have been established for the production of end-to-end or insertional fusions include overlap extension polymerase chain reaction, cloning, and recombination approaches. Depending on their flexibility and applicability, these methods offer various advantages to produce fusion genes in high throughput, different orientations, and including linker sequences to maximize the flexibility and performance of fusion partners. In this review, practical techniques to fuse genes are highlighted, enzymatic parameters to choose adequate enzymes for fusion approaches are summarized, and examples with biotechnological relevance are presented including a focus on plant biomass-degrading glycosyl hydrolases.

SU-F-T-01: Optimization of the Accelerated Partial Breast Brachytherapy Fractionation with Consideration of Physical Doses to Tumor and Organ at Risk

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, W; Huq, M

2016-06-15

Purpose: The accelerated partial breast irradiation (APBI) with brachytherapy prescribes 34Gy to be delivered in 10 fractions over 5 consecutive working days without considering the physical dose to the target and organs at risk (OARs) for an individual patient. The purpose of this study is to optimize the fractionation scheme by evaluating the radiation effect on tumor and OARs with a modified linear-quadratic (LQ) model based on dose-volume histograms (DVHs). Methods: Five breast patients treated with multilumen balloon brachytherapy were selected. The minimum skin and rib spacing were ranged from 2.5mm to 14.3mm and from 1.0mm to 25.0mm, respectively. Themore » LQ model parameters were set as: (1) breast: α=0.08, β=0.028, doubling time Tpot=14.4 days, and starting time Tk=21days; (2) skin: acute reaction α=0.101, β=0.009; late reaction α=0.064, β=0.029; (3) rib: α=0.3, β=0.12. Boundary dose Dt was 6 Gy for both target and OARs. The relation between radiation effects on the tumor (ET) and OARs (EOAR) were plotted for fraction number from 1 to 20. Results: The value of radiation effect from routine 3.4Gyx10 fractions was used as reference, ETref and EOARref. If set ET=ETref, the fractionation that results in minimum EOAR values correspond to the optimal fractionation. For these patients, the optimal numbers are 10 fractions for skin acute reaction, 18 fractions for skin and rib late reaction while the doses per fraction are 3.4Gy and 2.05–2.10Gy, respectively. If set EOAR=EOARref, the fractionation that results in a maximum ET value corresponds to the optimal fractionation. The optimal fractionation is 3.4Gyx10 fractions for skin acute reaction, and 2.10–2.25Gyx18 fractions for skin late reaction and rib. Conclusion: For APBI brachytherapy, the routine 3.4Gyx10 fractions is optimal fractionation for skin acute reaction, while 2.05–2.25Gyx18 fractions is optimal fractionation for late reaction of skin and rib.« less

Acute effects of heavy-load squats on consecutive squat jump performance.

PubMed

Weber, Kurt R; Brown, Lee E; Coburn, Jared W; Zinder, Steven M

2008-05-01

Postactivation potentiation (PAP) and complex training have generated interest within the strength and conditioning community in recent years, but much of the research to date has produced confounding results. The purpose of this study was to observe the acute effects of a heavy-load back squat [85% 1 repetition maximum (1RM)] condition on consecutive squat jump performance. Twelve in-season Division I male track-and-field athletes participated in two randomized testing conditions: a five-repetition back squat at 85% 1RM (BS) and a five-repetition squat jump (SJ). The BS condition consisted of seven consecutive squat jumps (BS-PRE), followed by five repetitions of the BS at 85% 1RM, followed by another set of seven consecutive squat jumps (BS-POST). The SJ condition was exactly the same as the BS condition except that five consecutive SJs replaced the five BSs, with 3 minutes' rest between each set. BS-PRE, BS-POST, SJ-PRE, and SJ-POST were analyzed and compared for mean and peak jump height, as well as mean and peak ground reaction force (GRF). The BS condition's mean and peak jump height and peak GRF increased 5.8% +/- 4.8%, 4.7% +/- 4.8%, and 4.6% +/- 7.4%, respectively, whereas the SJ condition's mean and peak jump height and peak GRF decreased 2.7% +/- 5.0%, 4.0% +/- 4.9%, and 1.3% +/- 7.5%, respectively. The results indicate that performing a heavy-load back squat before a set of consecutive SJs may enhance acute performance in average and peak jump height, as well as peak GRF.

Direct construction of diverse metallophthalocyanines by manifold substrates in a deep eutectic solvent

NASA Astrophysics Data System (ADS)

Shaabani, Ahmad; Hooshmand, Seyyed Emad; Afshari, Ronak; Shaabani, Shabnam; Ghasemi, Vahid; Atharnezhad, Mojtaba; Akbari, Masoud

2018-02-01

Direct access to a wide range of metal-free phthalocyanines and metallophthalocyanines in deep eutectic solvents (DESs), is reported. Substituted and unsubstituted phthalocyanines of Mn, Fe, Co, Ni, Cu, Zn, Pd, In, and Pt with various raw materials such as phthalonitriles, phthalimides, phthalic anhydrides and phthalic acids are successfully prepared in the DES based on choline chloride and urea in a very short reaction time with appropriate yields. It has been shown that DES as a green and rapidly degraded reaction medium in the environment plays a triple role as a solvent, organocatalyst, and reactant in this process. Moreover, the DES system could be separated and reused in four consecutive reaction runs with no considerable loss in catalytic activity.

Study of Chlamydia trachomatis in Military Women; Prevalence, Risk Factors, and a Cost Benefit Analysis of Early Diagnosis and Treatment

DTIC Science & Technology

1998-09-01

lymphogranuloma venereum (LGV). .?.■ Methods: One hundred and ninety seven consecutive men with a clinical presentation coasUtent with IJGV were...REACTION FOR THE DIAGNOSIS OF \\J 1 / Z> LYMPIIOGRANULOMA VENEREUM IN SOUTHERN AFRICA. Radebc F. Fehler HG, Ye Hrun. Tshabalala V, Ballard RC j V

Saudi Students' Reactions to Peer Response Groups in EFL Composition Classrooms

ERIC Educational Resources Information Center

Alqurashi, Fahad

2009-01-01

The aim of the present research was to investigate how Saudi college students would respond to peer response techniques introduced in composition classrooms. The study was conducted over two consecutive semesters, namely the Fall 2005 and Spring 2006. Throughout the two semesters students were grouped in small groups of three, required to look at…

The Effect of Cold Showering on Health and Work: A Randomized Controlled Trial

PubMed Central

Sierevelt, Inger N.; van der Heijden, Bas C. J. M.; Dijkgraaf, Marcel G.; Frings-Dresen, Monique H. W.

2016-01-01

Purpose The aim of this study was to determine the cumulative effect of a routine (hot-to-) cold shower on sickness, quality of life and work productivity. Methods Between January and March 2015, 3018 participants between 18 and 65 years without severe comorbidity and no routine experience of cold showering were randomized (1:1:1:1) to a (hot-to-) cold shower for 30, 60, 90 seconds or a control group during 30 consecutive days followed by 60 days of showering cold at their own discretion for the intervention groups. The primary outcome was illness days and related sickness absence from work. Secondary outcomes were quality of life, work productivity, anxiety, thermal sensation and adverse reactions. Results 79% of participants in the interventions groups completed the 30 consecutive days protocol. A negative binomial regression model showed a 29% reduction in sickness absence for (hot-to-) cold shower regimen compared to the control group (incident rate ratio: 0.71, P = 0.003). For illness days there was no significant group effect. No related serious advents events were reported. Conclusion A routine (hot-to-) cold shower resulted in a statistical reduction of self-reported sickness absence but not illness days in adults without severe comorbidity. Trial Registration Netherlands National Trial Register NTR5183 PMID:27631616

Polymer damage mitigation---predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self-healing applications

NASA Astrophysics Data System (ADS)

Hondred, Peter Raymond

Over the past 50 years, the industrial development and applications for polymers and polymer composites has become expansive. However, as with any young technology, the techniques for predicting material damage and resolving material failure are in need of continued development and refinement. This thesis work takes two approaches to polymer damage mitigation---material lifetime prediction and spontaneous damage repair through self-healing while incorporating bio-renewable feedstock. First, material lifetime prediction offers the benefit of identifying and isolating material failures before the effects of damage results in catastrophic failure. Second, self-healing provides a systematic approach to repairing damaged polymer composites, specifically in applications where a hands-on approach or removing the part from service are not feasible. With regard to lifetime prediction, we investigated three specific polymeric materials---polytetrafluoroethylene (PTFE), poly(ethylene-alt-tetrafluoroethylene) (ETFE), and Kapton. All three have been utilized extensively in the aerospace field as a wire insulation coating. Because of the vast amount of electrical wiring used in aerospace constructions and the potential for electrical and thermal failure, this work develops mathematical models for both the thermal degradation kinetics as well as a lifetime prediction model for electrothermal breakdown. Isoconversional kinetic methods, which plot activation energy as a function of the extent of degradation, present insight into the development each kinetic model. The models for PTFE, ETFE, and Kapton are one step, consecutive three-step, and competitive and consecutive five-step respectively. Statistical analysis shows that an nth order autocatalytic reaction best defined the reaction kinetics for each polymer's degradation. Self-healing polymers arrest crack propagation through the use of an imbedded adhesive that reacts when cracks form. This form of damage mitigation focuses on repairing damage before the damage causes a failure in the polymer's function. In this work, the healing agent (adhesive) is developed using bio-renewable oils instead of solely relying on petroleum based feedstocks. Several bio-renewable thermosetting polymers were successfully prepared from tung oil through cationic polymerization for the use as the healing agent in self-healing microencapsulated applications. Modifications to both the monomers in the resin and the catalyst for polymerization were made and the subsequent changes to mechanical, thermal, and structural properties were identified. Furthermore, compressive lap shear testing was used to confirm that the adhesive properties would be beneficial for self-healing applications. Finally, scanning electron microscopy of the crack plane was used to study the fracture mechanism of the crack.

Two Successive Reactions on a DNA Template: A Strategy for Improving Background and Specificity in Nucleic Acid Detection

PubMed Central

Franzini, Raphael M.

2015-01-01

We report a new strategy for template-mediated fluorogenic chemistry that results in enhanced performance for the fluorescence detection of nucleic acids. In this approach, two successive templated reactions are required to induce a fluorescence signal, rather than only one. These novel fluorescein-labeled oligonucleotide probes, termed 2-STAR probes, contain two quencher groups tethered by separate reductively cleavable linkers. When a 2-STAR quenched probe binds adjacent to either two successive mono triphenyl-phosphine (TPP)-DNAs or a dual TPP-DNA, the two quenchers are released, resulting in a fluorescence signal. Because of the requirement for two consecutive reactions, 2-STAR probes display an unprecedented level of sequence-specificity for template-mediated probe designs. At the same time, background emission generated by off-template reactions or incomplete quenching is among the lowest of any fluorogenic reactive probes for the detection of DNA or RNA. PMID:21294182

Glycosyltransferases as marker genes for the quantitative polymerase chain reaction-based detection of circulating tumour cells from blood samples of patients with breast cancer undergoing adjuvant therapy.

PubMed

Kölbl, Alexandra C; Hiller, Roman A; Ilmer, Mathias; Liesche, Friederike; Heublein, Sabine; Schröder, Lennard; Hutter, Stefan; Friese, Klaus; Jeschke, Udo; Andergassen, Ulrich

2015-08-01

Altered glycosylation is a predominant feature of tumour cells; it serves for cell adhesion and detachment, respectively, and facilitates the immune escape of these cells. Therefore changes in the expression of glycosyltransferase genes could help to identify circulating tumour cells (CTCs) in the blood samples of cancer patients using a quantitative polymerase chain reaction (PCR) approach. Blood samples of healthy donors were inoculated with certain numbers of established breast cancer cell line cells, thus creating a model system. These samples were analysed by quantitative PCR for the expression of six different glycosyltransferase genes. The three genes with the best results in the model system were consecutively applied to samples from adjuvant breast cancer patients and of healthy donors. FUT3 and GALNT6 showed the highest increase in relative expression, while GALNT6 and ST3GAL3 were the first to reach statistically significant different ∆CT-values comparing the sample with and without addition of tumour cells. These three genes were applied to patient samples, but did not show any significant results that may suggest the presence of CTCs in the blood. Although the relative expression of some of the glycosyltransferase genes exhibited reasonable results in the model system, their application to breast cancer patient samples will have to be further improved, e.g. by co-analysis of patient blood samples by gold-standard methods.

Theory of rotational transition in atom-diatom chemical reaction

NASA Astrophysics Data System (ADS)

Nakamura, Masato; Nakamura, Hiroki

1989-05-01

Rotational transition in atom-diatom chemical reaction is theoretically studied. A new approximate theory (which we call IOS-DW approximation) is proposed on the basis of the physical idea that rotational transition in reaction is induced by the following two different mechanisms: rotationally inelastic half collision in both initial and final arrangement channels, and coordinate transformation in the reaction zone. This theory gives a fairy compact expression for the state-to-state transition probability. Introducing the additional physically reasonable assumption that reaction (particle rearrangement) takes place in a spatially localized region, we have reduced this expression into a simpler analytical form which can explicitly give overall rotational state distribution in reaction. Numerical application was made to the H+H2 reaction and demonstrated its effectiveness for the simplicity. A further simplified most naive approximation, i.e., independent events approximation was also proposed and demonstrated to work well in the test calculation of H+H2. The overall rotational state distribution is expressed simply by a product sum of the transition probabilities for the three consecutive processes in reaction: inelastic transition in the initial half collision, transition due to particle rearrangement, and inelastic transition in the final half collision.

Vildagliptin ameliorates pulmonary fibrosis in lipopolysaccharide-induced lung injury by inhibiting endothelial-to-mesenchymal transition.

PubMed

Suzuki, Toshio; Tada, Yuji; Gladson, Santhi; Nishimura, Rintaro; Shimomura, Iwao; Karasawa, Satoshi; Tatsumi, Koichiro; West, James

2017-10-16

Pulmonary fibrosis is a late manifestation of acute respiratory distress syndrome (ARDS). Sepsis is a major cause of ARDS, and its pathogenesis includes endotoxin-induced vascular injury. Recently, endothelial-to-mesenchymal transition (EndMT) was shown to play an important role in pulmonary fibrosis. On the other hand, dipeptidyl peptidase (DPP)-4 was reported to improve vascular dysfunction in an experimental sepsis model, although whether DPP-4 affects EndMT and fibrosis initiation during lipopolysaccharide (LPS)-induced lung injury is unclear. The aim of this study was to investigate the anti-EndMT effects of the DPP-4 inhibitor vildagliptin in pulmonary fibrosis after systemic endotoxemic injury. A septic lung injury model was established by intraperitoneal injection of lipopolysaccharide (LPS) in eight-week-old male mice (5 mg/kg for five consecutive days). The mice were then treated with vehicle or vildagliptin (intraperitoneally, 10 mg/kg, once daily for 14 consecutive days from 1 day before the first administration of LPS.). Flow cytometry, immunohistochemical staining, and quantitative polymerase chain reaction (qPCR) analysis was used to assess cell dynamics and EndMT function in lung samples from the mice. Lung tissue samples from treated mice revealed obvious inflammatory reactions and typical interstitial fibrosis 2 days and 28 days after LPS challenge. Quantitative flow cytometric analysis showed that the number of pulmonary vascular endothelial cells (PVECs) expressing alpha-smooth muscle actin (α-SMA) or S100 calcium-binding protein A4 (S100A4) increased 28 days after LPS challenge. Similar increases in expression were also confirmed by qPCR of mRNA from isolated PVECs. EndMT cells had higher proliferative activity and migration activity than mesenchymal cells. All of these changes were alleviated by intraperitoneal injection of vildagliptin. Interestingly, vildagliptin and linagliptin significantly attenuated EndMT in the absence of immune cells or GLP-1. Inhibiting DPP-4 signaling by vildagliptin could ameliorate pulmonary fibrosis by downregulating EndMT in systemic LPS-induced lung injury.

Ground reaction forces on stairs. Part II: knee implant patients versus normals.

PubMed

Stacoff, Alex; Kramers-de Quervain, Inès A; Luder, Gerhard; List, Renate; Stüssi, Edgar

2007-06-01

The goal of this study was to compare selected parameters of vertical ground reaction forces (GRF) of good outcome patients with different prosthesis designs with a matched control group during level walking, stair ascent and descent. Forty subjects, 29 with three main implant designs (including four subjects with a passive knee flexion restriction), and 11 healthy controls were measured with 8-10 repetitions. Vertical ground reaction forces were measured during two consecutive steps with force plates embedded in the walkway and the staircase. Defined parameters of the force signals were used to compare the results of the test groups. The results show, that, postoperatively, good outcome patients produce gait patterns of the vertical ground reaction force which are comparable to normal healthy subjects with the exception of a few distinct differences: a significant reduction (p<0.05) in the vertical loading on the operated side during level walking at take-off, at weight acceptance and take-off during stair ascent of the normal stair. During stair descent, the patients did not reduce load on the operated side, but increased load variation and side-to-side asymmetry; thus, the mechanical loads on the implants were high, which may be important information with respect to loading protocols of knee implant simulators. No systematic differences in any of the test parameters were found between posterior cruciate-retaining (LCS MB and Innex CR) versus non-retaining (LCS RP and Innex UCOR) implant designs. The restricted group showed significant reductions (p<0.05) of several loading parameters as well as an increased side-to-side asymmetry. About one third of the force parameters of the good outcome patients showed a side-to-side asymmetry between two consecutive steps, which was over a proposed level of acceptance.

Live cell imaging combined with high-energy single-ion microbeam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Na; Du, Guanghua, E-mail: gh-du@impcas.ac.cn; Liu, Wenjing

DNA strand breaks can lead to cell carcinogenesis or cell death if not repaired rapidly and efficiently. An online live cell imaging system was established at the high energy microbeam facility at the Institute of Modern Physics to study early and fast cellular response to DNA damage after high linear energy transfer ion radiation. The HT1080 cells expressing XRCC1-RFP were irradiated with single high energy nickel ions, and time-lapse images of the irradiated cells were obtained online. The live cell imaging analysis shows that strand-break repair protein XRCC1 was recruited to the ion hit position within 20 s in themore » cells and formed bright foci in the cell nucleus. The fast recruitment of XRCC1 at the ion hits reached a maximum at about 200 s post-irradiation and then was followed by a slower release into the nucleoplasm. The measured dual-exponential kinetics of XRCC1 protein are consistent with the proposed consecutive reaction model, and the measurements obtained that the reaction rate constant of the XRCC1 recruitment to DNA strand break is 1.2 × 10{sup −3} s{sup −1} and the reaction rate constant of the XRCC1 release from the break-XRCC1 complex is 1.2 × 10{sup −2} s{sup −1}.« less

Single-Molecule Reaction Chemistry in Patterned Nanowells

PubMed Central

2016-01-01

A new approach to synthetic chemistry is performed in ultraminiaturized, nanofabricated reaction chambers. Using lithographically defined nanowells, we achieve single-point covalent chemistry on hundreds of individual carbon nanotube transistors, providing robust statistics and unprecedented spatial resolution in adduct position. Each device acts as a sensor to detect, in real-time and through quantized changes in conductance, single-point functionalization of the nanotube as well as consecutive chemical reactions, molecular interactions, and molecular conformational changes occurring on the resulting single-molecule probe. In particular, we use a set of sequential bioconjugation reactions to tether a single-strand of DNA to the device and record its repeated, reversible folding into a G-quadruplex structure. The stable covalent tether allows us to measure the same molecule in different solutions, revealing the characteristic increased stability of the G-quadruplex structure in the presence of potassium ions (K+) versus sodium ions (Na+). Nanowell-confined reaction chemistry on carbon nanotube devices offers a versatile method to isolate and monitor individual molecules during successive chemical reactions over an extended period of time. PMID:27270004

Macroradical initiated polymerisation of acrylic and methacrylic monomers.

PubMed

Mijangos, Irene; Guerreiro, António; Piletska, Elena; Whitcombe, Michael J; Karim, Kal; Chianella, Iva; Piletsky, Sergey

2009-10-01

An approach has been developed for the grafting of monomers onto poly(trimethylolpropane trimethacrylate) (polyTRIM) particles using 2,2-diethyl dithiocarbamic acid benzyl ester (DDCABE) as an initiator. A set of polymers was prepared with this technique over different lengths of time and the kinetics of the reaction studied experimentally. It was found that the grafting of initiator to the polymeric support followed a second order reaction, while the subsequent addition of monomers from solution into the polyTRIM macroradicals followed a first order reaction. The living nature of the iniferter modified macroradicals permits easy consecutive grafting of multiple polymeric layers, allowing straightforward functionalisation of particles. However, the effectiveness of the grafted initiator decreased with each cycle of polymerisation. This technique can be used for a wide range of applications in analytical and biochemistry.

Modelling and kinetics studies of a corn-rape blend combustion in an oxy-fuel atmosphere.

PubMed

López, R; Fernández, C; Martínez, O; Sánchez, M E

2015-05-01

A kinetic oxy-combustion study of a previously optimized lignocellulose blend is proposed. Kinetic and diffusion control mechanism are considered. The proposed correlations fit properly with the experimental results and diffusion effects are identified as be important enough to be taken into account. Afterwards, with the results obtained in the kinetic study, a detailed consecutive and parallel kinetic scheme is proposed for modelling the oxy-combustion of the blend. A discussion of the temperature and concentration profiles are included. Variation of products final distribution is considered. Smaller particles than 0.001 m are proposed for reducing temperature and concentration profiles and obtaining a good final product distribution. CO2-char reaction is identified as one of the most important step to be optimized for obtaining the lowest final residue. In this study, char is mainly oxidised at 950 K and this situation is attributed to an optimized blending of the bioresidues. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetics for the distribution of acrylamide in French fries, fried oil and vapour during frying of potatoes.

PubMed

Hsu, Hui-Tsung; Chen, Ming-Jen; Tseng, Tzu-Ping; Cheng, Li-Hsin; Huang, Li-Jen; Yeh, Tai-Sheng

2016-11-15

Kinetic analysis for the formation of acrylamide in heated foods has been typically performed using only measured data of acrylamide in foods; however, its possible loss caused by release from heated foods into fried oil and air has seldom been considered. The results obtained from the monitoring of acrylamide by frying French fries indicated that acrylamide is distributed in three phases: French fries, frying oil, and air. From the evolved gas analysis of acrylamide and the measured concentration profile of the total acrylamide amount present in these phases, the kinetic behaviour for acrylamide formation does not obey the commonly used model of two-step consecutive reactions during frying, while a lumped kinetic model was proposed for the total acrylamide amount. Moreover, a high acrylamide level in air was observed, implying that, apart from consumers of French fries, fast-food restaurant workers are potentially subject to occupational hazards from acrylamide inhalation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemoselective Hydrodehalogenation of Organic Halides Utilizing Two-Dimensional Anionic Electrons of Inorganic Electride [Ca2N]+·e^.

PubMed

Kim, Ye Ji; Kim, Sun Min; Yu, Chunghyeon; Yoo, YoungMin; Cho, Eun Jin; Yang, Jung Woon; Kim, Sung Wng

2017-01-31

Halogenated organic compounds are important anthropogenic chemicals widely used in chemical industry, biology, and pharmacology; however, the persistence and inertness of organic halides cause human health problems and considerable environmental pollution. Thus, the elimination or replacement of halogen atoms with organic halides has been considered a central task in synthetic chemistry. In dehalogenation reactions, the consecutive single-electron transfer from reducing agents generates the radical and corresponding carbanion and thus removes the halogen atom as the leaving group. Herein, we report a new strategy for an efficient chemoselective hydrodehalogenation through the formation of stable carbanion intermediates, which are simply achieved by using highly mobile two-dimensional electrons of inorganic electride [Ca 2 N] + ·e - with effective electron transfer ability. The consecutive single-electron transfer from inorganic electride [Ca 2 N] + ·e - stabilized free carbanions, which is a key step in achieving the selective reaction. Furthermore, a determinant more important than leaving group ability is the stability control of free carbanions according to the s character determined by the backbone structure. We anticipate that this approach may provide new insight into selective chemical formation, including hydrodehalogenation.

Computational Prediction of Excited-State Carbon Tunneling in the Two Steps of Triplet Zimmerman Di-π-Methane Rearrangement.

PubMed

Li, Xin; Liao, Tao; Chung, Lung Wa

2017-11-22

The photoinduced Zimmerman di-π-methane (DPM) rearrangement of polycyclic molecules to form synthetically useful cyclopropane derivatives was found experimentally to proceed in a triplet excited state. We have applied state-of-the-art quantum mechanical methods, including M06-2X, DLPNO-CCSD(T) and variational transition-state theory with multidimensional tunneling corrections, to an investigation of the reaction rates of the two steps in the triplet DPM rearrangement of dibenzobarrelene, benzobarrelene and barrelene. This study predicts a high probability of carbon tunneling in regions around the two consecutive transition states at 200-300 K, and an enhancement in the rates by 104-276/35-67% with carbon tunneling at 200/300 K. The Arrhenius plots of the rate constants were found to be curved at low temperatures. Moreover, the computed 12 C/ 13 C kinetic isotope effects were affected significantly by carbon tunneling and temperature. Our predictions of electronically excited-state carbon tunneling and two consecutive carbon tunneling are unprecedented. Heavy-atom tunneling in some photoinduced reactions with reactive intermediates and narrow barriers can be potentially observed at relatively low temperature in experiments.

Characterization of organic residues of size-resolved fog droplets and their atmospheric implications

NASA Astrophysics Data System (ADS)

Chakraborty, Abhishek; Ervens, Barbara; Gupta, Tarun; Tripathi, Sachchida N.

2016-04-01

Size-resolved fog water samples were collected in two consecutive winters at Kanpur, a heavily polluted urban area of India. Samples were analyzed by an aerosol mass spectrometer after drying and directly in other instruments. Residues of fine fog droplets (diameter: 4-16 µm) are found to be more enriched with oxidized (oxygen to carbon ratio, O/C = 0.88) and low volatility organics than residues of coarse (diameter > 22 µm) and medium size (diameter: 16-22 µm) droplets with O/C of 0.68 and 0.74, respectively. These O/C ratios are much higher than those observed for background ambient organic aerosols, indicating efficient oxidation in fog water. Accompanying box model simulations reveal that longer residence times, together with high aqueous OH concentrations in fine droplets, can explain these trends. High aqueous OH concentrations in smaller droplets are caused by their highest surface-volume ratio and high Fe and Cu concentrations, allowing more uptake of gas phase OH and enhanced Fenton reaction rates, respectively. Although some volatile organic species may have escaped during droplet evaporation, these findings indicate that aqueous processing of dissolved organics varies with droplet size. Therefore, large (regional, global)-scale models need to consider the variable reaction rates, together with metal-catalyzed radical formation throughout droplet populations for accurately predicting aqueous secondary organic aerosol formation.

Prevalence of Sexually Transmitted Diseases in Asymptomatic Renal Transplant Recipients.

PubMed

Sarier, Mehmet; Sepin Ozen, Nevgun; Guler, Hicran; Duman, Ibrahim; Yüksel, Yücel; Tekin, Sabri; Yavuz, Asuman Havva; Yucetin, Levent; Erdogan Yilmaz, Mine

2018-04-04

Sexually transmitted diseases, which may be asymptomatic, have the potential to cause serious health problems in renal transplant recipients. The aim of this study was to determine the prevalence of sexually transmitted diseases in sexually active asymptomatic renal transplant patients by using real-time multiplex polymerase chain reaction assays. This prospective controlled study was conducted between November 2016 and January 2017 in our hospital. Our study group included 80 consecutive, sexually active asymptomatic patients (40 men and 40 women) who had undergone renal transplant in our hospital and who presented to our outpatient clinic for routine follow-up. We also included a control group of 80 consecutive, sexually active nontransplant patients (40 men and 40 women). All patient samples were tested for Gardnerella vaginalis and obligate anaerobes (Prevotella bivia, Porphyromonas species), Candida species, Mycoplasma hominis, Mycoplasma genitalium, Ureaplasma species, Trichomonas vaginalis, Neisseria gonorrhoeae, Chlamydia trachomatis, herpes simplex virus 1 and 2, and Cytomegalovirus by real-time multiplex polymerase chain reaction. The prevalences of infection with Gardnerella vaginalis and obligate anaerobes (P = .043), Ureaplasma species (P = .02), and Cytomegalovirus (P = .016) were found to be significantly higher in the study group versus the control group. However, there was no difference between the 2 groups regarding the prevalence of Mycoplasma infection (P = .70). Sexually transmitted diseases may occur more frequently in sexually active asymptomatic renal transplant recipients than in nontransplanted individuals. Real-time multiplex polymerase chain reaction analysis may be a suitable method for determining these pathogens.

Optimizing the biocatalytic productivity of an engineered sialidase from Trypanosoma rangeli for 3'-sialyllactose production.

PubMed

Zeuner, Birgitte; Luo, Jianquan; Nyffenegger, Christian; Aumala, Ville; Mikkelsen, Jørn Dalgaard; Meyer, Anne S

2014-02-05

An engineered sialidase, Tr6, from Trypanosoma rangeli was used for biosynthetic production of 3'-sialyllactose, a human milk oligosaccharide case compound, from casein glycomacropeptide (CGMP) and lactose, components abundantly present in industrial dairy side streams. Four different enzyme re-use methods were compared to optimize the biocatalytic productivity, i.e. 3'-sialyllactose formation per amount of Tr6 employed: (i) His-tag immobilization on magnetic Cu²⁺-iminodiacetic acid-functionalized nanoparticles (MNPs), (ii) membrane immobilization, (iii) calcium alginate encapsulation of cross-linked Tr6, and (iv) Tr6 catalysis in a membrane reactor. Tr6 immobilized on MNPs gave a biocatalytic productivity of 84 mg 3'-sialyllactose/mg Tr6 after seven consecutive reaction runs. Calcium-alginate and membrane immobilization were inefficient. Using free Tr6 in a 10 kDa membrane reactor produced a 9-fold biocatalytic productivity increase compared to using free Tr6 in a batch reactor giving 306 mg 3'-sialyllactose/mg Tr6 after seven consecutive reaction runs. The 3'-sialyllactose yield on α-2,3-bound sialic acid in CGMP was 74%. Using circular dichroism, a temperature denaturation midpoint of Tr6, Tm, of 57.2 °C was determined. The thermal stability of free Tr6 was similarly high and the Tr6 was stable at the reaction temperature (25 °C) for at least 24 h. Copyright © 2013 Elsevier Inc. All rights reserved.

Characteristics and physiological functions of polyphenols from apples.

PubMed

Akazome, Yoko

2004-01-01

Apples contain many kinds of polyphenols, and the main components are oligomeric procyanidins. Applephenon is apple polyphenol extract produced commercially from unripe apples, and has been used as food additive in order to prevent oxidation of components in foods and its application in functional foods is expected. In a lipid metabolism regulation study, administration of Applephenon has the potential to exert strong anti-oxidative activity and to inhibit consumption of vitamin E and anti-oxidative enzymes. Double blind clinical trials of Applephenon on pediatric patients with atopic dermatitis, and tests using type I allergic model mice suggested that Applephenon might regulate allergic reactions. We found the no observed adverse effect level (NOAEL) of Applephenon is greater than 2000 mg/kg in a 90~day consecutive oral administration toxicity test in rats, and Applephenon is safe and acceptable based on mutagenicity tests.

Strategic enzyme patterning for microfluidic biofuel cells

NASA Astrophysics Data System (ADS)

Kjeang, E.; Sinton, D.; Harrington, D. A.

The specific character of biological enzyme catalysts enables combined fuel and oxidant channels and simplified non-compartmentalized fuel cell assemblies. In this work, a microstructured enzymatic biofuel cell architecture is proposed, and species transport phenomena combined with consecutive chemical reactions are studied computationally in order to provide guidelines for optimization. This is the first computational study of this technology, and a 2D CFD model for species transport coupled with laminar fluid flow and Michaelis-Menten enzyme kinetics is established. It is shown that the system is reaction rate limited, indicating that enzyme specific turnover numbers are key parameters for biofuel cell performance. Separated and mixed enzyme patterns in different proportions are analyzed for various Peclet numbers. High fuel utilization is achieved in the diffusion dominated and mixed species transport regimes with separated enzymes arranged in relation to individual turnover rates. However, the Peclet number has to be above a certain threshold value to obtain satisfying current densities. The mixed transport regime is particularly attractive while current densities are maintained close to maximum levels. Optimum performance is achieved by mixed enzyme patterning tailored with respect to individual turnover rates, enabling high current densities combined with nearly complete fuel utilization.

Kinetic dissection of individual steps in the poly(C)-directed oligoguanylate synthesis from guanosine 5'-monophosphate 2-methylimidazolide

NASA Technical Reports Server (NTRS)

Kanavarioti, A.; Bernasconi, C. F.; Alberas, D. J.; Baird, E. E.

1993-01-01

A kinetic study of oligoguanylate synthesis on a polycytidylate template, poly(C), as a function of the concentration of the activated monomer, guanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpG, is reported. Reactions were run with 0.005-0.045 M 2-MeImpG in the presence of 0.05 M poly(C) at 23 degrees C. The kinetic results are consistent with a reaction scheme (eq 1) that consists of a series of consecutive steps, each step representing the addition of one molecule of 2-MeImpG to the growing oligomer. This scheme allows the calculation of second-order rate constants for every step by analyzing the time-dependent growth of each oligomer. Computer simulations of the course of reaction based on the determined rate constants and eq 1 are in excellent agreement with the product distributions seen in the HPLC profiles. In accord with an earlier study (Fakhrai, H.; Inoue, T.; Orgel, L. E. Tetrahedron 1984, 40, 39), rate constants, ki, for the formation of the tetramer and longer oligomers up to the 16-mer were found to be independent of length and somewhat higher than k3 (formation of trimer), which in turn is much higher than k2 (formation of dimer). The ki (i > or = 4), k3, and k2 values are not true second-order rate constants but vary with monomer concentration. Mechanistic models for the dimerization (Scheme I) and elongation reactions (Scheme II) are proposed that are consistent with our results. These models take into account that the monomer associates with the template in a cooperative manner. Our kinetic analysis allowed the determination of rate constants for the elementary processes of covalent bond formation between two monomers (dimerization) and between an oligomer and a monomer (elongation) on the template. A major conclusion from our study is that bond formation between two monomer units or between a primer and a monomer is assisted by the presence of additional next-neighbor monomer units. This is consistent with recent findings with hairpin oligonucleotides (Wu, T.; Orgel, L. E. J. Am. Chem. Soc. 1992, 114, 317). Our study is the first of its kind that shows the feasibility of a thorough kinetic analysis of a template-directed oligomerization and provides a detailed mechanistic model of these reactions.

Evaluating the consistency of location of the most severe acute skin reaction and highest skin dose measured by thermoluminescent dosimeter during radiotherapy for breast cancer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Li-Min, E-mail: limin.sun@yahoo.com; Huang, Chih-Jen; Department of Faculty of Medicine, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung, Taiwan

We conducted this prospective study to evaluate whether the location of the most severe acute skin reaction matches the highest skin dose measured by thermoluminescent dosimeter (TLD) during adjuvant radiotherapy (RT) for patients with breast cancer after breast conservative surgery. To determine whether TLD measurement can reflect the location of the most severe acute skin reaction, 80 consecutive patients were enrolled in this prospective study. We divided the irradiated field into breast, axillary, inframammary fold, and areola/nipple areas. In 1 treatment session when obvious skin reaction occurred, we placed the TLD chips onto the 4 areas and measured the skinmore » dose. We determined whether the highest measured skin dose area is consistent with the location of the most severe skin reaction. The McNemar test revealed that the clinical skin reaction and TLD measurement are more consistent when the most severe skin reaction occurred at the axillary area, and the p = 0.0108. On the contrary, TLD measurement of skin dose is less likely consistent with clinical observation when the most severe skin reaction occurred at the inframammary fold, breast, and areola/nipple areas (all the p > 0.05). Considering the common site of severe skin reaction over the axillary area, TLD measurement may be an appropriate way to predict skin reaction during RT.« less

Direct Conversion of Cellulose into Ethyl Lactate in Supercritical Ethanol-Water Solutions.

PubMed

Yang, Lisha; Yang, Xiaokun; Tian, Elli; Lin, Hongfei

2016-01-08

Biomass-derived ethyl lactate is a green solvent with a growing market as the replacement for petroleum-derived toxic organic solvents. Here we report, for the first time, the production of ethyl lactate directly from cellulose with the mesoporous Zr-SBA-15 silicate catalyst in a supercritical mixture of ethanol and water. The relatively strong Lewis and weak Brønsted acid sites on the catalyst, as well as the surface hydrophobicity, were beneficial to the reaction and led to synergy during consecutive reactions, such as depolymerization, retro-aldol condensation, and esterification. Under the optimum reaction conditions, ∼33 % yield of ethyl lactate was produced from cellulose with the Zr-SBA-15 catalyst at 260 °C in supercritical 95:5 (w/w) ethanol/water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single turnover studies of oxidative halophenol dehalogenation by horseradish peroxidase reveal a mechanism involving two consecutive one electron steps: toward a functional halophenol bioremediation catalyst.

PubMed

Sumithran, Suganya; Sono, Masanori; Raner, Gregory M; Dawson, John H

2012-12-01

Horseradish peroxidase (HRP) catalyzes the oxidative para-dechlorination of the environmental pollutant/carcinogen 2,4,6-trichlorophenol (2,4,6-TCP). A possible mechanism for this reaction is a direct oxygen atom transfer from HRP compound I (HRP I) to trichlorophenol to generate 2,6-dichloro 1,4-benzoquinone, a two-electron transfer process. An alternative mechanism involves two consecutive one-electron transfer steps in which HRP I is reduced to compound II (HRP II) and then to the ferric enzyme as first proposed by Wiese et al. [F.W. Wiese, H.C. Chang, R.V. Lloyd, J.P. Freeman, V.M. Samokyszyn, Arch. Environ. Contam. Toxicol. 34 (1998) 217-222]. To probe the mechanism of oxidative halophenol dehalogenation, the reactions between 2,4,6-TCP and HRP compounds I or II have been investigated under single turnover conditions (i.e., without excess H(2)O(2)) using rapid scan stopped-flow spectroscopy. Addition of 2,4,6-TCP to HRP I leads rapidly to HRP II and then more slowly to the ferric resting state, consistent with a mechanism involving two consecutive one-electron oxidations of the substrate via a phenoxy radical intermediate. HRP II can also directly dechlorinate 2,4,6-TCP as judged by rapid scan stopped-flow and mass spectrometry. This observation is particularly significant since HRP II can only carry out one-electron oxidations. A more detailed understanding of the mechanism of oxidative halophenol dehalogenation will facilitate the use of HRP as a halophenol bioremediation catalyst. Copyright © 2012 Elsevier Inc. All rights reserved.

Potential impact of 1.5 °C and 2 °C global warming on consecutive dry and wet days over West Africa

NASA Astrophysics Data System (ADS)

Ama Browne Klutse, Nana; Ajayi, Vincent O.; Olabode Gbobaniyi, Emiola; Egbebiyi, Temitope S.; Kouadio, Kouakou; Nkrumah, Francis; Akumenyi Quagraine, Kwesi; Olusegun, Christiana; Diasso, Ulrich; Abiodun, Babatunde J.; Lawal, Kamoru; Nikulin, Grigory; Lennard, Christopher; Dosio, Alessandro

2018-05-01

We examine the impact of +1.5 °C and +2 °C global warming levels above pre-industrial levels on consecutive dry days (CDD) and consecutive wet days (CWD), two key indicators for extreme precipitation and seasonal drought. This is done using climate projections from a multi-model ensemble of 25 regional climate model (RCM) simulations. The RCMs take boundary conditions from ten global climate models (GCMs) under the RCP8.5 scenario. We define CDD as the maximum number of consecutive days with rainfall amount less than 1 mm and CWD as the maximum number of consecutive days with rainfall amount more than 1 mm. The differences in model representations of the change in CDD and CWD, at 1.5 °C and 2 °C global warming, and based on the control period 1971‑2000 are reported. The models agree on a noticeable response to both 1.5 °C and 2 °C warming for each index. Enhanced warming results in a reduction in mean rainfall across the region. More than 80% of ensemble members agree that CDD will increase over the Guinea Coast, in tandem with a projected decrease in CWD at both 1.5 °C and 2 °C global warming levels. These projected changes may influence already fragile ecosystems and agriculture in the region, both of which are strongly affected by mean rainfall and the length of wet and dry periods.

Lyral has been included in the patch test standard series in Germany.

PubMed

Geier, Johannes; Brasch, Jochen; Schnuch, Axel; Lessmann, Holger; Pirker, Claudia; Frosch, Peter J

2002-05-01

Lyral 5% pet. was tested in 3245 consecutive patch test patients in 20 departments of dermatology in order (i) to check the diagnostic quality of this patch test preparation, (ii) to examine concomitant reactions to Lyral and fragrance mix (FM), and (iii) to assess the frequency of contact allergy to Lyral in an unselected patch test population of German dermatological clinics. 62 patients reacted to Lyral, i.e. 1.9%. One third of the positive reactions were + + and + + +. The reaction index was 0.27. Thus, the test preparation can be regarded a good diagnostic tool. Lyral and fragrance mix (FM) were tested in parallel in 3185 patients. Of these, 300 (9.4%) reacted to FM, and 59 (1.9%) to Lyral. In 40 patients, positive reactions to both occurred, which is 13.3% of those reacting to FM, and 67.8% of those reacting to Lyral. So the concordance of positive test reactions to Lyral and FM was only slight. Based on these results, the German Contact Dermatitis Research Group (DKG) decided to add Lyral 5% pet. to the standard series.

Telescoping Reactions with Trifluorodiazoethane-Derived Aza-Wittig Reagents and Allenyl esters.

PubMed

Zhang, Fa-Guang; Zeng, Jun-Liang; Tian, Yi-Qiang; Zheng, Yan; Cahard, Dominique; Ma, Jun-An

2018-05-28

A telescoping process involving the consecutive addition of four reagents (trifluorodiazoethane, phosphine, allenyl ester, and acetic acid) into a single reactor was developed for the novel functionalization of allenyl esters. First, new phosphazenes derived from trifluorodiazoethane and phosphines were generated and reacted with allenyl esters to give unexpected α-iminophosphoranes through the creation of C=P, C=N, and C-H bonds at the α-, β-, and γ-carbon atoms, respectively, of the allenyl esters. The α-iminophosphoranes did not react with aldehydes in a classic Wittig reaction, but instead β-enamino esters were obtained. The overall sequence of reactions offered a formal hydrohydrazonation of allenyl esters. The method was extended to other related diazo compounds and applied to the preparation of novel 5-pyrazolone derivatives. Not only is the telescoping process described herein an effective approach for truncating the multistep synthesis, but also each step has been dissected to understand and support the reaction mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theory of Visual Attention (TVA) applied to mice in the 5-choice serial reaction time task.

PubMed

Fitzpatrick, C M; Caballero-Puntiverio, M; Gether, U; Habekost, T; Bundesen, C; Vangkilde, S; Woldbye, D P D; Andreasen, J T; Petersen, A

2017-03-01

The 5-choice serial reaction time task (5-CSRTT) is widely used to measure rodent attentional functions. In humans, many attention studies in healthy and clinical populations have used testing based on Bundesen's Theory of Visual Attention (TVA) to estimate visual processing speeds and other parameters of attentional capacity. We aimed to bridge these research fields by modifying the 5-CSRTT's design and by mathematically modelling data to derive attentional parameters analogous to human TVA-based measures. C57BL/6 mice were tested in two 1-h sessions on consecutive days with a version of the 5-CSRTT where stimulus duration (SD) probe length was varied based on information from previous TVA studies. Thereafter, a scopolamine hydrobromide (HBr; 0.125 or 0.25 mg/kg) pharmacological challenge was undertaken, using a Latin square design. Mean score values were modelled using a new three-parameter version of TVA to obtain estimates of visual processing speeds, visual thresholds and motor response baselines in each mouse. The parameter estimates for each animal were reliable across sessions, showing that the data were stable enough to support analysis on an individual level. Scopolamine HBr dose-dependently reduced 5-CSRTT attentional performance while also increasing reward collection latency at the highest dose. Upon TVA modelling, scopolamine HBr significantly reduced visual processing speed at both doses, while having less pronounced effects on visual thresholds and motor response baselines. This study shows for the first time how 5-CSRTT performance in mice can be mathematically modelled to yield estimates of attentional capacity that are directly comparable to estimates from human studies.

In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

PubMed

Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

2018-06-13

We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

The kinetics of dissolution of dolomite in CO2-H2O systems at 1.5 to 65oC and 0 to 1 atm PCO2.

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1982-01-01

Weight loss measurements at different T and PCO2 during experimental investigations of the dissolution kinetics of eight samples of dolomite permitted recognition of a two-stage process. During the first stage, which is brief, the surface composition of the dolomite becomes enriched with the MgCO3 component and the CaCO3 component dissolves faster. In the second and more important stage both components of the solid are released stoichiometrically, described quantitatively by three parallel consecutive forward reactions and one significant backward reaction. Dissolution rates are apparently more dependent on crystallographic order than on compositional variations. -M.S.

Reverse transcription polymerase chain reaction protocols for cloning small circular RNAs.

PubMed

Navarro, B; Daròs, J A; Flores, R

1998-07-01

A protocol is described for general application for cloning small circular RNAs which requires only minimal amounts of template (approximately 50 ng) of unknown sequence. Both cDNA strands are synthesized with a 26-mer primer whose six 3'-terminal positions are totally degenerate in two consecutive reactions catalyzed by reverse transcriptase and DNA polymerase, respectively. The cDNAs are then PCR-amplified, using a 20-mer primer with the non-degenerate sequence of the previous primer, cloned and sequenced. This information permits the synthesis of one or more pairs of specific and adjacent primers for obtaining full-length cDNA clones by a protocol which is also described.

The effects of consecutive night shifts and shift length on cognitive performance and sleepiness: a field study.

PubMed

Haidarimoghadam, Rashid; Kazemi, Reza; Motamedzadeh, Majid; Golmohamadi, Rostam; Soltanian, Alireza; Zoghipaydar, Mohamad Reza

2017-06-01

The aim of this study was to evaluate the effects of consecutive night shifts (CNS) and shift length on cognitive performance and sleepiness. This study evaluated the sleepiness and performance of 30 control room operators (CROs) working in 7 nights, 7 days, 7 days off (7N7D7O) and 30 CROs working in 4 nights, 7 days, 3 nights, 7 days off (4N7D3N7O) shift patterns in a petrochemical complex on the last night shift before swinging into the day shift. To assess cognitive performance, the n-back test, continuous performance test and simple reaction time test were employed. To assess sleepiness, the Karolinska sleepiness scale was used. Both schedules indicated that the correct responses and response times of working memory were reduced (p = 0.001), while intentional errors and sleepiness increased during the shift work (p = 0.001). CNS had a significant impact on reaction time and commission errors (p = 0.001). The main duty of CROs at a petrochemical plant is checking hazardous processes which require appropriate alertness and cognitive performance. As a result, planning for appropriate working hours and suitable number of CNS in a rotating shift system is a contribution to improving CRO performance and enhancing safety.

A 12-Day Course of Imiquimod 5% for the Treatment of Actinic Keratosis: Effectiveness and Local Reactions.

PubMed

Serra-Guillén, C; Nagore, E; Llombart, B; Sanmartín, O; Requena, C; Calomarde, L; Guillén, C

2018-04-01

Imiquimod is an excellent option for patients with actinic keratosis, although its use may be limited by the long course of treatment required (4 weeks) and the likelihood of local skin reactions. The objectives of the present study were to demonstrate the effectiveness of a 12-day course of imiquimod 5% for the treatment of actinic keratosis and to examine the association between treatment effectiveness and severity of local reactions. We included patients with at least 8 actinic keratoses treated with imiquimod 5% cream for 12 consecutive days. Local reactions were classified as mild, moderate, or severe. The statistical analysis of the association between local reactions and clinical response was based on the Pearson χ 2 test and the Spearman rank correlation test. Sixty-five patients completed the study. Complete response was recorded in 52.3% and partial response in 75.4%. We found a statistically significant association between severity of the local reaction and response to treatment in both the Pearson χ 2 test and the Spearman rank correlation test. A 12-day course of imiquimod 5% proved effective for the treatment of actinic keratosis. Severity of local reactions during treatment was correlated with clinical response. Copyright © 2017 AEDV. Publicado por Elsevier España, S.L.U. All rights reserved.

Structural and kinetic studies on the Ser101Ala variant of choline oxidase: Catalysis by compromise

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finnegan, S.; Orville, A.; Yuan, H.

2010-09-15

The oxidation of choline catalyzed by choline oxidase includes two reductive half-reactions where FAD is reduced by the alcohol substrate and by an aldehyde intermediate transiently formed in the reaction. Each reductive half-reaction is followed by an oxidative half-reaction where the reduced flavin is oxidized by oxygen. Here, we have used mutagenesis to prepare the Ser101Ala mutant of choline oxidase and have investigated the impact of this mutation on the structural and kinetic properties of the enzyme. The crystallographic structure of the Ser101Ala enzyme indicates that the only differences between the mutant and wild-type enzymes are the lack of amore » hydroxyl group on residue 101 and a more planar configuration of the flavin in the mutant enzyme. Kinetics established that replacement of Ser101 with alanine yields a mutant enzyme with increased efficiencies in the oxidative half-reactions and decreased efficiencies in the reductive half-reactions. This is accompanied by a significant decrease in the overall rate of turnover with choline. Thus, this mutation has revealed the importance of a specific residue for the optimization of the overall turnover of choline oxidase, which requires fine-tuning of four consecutive half-reactions for the conversion of an alcohol to a carboxylic acid.« less

The digital code driven autonomous synthesis of ibuprofen automated in a 3D-printer-based robot.

PubMed

Kitson, Philip J; Glatzel, Stefan; Cronin, Leroy

2016-01-01

An automated synthesis robot was constructed by modifying an open source 3D printing platform. The resulting automated system was used to 3D print reaction vessels (reactionware) of differing internal volumes using polypropylene feedstock via a fused deposition modeling 3D printing approach and subsequently make use of these fabricated vessels to synthesize the nonsteroidal anti-inflammatory drug ibuprofen via a consecutive one-pot three-step approach. The synthesis of ibuprofen could be achieved on different scales simply by adjusting the parameters in the robot control software. The software for controlling the synthesis robot was written in the python programming language and hard-coded for the synthesis of ibuprofen by the method described, opening possibilities for the sharing of validated synthetic 'programs' which can run on similar low cost, user-constructed robotic platforms towards an 'open-source' regime in the area of chemical synthesis.

The digital code driven autonomous synthesis of ibuprofen automated in a 3D-printer-based robot

PubMed Central

Kitson, Philip J; Glatzel, Stefan

2016-01-01

An automated synthesis robot was constructed by modifying an open source 3D printing platform. The resulting automated system was used to 3D print reaction vessels (reactionware) of differing internal volumes using polypropylene feedstock via a fused deposition modeling 3D printing approach and subsequently make use of these fabricated vessels to synthesize the nonsteroidal anti-inflammatory drug ibuprofen via a consecutive one-pot three-step approach. The synthesis of ibuprofen could be achieved on different scales simply by adjusting the parameters in the robot control software. The software for controlling the synthesis robot was written in the python programming language and hard-coded for the synthesis of ibuprofen by the method described, opening possibilities for the sharing of validated synthetic ‘programs’ which can run on similar low cost, user-constructed robotic platforms towards an ‘open-source’ regime in the area of chemical synthesis. PMID:28144350

Service workers' chain reactions to daily customer mistreatment: Behavioral linkages, mechanisms, and boundary conditions.

PubMed

Chi, Nai-Wen; Yang, Jixia; Lin, Chia-Ying

2018-01-01

Drawing on the stressor-emotion model, we examine how customer mistreatment can evoke service workers' passive forms of deviant behaviors (i.e., work withdrawal behavior [WWB]) and negative impacts on their home life (i.e., work-family conflict [WFC]), and whether individuals' core self-evaluations and customer service training can buffer the negative effects of customer mistreatment. Using the experience sampling method, we collect daily data from 77 customer service employees for 10 consecutive working days, yielding 546 valid daily responses. The results show that daily customer mistreatment increases service workers' daily WWB and WFC through negative emotions. Furthermore, employees with high core self-evaluations and employees who received customer service training are less likely to experience negative emotions when faced with customer mistreatment, and thus are less likely to engage in WWB or provoke WFC. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Canine leishmaniosis in three consecutive generations of dogs in Czech Republic.

PubMed

Svobodova, Vlasta; Svoboda, Miroslav; Friedlaenderova, Lucia; Drahotsky, Petr; Bohacova, Eva; Baneth, Gad

2017-04-15

Transmission of canine leishmaniosis (CanL) is described in three consecutive generations of female Boxers living in a non-endemic environment in the Czech Republic. Infection of the first generation female likely occurred during a breeding visit to Italy and the dog died with typical clinical signs of the disease but without definitive laboratory diagnosis. The second and third generation offsprings never left the Czech Republic, suffered from clinical CanL confirmed by polymerase chain reaction and serology, and were apparently infected by transplacental transmission. Persistence of CanL in the Czech Republic over 7 years with a suspected origin in an endemic region and progression of infection through subsequent generations in a non-endemic country exemplifies that this disease may establish itself also in areas where no obvious vectors are present. Copyright © 2017. Published by Elsevier B.V.

Rhodium-Catalyzed Synthesis of Chiral Spiro-9-silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters.

PubMed

Murai, Masahito; Takeuchi, Yutaro; Yamauchi, Kanae; Kuninobu, Yoichiro; Takai, Kazuhiko

2016-04-18

Mechanistic insight into the construction of quaternary silicon chiral centers by rhodium-catalyzed synthesis of spiro-9-silabifluorenes through dehydrogenative silylation is reported. The C2 -symmetric bisphosphine ligand, BINAP, was effective in controlling enantioselectivity, and axially chiral spiro-9-silabifluorenes were obtained in excellent yields with high enantiomeric excess. Monitoring of the reaction revealed the presence of a monohydrosilane intermediate as a mixture of two constitutional isomers. The reaction proceeded through two consecutive dehydrogenative silylations, and the absolute configuration was determined in the first silylative cyclization. Competitive reactions with electron-rich and electron-deficient dihydrosilanes indicated that the rate of silylative cyclization increased with decreasing electron density on the silicon atom of the starting dihydrosilane. Further investigation disclosed a rare interconversion between the two constitutional isomers of the monohydrosilane intermediate with retention of the absolute configuration. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The mechanism of hydrothermal hydrolysis for glycyrrhizic acid into glycyrrhetinic acid and glycyrrhetinic acid 3-O-mono-β-D-glucuronide in subcritical water.

PubMed

Fan, Rui; Li, Nan; Xu, Honggao; Xiang, Jun; Wang, Lei; Gao, Yanxiang

2016-01-01

To improve the bioactivity and sweetness properties of glycyrrhizic acid (GL), the hydrothermal hydrolysis of GL into glycyrrhetinic acid (GA) and glycyrrhetinic acid 3-O-mono-β-D-glucuronide (GAMG) in subcritical water was investigated. The effects of temperature, time and their interaction on the conversion ratios were analyzed and the reactions were elaborated with kinetics and thermodynamics. The results showed that GL hydrothermal hydrolysis was significantly (P < 0.05) affected by reaction time and temperature, as well as their interaction, and could be fitted into first-order kinetics. The thermodynamic analysis indicated that the hydrolysis of GL was endergonic and non-spontaneous. The hydrolytic pathways were composed of complex consecutive and parallel reactions. It was concluded that subcritical water may be a potential medium for producing GAMG and GA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reduction of biselenites into polyselenides in interlayer space of layered double hydroxides

NASA Astrophysics Data System (ADS)

Kim, Myeong Shin; Lee, Yongju; Park, Yong-Min; Cha, Ji-Hyun; Jung, Duk-Young

2018-06-01

A selenous acid (H2SeO3) precursor was intercalated as biselenite (HSeO3-) ions into the interlayer gallery of carbonated magnesium aluminum layered double hydroxide (MgAl-LDH) in aqueous solution. Reduction reaction of selenous ions by aqueous hydrazine solution produced polyselenide intercalated LDHs which were consecutively exchanged with iodide through redox reaction under iodine vapor. The polyselenide containing LDHs adsorbed iodine vapor spontaneously and triiodide was incorporated in the interlayer space followed by formation of selenium polycrystalline phase. Two dimensional framework of MgAl-LDH is strong enough to resist against the reducing power of hydrazine as well as oxidation condition of iodine. The SEM data demonstrated that the shapes of LDH polycrystalline have little changed after the above redox reactions. The polyselenide and iodide LDH products were analyzed by XRD, Infrared and Raman spectra which strongly suggested the horizontal arrangement of polyselenide and triiodide in gallery space of LDHs.

Automatic three-dimensional registration of intravascular optical coherence tomography images

NASA Astrophysics Data System (ADS)

Ughi, Giovanni J.; Adriaenssens, Tom; Larsson, Matilda; Dubois, Christophe; Sinnaeve, Peter R.; Coosemans, Mark; Desmet, Walter; D'hooge, Jan

2012-02-01

Intravascular optical coherence tomography (IV-OCT) is a catheter-based high-resolution imaging technique able to visualize the inner wall of the coronary arteries and implanted devices in vivo with an axial resolution below 20 μm. IV-OCT is being used in several clinical trials aiming to quantify the vessel response to stent implantation over time. However, stent analysis is currently performed manually and corresponding images taken at different time points are matched through a very labor-intensive and subjective procedure. We present an automated method for the spatial registration of IV-OCT datasets. Stent struts are segmented through consecutive images and three-dimensional models of the stents are created for both datasets to be registered. The two models are initially roughly registered through an automatic initialization procedure and an iterative closest point algorithm is subsequently applied for a more precise registration. To correct for nonuniform rotational distortions (NURDs) and other potential acquisition artifacts, the registration is consecutively refined on a local level. The algorithm was first validated by using an in vitro experimental setup based on a polyvinyl-alcohol gel tubular phantom. Subsequently, an in vivo validation was obtained by exploiting stable vessel landmarks. The mean registration error in vitro was quantified to be 0.14 mm in the longitudinal axis and 7.3-deg mean rotation error. In vivo validation resulted in 0.23 mm in the longitudinal axis and 10.1-deg rotation error. These results indicate that the proposed methodology can be used for automatic registration of in vivo IV-OCT datasets. Such a tool will be indispensable for larger studies on vessel healing pathophysiology and reaction to stent implantation. As such, it will be valuable in testing the performance of new generations of intracoronary devices and new therapeutic drugs.

Evaluating the consistency of location of the most severe acute skin reaction and highest skin dose measured by thermoluminescent dosimeter during radiotherapy for breast cancer.

PubMed

Sun, Li-Min; Huang, Chih-Jen; Chen, Hsiao-Yun; Chang, Gia-Hsin; Tsao, Min-Jen

2016-01-01

We conducted this prospective study to evaluate whether the location of the most severe acute skin reaction matches the highest skin dose measured by thermoluminescent dosimeter (TLD) during adjuvant radiotherapy (RT) for patients with breast cancer after breast conservative surgery. To determine whether TLD measurement can reflect the location of the most severe acute skin reaction, 80 consecutive patients were enrolled in this prospective study. We divided the irradiated field into breast, axillary, inframammary fold, and areola/nipple areas. In 1 treatment session when obvious skin reaction occurred, we placed the TLD chips onto the 4 areas and measured the skin dose. We determined whether the highest measured skin dose area is consistent with the location of the most severe skin reaction. The McNemar test revealed that the clinical skin reaction and TLD measurement are more consistent when the most severe skin reaction occurred at the axillary area, and the p = 0.0108. On the contrary, TLD measurement of skin dose is less likely consistent with clinical observation when the most severe skin reaction occurred at the inframammary fold, breast, and areola/nipple areas (all the p > 0.05). Considering the common site of severe skin reaction over the axillary area, TLD measurement may be an appropriate way to predict skin reaction during RT. Copyright © 2016 American Association of Medical Dosimetrists. Published by Elsevier Inc. All rights reserved.

Associations between number of consecutive night shifts and impairment of neurobehavioral performance during a subsequent simulated night shift.

PubMed

Magee, Michelle; Sletten, Tracey L; Ferguson, Sally A; Grunstein, Ronald R; Anderson, Clare; Kennaway, David J; Lockley, Steven W; Rajaratnam, Shantha Mw

2016-05-01

This study aimed to investigate sleep and circadian phase in the relationships between neurobehavioral performance and the number of consecutive shifts worked. Thirty-four shift workers [20 men, mean age 31.8 (SD 10.9) years] worked 2-7 consecutive night shifts immediately prior to a laboratory-based, simulated night shift. For 7 days prior, participants worked their usual shift sequence, and sleep was assessed with logs and actigraphy. Participants completed a 10-minute auditory psychomotor vigilance task (PVT) at the start (~21:00 hours) and end (~07:00 hours) of the simulated night shift. Mean reaction times (RT), number of lapses and RT distribution was compared between those who worked 2-3 consecutive night shifts versus those who worked 4-7 shifts. Following 4-7 shifts, night shift workers had significantly longer mean RT at the start and end of shift, compared to those who worked 2-3 shifts. The slowest and fastest 10% RT were significantly slower at the start, but not end, of shift among participants who worked 4-7 nights. Those working 4-7 nights also demonstrated a broader RT distribution at the start and end of shift and had significantly slower RT based on cumulative distribution analysis (5 (th), 25 (th), 50 (th), 75 (th)percentiles at the start of shift; 75th percentile at the end of shift). No group differences in sleep parameters were found for 7 days and 24 hours prior to the simulated night shift. A greater number of consecutive night shifts has a negative impact on neurobehavioral performance, likely due to cognitive slowing.

Evaluation of simultaneous reduction and transport of selenium in saturated soil columns

NASA Astrophysics Data System (ADS)

Guo, Lei; Frankenberger, William T.; Jury, William A.

1999-03-01

Speciation plays an important role in determining the overall leachability of selenium in soil. In this study we present a mathematical model and results of miscible displacement experiments that were conducted to evaluate simultaneous reduction and transport of selenate in saturated soil columns. The experiments were carried out in organic amended (compost manure or gluten) or unamended soil, with O2-sparged or nonsparged influent solution. In all columns, reduction of selenate was fast enough to produce selenite flux in the effluent and elemental Se in the soil profile during a mean residence time of ˜30 hours. Reduction was accelerated in the presence of organic amendments and under low O2 concentrations, resulting in an increased retardation of selenium transport as a whole. The results of our experiments show that although selenate does not sorb to solid surfaces during transport, it reduces rapidly to forms that are strongly retarded. On the basis of simulation with the consecutive reaction and transport model using parameters derived from this study, selenium is expected to be retained near the soil surface, even under extreme leaching conditions.

Rosen's (M,R) system in process algebra.

PubMed

Gatherer, Derek; Galpin, Vashti

2013-11-17

Robert Rosen's Metabolism-Replacement, or (M,R), system can be represented as a compact network structure with a single source and three products derived from that source in three consecutive reactions. (M,R) has been claimed to be non-reducible to its components and algorithmically non-computable, in the sense of not being evaluable as a function by a Turing machine. If (M,R)-like structures are present in real biological networks, this suggests that many biological networks will be non-computable, with implications for those branches of systems biology that rely on in silico modelling for predictive purposes. We instantiate (M,R) using the process algebra Bio-PEPA, and discuss the extent to which our model represents a true realization of (M,R). We observe that under some starting conditions and parameter values, stable states can be achieved. Although formal demonstration of algorithmic computability remains elusive for (M,R), we discuss the extent to which our Bio-PEPA representation of (M,R) allows us to sidestep Rosen's fundamental objections to computational systems biology. We argue that the behaviour of (M,R) in Bio-PEPA shows life-like properties.

Deamidation and transamidation of substance P by tissue transglutaminase revealed by electron-capture dissociation fourier transform mass spectrometry.

PubMed

Fornelli, Luca; Schmid, Adrien W; Grasso, Luigino; Vogel, Horst; Tsybin, Yury O

2011-01-10

Tissue transglutaminase (tTGase) catalyzes both deamidation and transamidation of peptides and proteins by using a peptidyl glutamine as primary substrate. A precise consensus sequence for the enzyme is unknown and the ratio between deamidated and transamidated (or cross-linked) reaction products is highly substrate-dependent. Due to its overlapping body distribution with tTGase and ease of manipulation with tandem mass spectrometry, we used the neuropeptide substance P as a model to investigate the associated enzymatic kinetics and reaction products. Online liquid-chromatography Fourier-transform ion-cyclotron-resonance mass spectrometry (FT-ICR MS) combined with electron-capture dissociation (ECD) was employed to study the tTGase-induced modifications of substance P. A particular strength of ECD for peptide-enzyme reaction product monitoring is its ability to distinguish isomeric amino acids, for example, Glu and iso-Glu, by signature product ions. Our studies show that the primary reaction observed is deamidation, with the two consecutive glutamine residues converted sequentially into glutamate: first Gln(5) , and subsequently Gln(6) . We then applied ECD FT-ICR MS to identify the transamidation site on an enzymatically cross-linked peptide, which turned out to correspond to Gln(5) . Three populations of substance-P dimers were detected that differed by the number of deamidated Gln residues. The higher reactivity of Gln(5) over Gln(6) was further confirmed by cross-linking SP with monodansylcadaverine (MDC). Overall, our approach described herein is of a general importance for mapping both enzymatically induced post-translational protein modifications and cross-linking. Finally, in vitro Ca-signaling assays revealed that the main tTGase reaction product, the singly deamidated SP (RPKPEQFFGLM-NH(2) ), has increased agonist potency towards its natural receptor, thus confirming the biologically relevant role of deamidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bifunctional CYP81AA proteins catalyse identical hydroxylations but alternative regioselective phenol couplings in plant xanthone biosynthesis

PubMed Central

El-Awaad, Islam; Bocola, Marco; Beuerle, Till; Liu, Benye; Beerhues, Ludger

2016-01-01

Xanthones are natural products present in plants and microorganisms. In plants, their biosynthesis starts with regioselective cyclization of 2,3′,4,6-tetrahydroxybenzophenone to either 1,3,5- or 1,3,7-trihydroxyxanthones, catalysed by cytochrome P450 (CYP) enzymes. Here we isolate and express CYP81AA-coding sequences from Hypericum calycinum and H. perforatum in yeast. Microsomes catalyse two consecutive reactions, that is, 3′-hydroxylation of 2,4,6-trihydroxybenzophenone and C–O phenol coupling of the resulting 2,3′,4,6-tetrahydroxybenzophenone. Relative to the inserted 3′-hydroxyl, the orthologues Hc/HpCYP81AA1 cyclize via the para position to form 1,3,7-trihydroxyxanthone, whereas the paralogue HpCYP81AA2 directs cyclization to the ortho position, yielding the isomeric 1,3,5-trihydroxyxanthone. Homology modelling and reciprocal mutagenesis reveal the impact of S375, L378 and A483 on controlling the regioselectivity of HpCYP81AA2, which is converted into HpCYP81AA1 by sextuple mutation. However, the reciprocal mutations in HpCYP81AA1 barely affect its regiospecificity. Product docking rationalizes the alternative C–O phenol coupling reactions. Our results help understand the machinery of bifunctional CYPs. PMID:27145837

Bifunctional CYP81AA proteins catalyse identical hydroxylations but alternative regioselective phenol couplings in plant xanthone biosynthesis.

PubMed

El-Awaad, Islam; Bocola, Marco; Beuerle, Till; Liu, Benye; Beerhues, Ludger

2016-05-05

Xanthones are natural products present in plants and microorganisms. In plants, their biosynthesis starts with regioselective cyclization of 2,3',4,6-tetrahydroxybenzophenone to either 1,3,5- or 1,3,7-trihydroxyxanthones, catalysed by cytochrome P450 (CYP) enzymes. Here we isolate and express CYP81AA-coding sequences from Hypericum calycinum and H. perforatum in yeast. Microsomes catalyse two consecutive reactions, that is, 3'-hydroxylation of 2,4,6-trihydroxybenzophenone and C-O phenol coupling of the resulting 2,3',4,6-tetrahydroxybenzophenone. Relative to the inserted 3'-hydroxyl, the orthologues Hc/HpCYP81AA1 cyclize via the para position to form 1,3,7-trihydroxyxanthone, whereas the paralogue HpCYP81AA2 directs cyclization to the ortho position, yielding the isomeric 1,3,5-trihydroxyxanthone. Homology modelling and reciprocal mutagenesis reveal the impact of S375, L378 and A483 on controlling the regioselectivity of HpCYP81AA2, which is converted into HpCYP81AA1 by sextuple mutation. However, the reciprocal mutations in HpCYP81AA1 barely affect its regiospecificity. Product docking rationalizes the alternative C-O phenol coupling reactions. Our results help understand the machinery of bifunctional CYPs.

Automatic identification of bullet signatures based on consecutive matching striae (CMS) criteria.

PubMed

Chu, Wei; Thompson, Robert M; Song, John; Vorburger, Theodore V

2013-09-10

The consecutive matching striae (CMS) numeric criteria for firearm and toolmark identifications have been widely accepted by forensic examiners, although there have been questions concerning its observer subjectivity and limited statistical support. In this paper, based on signal processing and extraction, a model for the automatic and objective counting of CMS is proposed. The position and shape information of the striae on the bullet land is represented by a feature profile, which is used for determining the CMS number automatically. Rapid counting of CMS number provides a basis for ballistics correlations with large databases and further statistical and probability analysis. Experimental results in this report using bullets fired from ten consecutively manufactured barrels support this developed model. Published by Elsevier Ireland Ltd.

[Effects of aspirin on dendritic cells in the inflammatory microenvironment of rabbit buccal VX-2 squamous cell carcinoma].

PubMed

Chen, Zhihong; Huang, Guilin; Zhang, Nini; Yi, Jie; Yao, Li; Zhang, Lin

2016-04-01

To explore the effects of aspirin and inflammation on the maturation and function of dendritic cells (DC) on the supernatant of VX-2 squamous cell carcinoma. The rabbit buccal VX-2 squamous cell carcinoma models with inflammation were established by tumor particle implantation, mechanical trauma, and high sugar diet. The rabbits were divided into three groups. For the experimental group (rabbit buccal VX-2 squamous cell carcinoma with local inflammation), aspirin were given by gavage for three consecutive days. For the control group (rabbit buccal VX-2 squamous cell carcinoma with local inflammation), normal saline was given by gavage for three consecutive days. For the blank group (tumor without inflammation), normal saline was given by gavage for three consecutive days. Each tumor specimens were collected in three days and made into tissue homogenate. The supernatant was collected after centrifugation. Normal rabbit peripheral blood mononuclear cells were separated and co-cultured with different states of supernatant. The expression of DC surface markers CD83, CD86, and human leukocyte antigen-DR (HLA-DR) were detected by flow cytometry. The state of function of DC was tested by mixed lymphocyte reaction. The positive rate of CD83, CD86, and HLA-DR of the experimental and control groups were both lower than that of the blank group (P<0.05). In addition, the ability to stimulate T cell proliferation of the experimental and control groups were weaker than that of the blank group (P<0.05). No significant difference was observed between the experi- and HLADR of DC. The short-term administration of aspirin is not conducive to the phenoty and function of DC in a rabbit mental and control groups (P>0.05). Inflammation may inhibit the function and expression of CD83, CD86, buccal VX-2 squamous cell carcinoma inflammatory environment

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

PubMed

Hayyan, Adeeb; Mjalli, Farouq S; Hashim, Mohd Ali; Hayyan, Maan; AlNashef, Inas M; Al-Zahrani, Saeed M; Al-Saadi, Mohammed A

2011-10-01

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751). Copyright © 2011 Elsevier Ltd. All rights reserved.

Complex dynamics and enhanced photosensitivity in a modified Belousov-Zhabotinsky reaction

NASA Astrophysics Data System (ADS)

Li, Nan; Zhao, Jinpei; Wang, Jichang

2008-06-01

This study presents an experimental investigation of nonlinear dynamics in a modified Belousov-Zhabotinsky (BZ) reaction, in which the addition of 1,4-benzoquinone induced various complex behaviors such as mixed-mode oscillations and consecutive period-adding bifurcations. In addition, the presence of 1,4-benzoquinone significantly enhanced the photosensitivity of the ferroin-catalyzed BZ system, in which light-induced transitions between simple and complex oscillations have been achieved. Mechanistic study suggests that the influence of benzoquinone may arise from its interactions with the metal catalyst ferroin/ferriin, where cyclic voltammograms illustrate that the presence of benzoquinone causes an increase in the redox potential of ferroin/ferriin couple, which may consequently alternate the oxidation and reduction paths of the catalyst.

Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

DOEpatents

Ramprasad, D.; Waller, F.J.

1999-04-06

This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, D.; Waller, F.J.

1998-04-28

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Excited State Intramolecular Proton Transfer of 2,5-bis(5-ethyl-2-benzoxazolyl)-hydroquinone and its OH/OD-isotopomers studied in supersonic jets

NASA Astrophysics Data System (ADS)

Peukert, Sebastian; Gil, Michał; Kijak, Michał; Sepioł, Jerzy

2015-11-01

The Excited State Intramolecular Proton Transfer (ESIPT) reactions of dually fluorescent 2,5-bis(5-ethyl-2-benzoxazolyl)-hydroquinone (DE-BBHQ) and its isotopomers have been studied in the supersonic jet applying laser induced fluorescence (LIF) and fluorescence-depletion (F-D) spectroscopy. LIF-spectra measured at photo-tautomeric (red) fluorescence exhibit a characteristic triplet pattern of vibronic bands, which gradually collapses upon successive deuteration. Complementary TDDFT calculations indicate the possibility of 2 consecutive ESIPT reactions yielding an excited state diketo-tautomer. However, concerning this matter the present experimental results are not unambiguous and could be also rationalized without assuming the formation of an additional photo-tautomer.

Resveratrol products resulting by free radical attack

NASA Astrophysics Data System (ADS)

Bader, Yvonne; Quint, R. M.; Getoff, Nikola

2008-06-01

Trans-resveratrol ( trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1999-01-01

This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Malaria, a difficult diagnosis in a febrile patient with sub-microscopic parasitaemia and polyclonal lymphocyte activation outside the endemic region, in Brazil

PubMed Central

2013-01-01

A case of autochthonous Plasmodium vivax malaria with sub-microscopic parasitaemia and polyclonal B-cell activation (PBA) (as reflected by positive IgM and IgG serology for toxoplasmosis, cytomegalovirus, and antinuclear and rheumatoid factors) was diagnosed by polymerase chain reaction (PCR) after consecutive negative rapid diagnostic test results and blood films. The patient, a 44-year-old man from Rio de Janeiro state, Brazil, had visited the Atlantic Forest, a tourist, non-malaria-endemic area where no autochthonous cases of ’bromeliad malaria‘ has ever been described. The characteristic pattern of fever, associated with PBA, was the clue to malaria diagnosis, despite consecutive negative thick blood smears. The study highlights a need for changes in clinical and laboratory diagnostic approaches, namely the incorporation of PCR as part of the current routine malaria diagnostic methods in non-endemic areas. PMID:24200365

Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

NASA Astrophysics Data System (ADS)

Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

2016-04-01

Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.

Two-stage, acetic acid-aqueous ammonia, fractionation of empty fruit bunches for increased lignocellulosic biomass utilization.

PubMed

Kim, Dong Young; Kim, Young Soo; Kim, Tae Hyun; Oh, Kyeong Keun

2016-01-01

Fractionation of EFB was conducted in two consecutive steps using a batch reaction system: hemicellulose hydrolysis using acetic acid (AA; 3.0-7.0 wt.%) at 170-190°C for 10-20 min in the first stage, and lignin solubilization using ammonium hydroxide (5-20 wt.%) at 140-220°C for 5-25 min in the second stage. The two-stage process effectively fractionated empty fruit bunches (EFB) in terms of hemicellulose hydrolysis (53.6%) and lignin removal (59.5%). After the two-stage treatment, the fractionated solid contained 65.3% glucan. Among three investigated process parameters, reaction temperature and ammonia concentration had greater impact on the delignification reaction in the second stage than reaction time. The two-stage fractionation processing improved the enzymatic digestibility to 72.9% with 15 FPU of cellulase/g of glucan supplemented with 70 pNPG of β-glycosidase (Novozyme 188)/g-glucan, which was significantly enhanced from the equivalent digestibility of 28.3% for untreated EFB and 45.7% for AAH-fractionated solid. Copyright © 2015 Elsevier Ltd. All rights reserved.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

PubMed

Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

2017-02-01

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C 1∼4 and C A sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C 1∼4 positions are kinetically comparable with those occurring at nonfluorinated C 1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C 1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C 1 position has more adverse effects than substitution at other sites. The succedent O 2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (Δ r G ≠ ). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols. Copyright © 2016 Elsevier Ltd. All rights reserved.

Early stage oxynitridation process of Si(001) surface by NO gas: Reactive molecular dynamics simulation study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Haining; Kim, Seungchul; Lee, Kwang-Ryeol, E-mail: krlee@kist.re.kr

2016-03-28

Initial stage of oxynitridation process of Si substrate is of crucial importance in fabricating the ultrathin gate dielectric layer of high quality in advanced MOSFET devices. The oxynitridation reaction on a relaxed Si(001) surface is investigated via reactive molecular dynamics (MD) simulation. A total of 1120 events of a single nitric oxide (NO) molecule reaction at temperatures ranging from 300 to 1000 K are statistically analyzed. The observed reaction kinetics are consistent with the previous experimental or calculation results, which show the viability of the reactive MD technique to study the NO dissociation reaction on Si. We suggest the reaction pathwaymore » for NO dissociation that is characterized by the inter-dimer bridge of a NO molecule as the intermediate state prior to NO dissociation. Although the energy of the inter-dimer bridge is higher than that of the intra-dimer one, our suggestion is supported by the ab initio nudged elastic band calculations showing that the energy barrier for the inter-dimer bridge formation is much lower. The growth mechanism of an ultrathin Si oxynitride layer is also investigated via consecutive NO reactions simulation. The simulation reveals the mechanism of self-limiting reaction at low temperature and the time evolution of the depth profile of N and O atoms depending on the process temperature, which would guide to optimize the oxynitridation process condition.« less

Comparison of single and consecutive dual frequency induction surface hardening of gear wheels

NASA Astrophysics Data System (ADS)

Barglik, J.; Ducki, K.; Kukla, D.; Mizera, J.; Mrówka-Nowotnik, G.; Sieniawski, J.; Smalcerz, A.

2018-05-01

Mathematical modelling of single and consecutive dual - frequency induction surface hardening systems are presented and compared. The both models are solved by the 3D FEM-based professional software supported by a number of own numerical procedures. The methodology is illustrated with some examples of surface induction hardening of a gear wheel made of steel 41Cr4. The computations are in a good accordance with experiments provided on the laboratory stand.

Diagnostic patch testing following tuberculosis-associated cutaneous adverse drug reactions induces systemic reactions in HIV-infected persons.

PubMed

Lehloenya, R J; Todd, G; Wallace, J; Ngwanya, M R; Muloiwa, R; Dheda, K

2016-07-01

The incidence of cutaneous adverse drug reactions (CADRs) to first-line antituberculosis drugs (FLTDs) is higher in HIV-tuberculosis coinfection. However, the utility of patch testing to identify the offending drug in this patient subgroup has been poorly studied. To identify drugs causing adverse drug reactions in patients with HIV-tuberculosis coinfection. Fourteen consecutive patients underwent diagnostic work-up (patch testing followed by a skin prick test and an oral rechallenge) to pinpoint the offending drug after developing FLTD-associated CADR, which included drug rash with eosinophilia and systemic symptoms (n = 12), Stevens-Johnson syndrome (SJS, n = 1) and toxic epidermal necrolysis/SJS overlap (n = 1). A positive reaction to any of the three diagnostic modalities eliminated that drug from the regimen. Once patients were clinically stable postreaction, sequential and additive rechallenge with FLTDs was initiated. Eleven of the 14 participants with FLTD-associated CADR were HIV infected (median CD4 count 149 cells mm(-3) ). In this subgroup, patch testing resulted in generalized systemic reactions in 10 of 11 patients (91%). These included rash in 10 of 13 reactions (77%), eosinophilia in eight (62%), transaminitis in seven (54%) and fever in five (38%). Isoniazid caused six of 13 (46%) generalized systemic reactions, rifampicin four (31%), ethambutol two (15%) and pyrazinamide one reaction. Using the Common Terminology Criteria for Adverse Events, five of 13 reactions were mild, six were moderate and two were severe. There were no life-threatening or fatal reactions. In HIV-infected persons with tuberculosis-associated CADR, although patch-testing reactions to FLTD are common and tend to be associated with systemic features, they are not life threatening or fatal. These data inform clinical practice in HIV-endemic settings. © 2016 British Association of Dermatologists.

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaudhuri, T.K.; Fink, S.

The records of 18 consecutive patients referred to a Veterans Administration Hospital nuclear medicine service for renal scintigraphic tests to rule out renovascular hypertension were reviewed. The men were elderly (mean age, 62 years), and risk factors for untoward reactions, including long-standing hypertension, severe peripheral vascular disease, diabetes, chronic renal failure, and recent diuretic use were present. Despite these risks, there was no test morbidity, and the authors conclude that the renal scintigraphic test with captopril enhancement is well tolerated and deserves continued application and evaluation.

Positive patch test reactions to oxidized limonene: exposure and relevance.

PubMed

Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Gimenez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

2014-11-01

R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reaction to oxidized R-limonene. To study the exposure to limonene among consecutive dermatitis patients reacting to oxidized R-limonene in an international setting, and to assess the relevance of the exposure for the patients' dermatitis. Oxidized R-limonene 3.0% (containing limonene hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. Overall, exposure to products containing limonene was found and assessed as being probably relevant for the patients' dermatitis in 36% of the limonene-allergic patients. In Barcelona and Copenhagen, > 70% of the patients were judged to have had an exposure to limonene assessed as relevant. Oxidized R-limonene is a common fragrance allergen, and limonene was frequently found in the labelling on the patients' products, and assessed as relevant for the patients' dermatitis. A large number of domestic and occupational sources for contact with R-limonene were identified. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Factors influencing response to ingenol mebutate therapy for actinic keratosis of face and scalp

PubMed Central

Skroza, Nevena; Proietti, Ilaria; Bernardini, Nicoletta; Balduzzi, Veronica; Mambrin, Alessandra; Marchesiello, Anna; Tolino, Ersilia; Zuber, Sara; La Torre, Giuseppe; Potenza, Concetta

2017-01-01

AIM To determine factors independently influencing response to ingenol mebutate therapy and assess efficacy on clinical setting of non-hypertrophic non-hyperkeratotic actinic keratosis (AK). METHODS Consecutive patients affected by non-hypertrophic non-hyperkeratotic AKs of the face or scalp were enrolled to receive ingenol mebutate 0.015% gel on a selected skin area of 25 cm2 for 3 consecutive days. Local skin reactions were calculated at each follow up visit using a validated composite score. Efficacy was evaluated by the comparison of clinical and dermoscopic pictures before the treatment and at day 57, and classified as complete, partial and poor response. RESULTS A number of 130 patients were enrolled, of which 101 (77.7%) were treated on the face, while 29 (22.3%) on the scalp. The great majority of our study population (n = 119, 91.5%) reached at least a 75% clearance of AKs and, in particular, 58 patients (44.6%) achieved a complete response while 61 (46.9%) a partial one. Logistic backward multivariate analysis showed that facial localization, level of local skin reaction (LSR) at day 2, the highest LSR values and level of crusts at day 8 were factors independently associated with the achievement of a complete response. CONCLUSION Ingenol mebutate 0.015% gel, when properly applied, is more effective on the face than on the scalp and efficacy is directly associated to LSR score. PMID:29067277

Current patch test results in consecutive patients with, and chemical analysis of, disperse blue (DB) 106, DB 124, and the mix of DB 106 and 124.

PubMed

Uter, Wolfgang; Hildebrandt, Stephan; Geier, Johannes; Schnuch, Axel; Lessmann, Holger

2007-10-01

Disperse blue (DB) 106 and 124 are important textile dye allergens. However, the dye raw material is impure, leading to uncertainty regarding the actual patch test (PT) concentration. To examine, (i) the allergen content of previously and currently used DB 106 and 124 and a respective mix, and (ii) the frequency of positive PT reactions to the DB 106/124 mix and to the single compounds in consecutive PT patients. High performance liquid chromatography (HPLC) analysis and purification of DB 106 and 124, respectively. Descriptive analysis of PT data from the Information network of departments of dermatology obtained between January 2003 and December 2005. Retrospectively, 2 batches of the DB 106/124 mix proved to contain an amount of allergen different to the 1 declared (based on information of suppliers of raw material). However, since February 2005, DB 106 and 124, respectively, are available at a reliable concentration of 0.3% petrolatum. In 2005, the prevalence of positive PT reactions to both the mix (0.89%) and the single constituents combined (0.56%) did not qualify them for inclusion in the standard series. Quality control, providing accurate test concentrations of allergens based on technical grade purity raw materials is necessary for valid diagnosis of contact allergy and comparable epidemiological data.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Analytical model for BTEX natural attenuation in the presence of fuel ethanol and its anaerobic metabolite acetate.

PubMed

da Silva, Marcio L B; Gomez, Diego E; Alvarez, Pedro J J

2013-03-01

Flow-through column studies were conducted to mimic the natural attenuation of ethanol and BTEX mixtures, and to consider potential inhibitory effects of ethanol and its anaerobic metabolite acetate on BTEX biodegradation. Results were analyzed using a one-dimensional analytical model that was developed using consecutive reaction differential equations based on first-order kinetics. Decrease in pH due to acetogenesis was also modeled, using charge balance equations under CaCO(3) dissolution conditions. Delay in BTEX removal was observed and simulated in the presence of ethanol and acetate. Acetate was the major volatile fatty acid intermediate produced during anaerobic ethanol biodegradation (accounting for about 58% of the volatile fatty acid mass) as suggested by the model data fit. Acetate accumulation (up to 1.1 g/L) near the source zone contributed to a pH decrease by almost one unit. The anaerobic degradation of ethanol (2 g/L influent concentration) at the source zone produced methane at concentrations exceeding its solubility (~/=26mg/L). Overall, this simple analytical model adequately described ethanol degradation, acetate accumulation and methane production patterns, suggesting that it could be used as a screening tool to simulate lag times in BTEX biodegradation, changes in groundwater pH and methane generation following ethanol-blended fuel releases. Copyright © 2012 Elsevier B.V. All rights reserved.

Types and predictors of partner reactions to HIV status disclosure among HIV-infected adult Nigerians in a tertiary hospital in the Niger Delta.

PubMed

Ogoina, Dimie; Ikuabe, Peter; Ebuenyi, Ikenna; Harry, Tubonye; Inatimi, Otonyo; Chukwueke, Ogechi

2015-03-01

Our aim was to describe the types and determinants of partner reactions to HIV-status disclosure among adults attending an antiretroviral therapy-(ART) clinic in the Bayelsa State, Nigeria. A cross-sectional study was undertaken between January and March 2013 among consecutive adult patients who had disclosed their HIV-status to their current sexual partner. Sociodemograhic data and types of initial and subsequent partner reactions to disclosure were obtained using interviewer-administered standardized-questionnaire. Independent determinants of reactions to disclosure were ascertained by unconditional logistic regression. Out of 123 study participants, 57.7% were females, 92% were receiving ART and 86.1% were currently married. Majority of the participants reported predominant positive or supportive initial (72.4%) and subsequent (89.5%) partner reactions to disclosure, with significant increase in positive reactions over time. Positive initial partner reactions were independently associated with prior post-test counselling-(Odds ratio [OR]-6.5, 95% Confidence interval [CI]-1.3-31.6-p=0.02), age>35 years-(OR-5.8, 95% CI-1.6-20.9-p=0.008) and being healthy at time of disclosure-(OR-7.8, 95% CI-1.7-35.4-p=0.008). Subsequent positive partner reactions were significantly associated with receiving antiretroviral therapy and having only one lifetime sexual partner. Our results indicate that partner reactions to HIV-status disclosure are predominantly supportive. Disclosure counselling and early initiation of ART may be effective in improving HIV-status disclosure in Nigeria.

Chemical sensors from the cooperative actuation of multistep electrochemical molecular machines of polypyrrole: potentiostatic study. Trying to replicate muscle’s fatigue signals

NASA Astrophysics Data System (ADS)

Beaumont, Samuel; Otero, Toribio F.

2018-07-01

Polypyrrole film electrodes are constituted by multielectronic electrochemical molecular machines (every polymeric molecule) counterions and water, mimicking the intracellular matrix of muscular cells. The influence of the electrolyte concentration on the reversible oxidation/reduction of polypyrrole films was studied in NaCl aqueous solutions by consecutive square potential waves. The consumed redox charge and the consumed electrical energy change as a function of the concentration. That means that the extension (the consumed charge) of the reaction involving conformational, or allosteric, movements of the reacting polymeric chains (molecular machines) responds to (senses) the chemical energy of the reaction ambient. A theoretical description of the attained empirical results is presented getting the sensing equations and the concomitant sensitivities. Those results could indicate the origin and nature of the neural signals sent to the brain from biological haptic muscles working by cooperative actuation of the actin-myosin molecular machines driven by chemical reactions and sensing, simultaneously, the fatigue state of the muscle.

Nasal reaction to changes in whole body temperature.

PubMed

Lundqvist, G R; Pedersen, O F; Hilberg, O; Nielsen, B

1993-11-01

The changes in nasal patency following a 1.5 degrees C decrease or increase in whole body temperature were measured in 8 healthy young males, during and after 30 min of immersion in a 15 degrees C cold or a 40 degrees C warm bath, breathing air at the same temperature, in a cross-over experimental design. The nasal reactions were traced by consecutive measurements of changes in nasal cavity volumes by acoustic rhinometry. Swelling of the mucosa during cooling and an almost maximal shrinkage of the mucosa during heating were indicated by respectively a decrease and an increase in nasal cavity volumes. The reactions were determined predominantly by the whole body thermal balance, but were also influenced by the temperature of the inhaled air, either enhanced, reduced or temporarily reversed. The greatest change occurred in the nasal cavity, left or right, which differed most from the final state at the beginning of exposure due to the actual state of nasal cycle.

Early detection of tumor relapse/regrowth by consecutive minimal residual disease monitoring in high-risk neuroblastoma patients

PubMed Central

Hirase, Satoshi; Saitoh, Atsuro; Hartomo, Tri Budi; Kozaki, Aiko; Yanai, Tomoko; Hasegawa, Daiichiro; Kawasaki, Keiichiro; Kosaka, Yoshiyuki; Matsuo, Masafumi; Yamamoto, Nobuyuki; Mori, Takeshi; Hayakawa, Akira; Iijima, Kazumoto; Nishio, Hisahide; Nishimura, Noriyuki

2016-01-01

Neuroblastoma is an aggressive pediatric tumor accounting for ~15% of cancer-associated mortalities in children. Despite the current intensive therapy, >50% of high-risk patients experience tumor relapse or regrowth caused by the activation of minimal residual disease (MRD). Although several MRD detection protocols using various reverse transcription-quantitative polymerase chain reaction (RT-qPCR) markers have been reported to evaluate the therapeutic response and disease status of neuroblastoma patients, their clinical significance remains elusive. The present study reports two high-risk neuroblastoma patients, whose MRD was consecutively monitored using 11 RT-qPCR markers (CHRNA3, CRMP1, DBH, DCX, DDC, GABRB3, GAP43, ISL1, KIF1A, PHOX2B and TH) during their course of treatment. The two patients initially responded to the induction therapy and reached MRD-negative status. The patients' MRD subsequently became positive with no elevation of their urinary homovanillic acid, urinary vanillylmandelic acid and serum neuron-specific enolase levels at 13 or 19 weeks prior to the clinical diagnosis of tumor relapse or regrowth. The present cases highlight the possibility of consecutive MRD monitoring using 11 markers to enable an early detection of tumor relapse or regrowth in high-risk neuroblastoma patients. PMID:27446404

RIPL - Reference Input Parameter Library for Calculation of Nuclear Reactions and Nuclear Data Evaluations

NASA Astrophysics Data System (ADS)

Capote, R.; Herman, M.; Obložinský, P.; Young, P. G.; Goriely, S.; Belgya, T.; Ignatyuk, A. V.; Koning, A. J.; Hilaire, S.; Plujko, V. A.; Avrigeanu, M.; Bersillon, O.; Chadwick, M. B.; Fukahori, T.; Ge, Zhigang; Han, Yinlu; Kailas, S.; Kopecky, J.; Maslov, V. M.; Reffo, G.; Sin, M.; Soukhovitskii, E. Sh.; Talou, P.

2009-12-01

We describe the physics and data included in the Reference Input Parameter Library, which is devoted to input parameters needed in calculations of nuclear reactions and nuclear data evaluations. Advanced modelling codes require substantial numerical input, therefore the International Atomic Energy Agency (IAEA) has worked extensively since 1993 on a library of validated nuclear-model input parameters, referred to as the Reference Input Parameter Library (RIPL). A final RIPL coordinated research project (RIPL-3) was brought to a successful conclusion in December 2008, after 15 years of challenging work carried out through three consecutive IAEA projects. The RIPL-3 library was released in January 2009, and is available on the Web through http://www-nds.iaea.org/RIPL-3/. This work and the resulting database are extremely important to theoreticians involved in the development and use of nuclear reaction modelling (ALICE, EMPIRE, GNASH, UNF, TALYS) both for theoretical research and nuclear data evaluations. The numerical data and computer codes included in RIPL-3 are arranged in seven segments: MASSES contains ground-state properties of nuclei for about 9000 nuclei, including three theoretical predictions of masses and the evaluated experimental masses of Audi et al. (2003). DISCRETE LEVELS contains 117 datasets (one for each element) with all known level schemes, electromagnetic and γ-ray decay probabilities available from ENSDF in October 2007. NEUTRON RESONANCES contains average resonance parameters prepared on the basis of the evaluations performed by Ignatyuk and Mughabghab. OPTICAL MODEL contains 495 sets of phenomenological optical model parameters defined in a wide energy range. When there are insufficient experimental data, the evaluator has to resort to either global parameterizations or microscopic approaches. Radial density distributions to be used as input for microscopic calculations are stored in the MASSES segment. LEVEL DENSITIES contains phenomenological parameterizations based on the modified Fermi gas and superfluid models and microscopic calculations which are based on a realistic microscopic single-particle level scheme. Partial level densities formulae are also recommended. All tabulated total level densities are consistent with both the recommended average neutron resonance parameters and discrete levels. GAMMA contains parameters that quantify giant resonances, experimental gamma-ray strength functions and methods for calculating gamma emission in statistical model codes. The experimental GDR parameters are represented by Lorentzian fits to the photo-absorption cross sections for 102 nuclides ranging from 51V to 239Pu. FISSION includes global prescriptions for fission barriers and nuclear level densities at fission saddle points based on microscopic HFB calculations constrained by experimental fission cross sections.

RIPL - Reference Input Parameter Library for Calculation of Nuclear Reactions and Nuclear Data Evaluations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capote, R.; Herman, M.; Oblozinsky, P.

We describe the physics and data included in the Reference Input Parameter Library, which is devoted to input parameters needed in calculations of nuclear reactions and nuclear data evaluations. Advanced modelling codes require substantial numerical input, therefore the International Atomic Energy Agency (IAEA) has worked extensively since 1993 on a library of validated nuclear-model input parameters, referred to as the Reference Input Parameter Library (RIPL). A final RIPL coordinated research project (RIPL-3) was brought to a successful conclusion in December 2008, after 15 years of challenging work carried out through three consecutive IAEA projects. The RIPL-3 library was released inmore » January 2009, and is available on the Web through (http://www-nds.iaea.org/RIPL-3/). This work and the resulting database are extremely important to theoreticians involved in the development and use of nuclear reaction modelling (ALICE, EMPIRE, GNASH, UNF, TALYS) both for theoretical research and nuclear data evaluations. The numerical data and computer codes included in RIPL-3 are arranged in seven segments: MASSES contains ground-state properties of nuclei for about 9000 nuclei, including three theoretical predictions of masses and the evaluated experimental masses of Audi et al. (2003). DISCRETE LEVELS contains 117 datasets (one for each element) with all known level schemes, electromagnetic and {gamma}-ray decay probabilities available from ENSDF in October 2007. NEUTRON RESONANCES contains average resonance parameters prepared on the basis of the evaluations performed by Ignatyuk and Mughabghab. OPTICAL MODEL contains 495 sets of phenomenological optical model parameters defined in a wide energy range. When there are insufficient experimental data, the evaluator has to resort to either global parameterizations or microscopic approaches. Radial density distributions to be used as input for microscopic calculations are stored in the MASSES segment. LEVEL DENSITIES contains phenomenological parameterizations based on the modified Fermi gas and superfluid models and microscopic calculations which are based on a realistic microscopic single-particle level scheme. Partial level densities formulae are also recommended. All tabulated total level densities are consistent with both the recommended average neutron resonance parameters and discrete levels. GAMMA contains parameters that quantify giant resonances, experimental gamma-ray strength functions and methods for calculating gamma emission in statistical model codes. The experimental GDR parameters are represented by Lorentzian fits to the photo-absorption cross sections for 102 nuclides ranging from {sup 51}V to {sup 239}Pu. FISSION includes global prescriptions for fission barriers and nuclear level densities at fission saddle points based on microscopic HFB calculations constrained by experimental fission cross sections.« less

RIPL-Reference Input Parameter Library for Calculation of Nuclear Reactions and Nuclear Data Evaluations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capote, R.; Herman, M.; Capote,R.

We describe the physics and data included in the Reference Input Parameter Library, which is devoted to input parameters needed in calculations of nuclear reactions and nuclear data evaluations. Advanced modelling codes require substantial numerical input, therefore the International Atomic Energy Agency (IAEA) has worked extensively since 1993 on a library of validated nuclear-model input parameters, referred to as the Reference Input Parameter Library (RIPL). A final RIPL coordinated research project (RIPL-3) was brought to a successful conclusion in December 2008, after 15 years of challenging work carried out through three consecutive IAEA projects. The RIPL-3 library was released inmore » January 2009, and is available on the Web through http://www-nds.iaea.org/RIPL-3/. This work and the resulting database are extremely important to theoreticians involved in the development and use of nuclear reaction modelling (ALICE, EMPIRE, GNASH, UNF, TALYS) both for theoretical research and nuclear data evaluations. The numerical data and computer codes included in RIPL-3 are arranged in seven segments: MASSES contains ground-state properties of nuclei for about 9000 nuclei, including three theoretical predictions of masses and the evaluated experimental masses of Audi et al. (2003). DISCRETE LEVELS contains 117 datasets (one for each element) with all known level schemes, electromagnetic and {gamma}-ray decay probabilities available from ENSDF in October 2007. NEUTRON RESONANCES contains average resonance parameters prepared on the basis of the evaluations performed by Ignatyuk and Mughabghab. OPTICAL MODEL contains 495 sets of phenomenological optical model parameters defined in a wide energy range. When there are insufficient experimental data, the evaluator has to resort to either global parameterizations or microscopic approaches. Radial density distributions to be used as input for microscopic calculations are stored in the MASSES segment. LEVEL DENSITIES contains phenomenological parameterizations based on the modified Fermi gas and superfluid models and microscopic calculations which are based on a realistic microscopic single-particle level scheme. Partial level densities formulae are also recommended. All tabulated total level densities are consistent with both the recommended average neutron resonance parameters and discrete levels. GAMMA contains parameters that quantify giant resonances, experimental gamma-ray strength functions and methods for calculating gamma emission in statistical model codes. The experimental GDR parameters are represented by Lorentzian fits to the photo-absorption cross sections for 102 nuclides ranging from {sup 51}V to {sup 239}Pu. FISSION includes global prescriptions for fission barriers and nuclear level densities at fission saddle points based on microscopic HFB calculations constrained by experimental fission cross sections.« less

Essential Oils, Part IV: Contact Allergy.

PubMed

de Groot, Anton C; Schmidt, Erich

2016-01-01

Nearly 80 essential oils (including 2 jasmine absolutes) have caused contact allergy. Fifty-five of these have been tested in consecutive patients suspected of contact dermatitis, and nine (laurel, turpentine, orange, tea tree, citronella, ylang-ylang, sandalwood, clove, and costus root) showed greater than 2% positive patch test reactions. Relevance data are generally missing or inadequate. Most reactions are caused by application of pure oils or high-concentration products. The clinical picture depends on the responsible product. Occupational contact dermatitis may occur in professionals performing massages. The (possible) allergens in essential oils are discussed. Several test allergens are available, but patients should preferably be tested with their own products. Co-reactivity with other essential oils and the fragrance mix is frequent, which may partly be explained by common ingredients. Patch test concentrations for essential oils are suggested.

N-Tosylhydrazone directed annulation via C-H/N-N bond activation in Ru(ii)/PEG-400 as homogeneous recyclable catalytic system: a green synthesis of isoquinolines.

PubMed

Deshmukh, Dewal S; Bhanage, Bhalchandra M

2018-06-21

A green and sustainable methodology for the synthesis of isoquinolines using Ru(ii)/PEG-400 as a homogeneous recyclable catalytic system has been demonstrated. N-Tosylhydrazone, a rarely explored directing group, has been successfully employed for an annulation type of reaction with alkynes via C-H/N-N activation. A short reaction time with a simple extraction procedure, a wide substrate scope with high yields of products, easily prepared substrates, biodegradable solvent, and scalability up to the gram level enhance the efficiency and sustainability of the proposed protocol. Further, the expensive ruthenium-based homogeneous catalytic system could be reused up to a fourth consecutive cycle without any loss in its activity.

Multiple Consecutive Infections Might Explain the Lack of Protection by BCG

PubMed Central

Cardona, Pere-Joan; Vilaplana, Cristina

2014-01-01

Although contacts between tuberculosis patients may result in multiple consecutive infections (MCI), no experimental animal models consider this fact when used in basic studies. Moreover, the current TB vaccine (BCG) has demonstrated a limited protection in humans. In this study we evaluate the effect of tuberculosis MCI by way of a simple mathematical analysis using data from the low dose aerosol murine experimental model. The results show that a higher number of, or shorter intervals between, multiple consecutive infections reduce the protective effect of BCG. This is due to both the increase in bacillary load at the stationary level of the infection, and the protective immune response induced by the infection itself. This factor must therefore be taken into account when designing new prophylactic strategies as candidate vaccines for the replacement of BCG. PMID:24740286

Multiple consecutive infections might explain the lack of protection by BCG.

PubMed

Cardona, Pere-Joan; Vilaplana, Cristina

2014-01-01

Although contacts between tuberculosis patients may result in multiple consecutive infections (MCI), no experimental animal models consider this fact when used in basic studies. Moreover, the current TB vaccine (BCG) has demonstrated a limited protection in humans. In this study we evaluate the effect of tuberculosis MCI by way of a simple mathematical analysis using data from the low dose aerosol murine experimental model. The results show that a higher number of, or shorter intervals between, multiple consecutive infections reduce the protective effect of BCG. This is due to both the increase in bacillary load at the stationary level of the infection, and the protective immune response induced by the infection itself. This factor must therefore be taken into account when designing new prophylactic strategies as candidate vaccines for the replacement of BCG.

Double-helix micro-channels on microfluidic chips for enhanced continuous on-chip derivatization followed by electrophoretic separation.

PubMed

Peng, Xianglu; Zhao, Lei; Guo, Jinxiu; Yang, Shenghong; Ding, Hui; Wang, Xiayan; Pu, Qiaosheng

2015-10-15

Micro-channels that contain a special inner structure are critical for efficient mixing and chemical reactions. In this paper, we described the facile fabrication of an integrated microchip with double-helix type micro-channels to improve mixing efficiency and to facilitate multi-step derivatization reactions prior to electrophoretic separation. With a prepared microchip, reagents, samples and reaction products could be driven through micro-channels by siphon, and no other pumping device was necessary. To test its performance, reductive amination of aldehydes with 8-aminonaphthalene-1,3,6-trisulfonate acid disodium (ANTS) was attempted via microchip electrophoresis with laser induced fluorescence (LIF). The effect of the geometry of the reaction micro-channel on the reaction's efficiency was evaluated. Under the selected conditions, successful derivatization of five aldehydes was realized for highly reproducible analysis. The relative standard deviations of the peak areas for 30 consecutive injections were in the range of 0.28-1.61%. The method was applied for the determination of aldehydes in real samples with standard addition recoveries of 87.8-102.8%. Good tolerance of organic solvents was achieved, and the proposed method can potentially be employed for rapid screening of excessively added aldehyde food flavoring. Copyright © 2015 Elsevier B.V. All rights reserved.

Rate-dependent carbon and nitrogen kinetic isotope fractionation in hydrolysis of isoproturon.

PubMed

Penning, Holger; Cramer, Christopher J; Elsner, Martin

2008-11-01

Stable isotope fractionation permits quantifying contaminant degradation in the field when the transformation reaction is associated with a consistent isotope enrichment factor epsilon. When interpreted in conjunction with dual isotope plots, isotope fractionation is also particularly useful for elucidating reaction mechanisms. To assess the consistency of epsilon and dual isotope slopes in a two-step reaction, we investigated the abiotic hydrolysis of the herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) using a fragmentation method that allows measuring isotope ratios in different parts of the molecule. Carbon and nitrogen position-specific isotope fractionation, as well as slopes in dual isotope plots, varied linearly with rate constants k(obs) depending on the presence of buffers that mediate the initial zwitterion formation. The correlation can be explained by two consecutive reaction steps (zwitterion formation followed by dimethylamine elimination) each of which has a different kinetic isotope effect and may be rate-limiting. Intrinsic isotope effects for both steps, extracted from our kinetic data using a novel theoretical treatment, agree well with values computed from density functional calculations. Our study therefore demonstrates that more variable isotope fractionation may be observed in simple chemical reactions than commonly thought, but that consistent epsilon or dual isotope slopes may nonetheless be encountered in certain molecular fragments.

Comparison of histopathology and real-time polymerase chain reaction (RT-PCR) for detection of Mycobacterium tuberculosis in fistula-in-ano.

PubMed

Garg, Pankaj

2017-07-01

Histopathology is commonly used to diagnose tuberculosis in fistula-in-ano. The aim was to compare the sensitivity of polymerase chain reaction and histopathology in detecting tuberculosis in fistula-in-ano. The histopathology and polymerase chain-reaction of tissue (fistula tract) was done in all the consecutive operated cases. When pus sample was also available, polymerase chain reaction-pus was also done RESULTS: Three hundred forty seven samples (179 patients) were tested over 2 years (median 6.5 months). The mean age was 38.8 ± 10.7 years, and male/female was 170/9. Histopathology and polymerase chain reaction of tissue (fistula tract) was done in 152 and 165 patients, respectively. Polymerase chain reaction (pus) could be done in 30 patients. Overall, tuberculosis was detected in 20/179 (11.2%) patients. Of these, tuberculosis was detected by histopathology (tissue) in 1/152 (0.7%) and by polymerase chain reaction (tissue) in 14/165 (8.5%) patients. In pus, polymerase chain reaction detected tuberculosis in 6/30 (20%) patients. Both polymerase chain reaction of tissue and pus were positive in one patient. Polymerase chain reaction (tissue) and polymerase chain reaction (pus) were significantly more sensitive than histopathology (tissue) for detecting tuberculosis [histopathology 1/152 vs. polymerase chain reaction (tissue) 14/165, p = 0.0009] [histopathology 1/152 vs. polymerase chain reaction (pus) 6/30, p < 0.0001]. In 20 patients detected to have tuberculosis, four drug anti-tubercular therapy was recommended for 6 months. The therapy was completed in 13 patients and 12/13 (92.3%) were cured. The therapy is continuing in 3/20 patients. Four patients did not take the therapy. None of them was cured. Polymerase chain reaction was significantly more sensitive than histopathology in detecting tuberculosis in fistula-in-ano. Histopathology might be missing out tuberculosis in many patients leading to recurrence of the fistula.

Determination of nitrite and nitrate in water samples by an automated hydrodynamic sequential injection method.

PubMed

Somnam, Sarawut; Jakmunee, Jaroon; Grudpan, Kate; Lenghor, Narong; Motomizu, Shoji

2008-12-01

An automated hydrodynamic sequential injection (HSI) system with spectrophotometric detection was developed. Thanks to the hydrodynamic injection principle, simple devices can be used for introducing reproducible microliter volumes of both sample and reagent into the flow channel to form stacked zones in a similar fashion to those in a sequential injection system. The zones were then pushed to the detector and a peak profile was recorded. The determination of nitrite and nitrate in water samples by employing the Griess reaction was chosen as a model. Calibration graphs with linearity in the range of 0.7 - 40 muM were obtained for both nitrite and nitrate. Detection limits were found to be 0.3 muM NO(2)(-) and 0.4 muM NO(3)(-), respectively, with a sample throughput of 20 h(-1) for consecutive determination of both the species. The developed system was successfully applied to the analysis of water samples, employing simple and cost-effective instrumentation and offering higher degrees of automation and low chemical consumption.

Semi-automatic brain tumor segmentation by constrained MRFs using structural trajectories.

PubMed

Zhao, Liang; Wu, Wei; Corso, Jason J

2013-01-01

Quantifying volume and growth of a brain tumor is a primary prognostic measure and hence has received much attention in the medical imaging community. Most methods have sought a fully automatic segmentation, but the variability in shape and appearance of brain tumor has limited their success and further adoption in the clinic. In reaction, we present a semi-automatic brain tumor segmentation framework for multi-channel magnetic resonance (MR) images. This framework does not require prior model construction and only requires manual labels on one automatically selected slice. All other slices are labeled by an iterative multi-label Markov random field optimization with hard constraints. Structural trajectories-the medical image analog to optical flow and 3D image over-segmentation are used to capture pixel correspondences between consecutive slices for pixel labeling. We show robustness and effectiveness through an evaluation on the 2012 MICCAI BRATS Challenge Dataset; our results indicate superior performance to baselines and demonstrate the utility of the constrained MRF formulation.

Risk of cutaneous adverse events with febuxostat treatment in patients with skin reaction to allopurinol. A retrospective, hospital-based study of 101 patients with consecutive allopurinol and febuxostat treatment.

PubMed

Bardin, Thomas; Chalès, Gérard; Pascart, Tristan; Flipo, René-Marc; Korng Ea, Hang; Roujeau, Jean-Claude; Delayen, Aurélie; Clerson, Pierre

2016-05-01

To investigate the cutaneous tolerance of febuxostat in gouty patients with skin intolerance to allopurinol. We identified all gouty patients who had sequentially received allopurinol and febuxostat in the rheumatology departments of 4 university hospitals in France and collected data from hospital files using a predefined protocol. Patients who had not visited the prescribing physician during at least 2 months after febuxostat prescription were excluded. The odds ratio (OR) for skin reaction to febuxostat in patients with a cutaneous reaction to allopurinol versus no reaction was calculated. For estimating the 95% confidence interval (95% CI), we used the usual Wald method and a bootstrap method. In total, 113 gouty patients had sequentially received allopurinol and febuxostat; 12 did not visit the prescribing physician after febuxostat prescription and were excluded. Among 101 patients (86 males, mean age 61±13.9 years), 2/22 (9.1%) with a history of cutaneous reactions to allopurinol showed skin reactions to febuxostat. Two of 79 patients (2.5%) without a skin reaction to allopurinol showed skin intolerance to febuxostat. The ORs were not statistically significant with the usual Wald method (3.85 [95% CI 0.51-29.04]) or bootstrap method (3.86 [95% CI 0.80-18.74]). The risk of skin reaction with febuxostat seems moderately increased in patients with a history of cutaneous adverse events with allopurinol. This moderate increase does not support the cross-reactivity of the two drugs. Copyright © 2015. Published by Elsevier SAS.

Cross-reactions between xanthates and rubber additives.

PubMed

Sasseville, Denis; Al-Sowaidi, Mowza; Moreau, Linda

2007-09-01

We previously described allergic contact dermatitis from xanthates used in the recovery of metals from mining ores. We observed cross-reactions with carbamates, believed to be due to the common "dithio" nucleus shared by both groups. The present study was undertaken to establish the rate of cross-reactions between xanthates and rubber additives. Between November 2002 and December 2005, 1,220 consecutive patients were patch-tested with sodium isopropyl xanthate 10% in petrolatum (pet) and with potassium amyl xanthate 10% pet and later 5% pet, in addition to the North American Contact Dermatitis Group standard series and other series as required by their conditions. Fifty-one patients reacted to xanthates, carbamates, or thiurams; 26 reacted to xanthates only, and these reactions were felt to be irritant. Twenty-five patients reacted to xanthates and/or to one or more of the rubber additives, 12 had positive reactions to xanthates and to either carba mix or thiuram mix, 10 reacted to xanthates and carba mix, 9 reacted to xanthates and thiuram mix, and 8 showed positive reactions to xanthates and both mixes. However, 13 patients had positive reactions to carba mix and thiuram mix but did not react to xanthates. Six patients reacted to other rubber additives such as mercaptobenzothiazole, black rubber mix, and mixed dialkyl thioureas. Five of these patients also reacted to xanthates, 4 reacted to xanthates and carba mix, and 3 reacted to xanthates, carba mix, and thiuram mix. Of patients sensitized to carbamates, thiurams, or mercaptobenzothiazole, 50% exhibit cross-reactions with xanthates. Xanthates are irritants, and their patch-test concentrations should be lowered to 5% or less.

Prevention of murine cerebral malaria by low-dose cyclosporin A.

PubMed Central

Grau, G E; Gretener, D; Lambert, P H

1987-01-01

The effects of cyclosporin A (CsA) were investigated in an experimental model of cerebral malaria. In this model, Plasmodium berghei ANKA-infected CBA/Ca mice develop a clinically and histologically characterized neurological syndrome which is considered to be the result of immunopathological reactions mediated by L3T4+ T cells. It was shown that CsA displayed a strong protective effect on neurological complications when given at a dose 1 mg/kg/day for 5 consecutive days (Days 4-8), which had no effect on the parasite. Paradoxically, this protection against neurological complications was not seen when parasiticidal doses were used during this limited 5-day period. A similar protective effect was observed with two CsA derivatives, C5-34 and H7-94. The mechanisms by which CsA and the two derivatives could prevent murine cerebral malaria are unknown but can be related to exquisite effects on some lymphocyte functions. In view of these results, it might be conceivable to investigate the benefits of using low doses of CsA in man, in conjunction with the classical antiparasite therapy, for the management of cerebral malaria. PMID:3327806

Prevention of murine cerebral malaria by low-dose cyclosporin A.

PubMed

Grau, G E; Gretener, D; Lambert, P H

1987-08-01

The effects of cyclosporin A (CsA) were investigated in an experimental model of cerebral malaria. In this model, Plasmodium berghei ANKA-infected CBA/Ca mice develop a clinically and histologically characterized neurological syndrome which is considered to be the result of immunopathological reactions mediated by L3T4+ T cells. It was shown that CsA displayed a strong protective effect on neurological complications when given at a dose 1 mg/kg/day for 5 consecutive days (Days 4-8), which had no effect on the parasite. Paradoxically, this protection against neurological complications was not seen when parasiticidal doses were used during this limited 5-day period. A similar protective effect was observed with two CsA derivatives, C5-34 and H7-94. The mechanisms by which CsA and the two derivatives could prevent murine cerebral malaria are unknown but can be related to exquisite effects on some lymphocyte functions. In view of these results, it might be conceivable to investigate the benefits of using low doses of CsA in man, in conjunction with the classical antiparasite therapy, for the management of cerebral malaria.

Surface invasive cleavage assay on a maskless light-directed diamond DNA microarray for genome-wide human SNP mapping.

PubMed

Nie, Bei; Yang, Min; Fu, Weiling; Liang, Zhiqing

2015-07-07

The surface invasive cleavage assay, because of its innate accuracy and ability for self-signal amplification, provides a potential route for the mapping of hundreds of thousands of human SNP sites. However, its performance on a high density DNA array has not yet been established, due to the unusual "hairpin" probe design on the microarray and the lack of chemical stability of commercially available substrates. Here we present an applicable method to implement a nanocrystalline diamond thin film as an alternative substrate for fabricating an addressable DNA array using maskless light-directed photochemistry, producing the most chemically stable and biocompatible system for genetic analysis and enzymatic reactions. The surface invasive cleavage reaction, followed by degenerated primer ligation and post-rolling circle amplification is consecutively performed on the addressable diamond DNA array, accurately mapping SNP sites from PCR-amplified human genomic target DNA. Furthermore, a specially-designed DNA array containing dual probes in the same pixel is fabricated by following a reverse light-directed DNA synthesis protocol. This essentially enables us to decipher thousands of SNP alleles in a single-pot reaction by the simple addition of enzyme, target and reaction buffers.

Comparison of psychomotor function between music students and students participating in music training.

PubMed

Chansirinukor, Wunpen; Khemthong, Supalak

2014-07-01

To compare psychomotor function between a music student group who had music education and a non-music student group who participated in music training. Consecutive sampling was used for completing questionnaires, testing reaction times (visual, auditory, and tactile system), measuring electromyography of upper trapezius muscles both sides and taking photos of the Craniovertebral (CV) angle in the sitting position. Data collection was made twice for each student group: the music students at one-hour intervals for resting and conducting nonmusic activities, the non-music students at two-day intervals, 20 minutes/session, and performed music training (by a manual of keyboard notation). The non-music students (n = 65) improved reaction times, but responded slower than the music students except for the tactile system. The music students (n = 28) showed faster reaction times and higher activities of the trapezius muscle than the non-music students at post-test. In addition, the CV angle of the non-music students was significantly improved. The level of musical ability may influence the psychomotor function. Significant improvement was observed in visual, auditory and tactile reaction time, and CV angle in the non-music students. However upper trapezius muscle activities between both student groups were unchanged.

Three H₂O₂ molecules are involved in the "Fenton-like" reaction between Co(H₂O)₆²⁺ and H₂O₂.

PubMed

Burg, Ariela; Shusterman, Inna; Kornweitz, Haya; Meyerstein, Dan

2014-06-28

Co(II) complexes and Co(H2O)6(2+) are used as catalysts in advanced oxidation processes. Therefore it was decided to study the kinetics of reaction of Co(H2O)6(2+) with H2O2. Surprisingly, the kinetic results point out that the process involves three consecutive reactions, each of them requiring an H2O2 molecule, i.e. three H2O2 molecules ligate to the central cobalt cation prior to the formation of radicals. DFT analysis suggests that the transient (H2O)3Co(II)(OOH)2(H2O2) decomposes via: (H2O)3Co(II)(OOH)2(H2O2) → (H2O)3Co(II)(OOH)(˙OOH)(OH) + ˙OH ΔG(0) = -5.975 kcal mol(-1), with no evidence for the formation of a Co(III) transient. It is proposed that analogous mechanisms are involved whenever the redox potential of the central cation is too high to enable the reaction: M(H2O)6(n+) + H2O2 → M((n+1)+)aq + ˙OH + OH(-).

Recommendation to test limonene hydroperoxides 0·3% and linalool hydroperoxides 1·0% in the British baseline patch test series.

PubMed

Wlodek, C; Penfold, C M; Bourke, J F; Chowdhury, M M U; Cooper, S M; Ghaffar, S; Green, C; Holden, C R; Johnston, G A; Mughal, A A; Reckling, C; Sabroe, R A; Stone, N M; Thompson, D; Wilkinson, S M; Buckley, D A

2017-12-01

There is a significant rate of sensitization worldwide to the oxidized fragrance terpenes limonene and linalool. Patch testing to oxidized terpenes is not routinely carried out; the ideal patch test concentration is unknown. To determine the best test concentrations for limonene and linalool hydroperoxides, added to the British baseline patch test series, to optimize detection of true allergy and to minimize irritant reactions. During 2013-2014, 4563 consecutive patients in 12 U.K. centres were tested to hydroperoxides of limonene in petrolatum (pet.) 0·3%, 0·2% and 0·1%, and hydroperoxides of linalool 1·0%, 0·5% and 0·25% pet. Irritant reactions were recorded separately from doubtful reactions. Concomitant reactions to other fragrance markers and clinical relevance were documented. Limonene hydroperoxide 0·3% gave positive reactions in 241 (5·3%) patients, irritant reactions in 93 (2·0%) and doubtful reactions in 110 (2·4%). Linalool hydroperoxide 1·0% gave positive reactions in 352 (7·7%), irritant reactions in 178 (3·9%) and doubtful reactions in 132 (2·9%). A total of 119 patients with crescendo reactions to 0·3% limonene would have been missed if only tested with 0·1% and 131 patients with crescendo reactions to 1·0% linalool would have been missed if only tested with 0·25%. In almost two-thirds of patients with positive patch tests to limonene and linalool the reaction was clinically relevant. The majority of patients did not react to any fragrance marker in the baseline series. We recommend that limonene hydroperoxides be tested at 0·3% and linalool hydroperoxides at 1·0% in the British baseline patch test series. © 2017 British Association of Dermatologists.

Effect of variability of sequence length of go trials preceding a stop trial on ability of response inhibition in stop-signal task.

PubMed

Hiraoka, Koichi; Kinoshita, Atsushi; Kunimura, Hiroshi; Matsuoka, Masakazu

2018-05-31

This study investigated whether the variability of the sequence length of the go trials preceding a stop trial enhanced or interfered with inhibitory control. The hypotheses tested were either inhibitory control improves when the sequence length of the go trials varies as a consequence of increased preparatory effort or it degrades as a consequence of the switching cost from the go trial to the stop trial. The right-handed participants abducted the left or right index finger in response to a go cue during the go trials. A stop cue was given at 50, 90, or 130 ms after the go cue, with 0.25 probability in the stop trial. In the less variable session, a stop trial was presented after two, three, or four consecutive go trials. In the variable session, a stop trial was presented after one, two, three, four, or five consecutive go trials. The reaction time and stop-signal reaction time were not significantly different between the sessions and between the response sides. Nevertheless, the probability of successful inhibition of the right-hand response in the variable session was higher than that in the less variable session when the stop cue was given 50 ms after a go cue. This finding supports the view that preparatory effort due to less predictability of the chance of a forthcoming response inhibition enhances the ability of the right-hand response inhibition when the stop process begins earlier.

Hot atoms in cosmic chemistry.

PubMed

Rossler, K; Jung, H J; Nebeling, B

1984-01-01

High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. "Hot" atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10(8)-10(10) atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime. Experimental results are given for the systems: C/H2O (gas), C/H2O (solid, 77 K), N/CH4 (solid, 77K) and C/NH3 (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: N(p,alpha) 11C, 16O(p,alpha pn) 11C and 12C(d,n) 13N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO2, CH4, CH2O, CH3OH, HCOOH, NH3, CH3NH2, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed.

Evaluating candidate reactions to selection practices using organisational justice theory.

PubMed

Patterson, Fiona; Zibarras, Lara; Carr, Victoria; Irish, Bill; Gregory, Simon

2011-03-01

This study aimed to examine candidate reactions to selection practices in postgraduate medical training using organisational justice theory. We carried out three independent cross-sectional studies using samples from three consecutive annual recruitment rounds. Data were gathered from candidates applying for entry into UK general practice (GP) training during 2007, 2008 and 2009. Participants completed an evaluation questionnaire immediately after the short-listing stage and after the selection centre (interview) stage. Participants were doctors applying for GP training in the UK. Main outcome measures were participants' evaluations of the selection methods and perceptions of the overall fairness of each selection stage (short-listing and selection centre). A total of 23,855 evaluation questionnaires were completed (6893 in 2007, 10,497 in 2008 and 6465 in 2009). Absolute levels of perceptions of fairness of all the selection methods at both the short-listing and selection centre stages were consistently high over the 3years. Similarly, all selection methods were considered to be job-related by candidates. However, in general, candidates considered the selection centre stage to be significantly fairer than the short-listing stage. Of all the selection methods, the simulated patient consultation completed at the selection centre stage was rated as the most job-relevant. This is the first study to use a model of organisational justice theory to evaluate candidate reactions during selection into postgraduate specialty training. The high-fidelity selection methods are consistently viewed as more job-relevant and fairer by candidates. This has important implications for the design of recruitment systems for all specialties and, potentially, for medical school admissions. Using this approach, recruiters can systematically compare perceptions of the fairness and job relevance of various selection methods. © Blackwell Publishing Ltd 2011.

Acute versus chronic partial sleep deprivation in middle-aged people: differential effect on performance and sleepiness.

PubMed

Philip, Pierre; Sagaspe, Patricia; Prague, Mélanie; Tassi, Patricia; Capelli, Aurore; Bioulac, Bernard; Commenges, Daniel; Taillard, Jacques

2012-07-01

To evaluate the effects of acute sleep deprivation and chronic sleep restriction on vigilance, performance, and self-perception of sleepiness. Habitual night followed by 1 night of total sleep loss (acute sleep deprivation) or 5 consecutive nights of 4 hr of sleep (chronic sleep restriction) and recovery night. Eighteen healthy middle-aged male participants (age [(± standard deviation] = 49.7 ± 2.6 yr, range 46-55 yr). Multiple sleep latency test trials, Karolinska Sleepiness Scale scores, simple reaction time test (lapses and 10% fastest reaction times), and nocturnal polysomnography data were recorded. Objective and subjective sleepiness increased immediately in response to sleep restriction. Sleep latencies after the second and third nights of sleep restriction reached levels equivalent to those observed after acute sleep deprivation, whereas Karolinska Sleepiness Scale scores did not reach these levels. Lapse occurrence increased after the second day of sleep restriction and reached levels equivalent to those observed after acute sleep deprivation. A statistical model revealed that sleepiness and lapses did not progressively worsen across days of sleep restriction. Ten percent fastest reaction times (i.e., optimal alertness) were not affected by acute or chronic sleep deprivation. Recovery to baseline levels of alertness and performance occurred after 8-hr recovery night. In middle-aged study participants, sleep restriction induced a high increase in sleep propensity but adaptation to chronic sleep restriction occurred beyond day 3 of restriction. This sleepiness attenuation was underestimated by the participants. One recovery night restores daytime sleepiness and cognitive performance deficits induced by acute or chronic sleep deprivation. Philip P; Sagaspe P; Prague M; Tassi P; Capelli A; Bioulac B; Commenges D; Taillard J. Acute versus chronic partial sleep deprivation in middle-aged people: differential effect on performance and sleepiness. SLEEP 2012;35(7):997-1002.

The effects of intra-particle concentration gradient on consecutive adsorption-desorption of oryzanol from rice bran oil in packed-column

NASA Astrophysics Data System (ADS)

Susanti, Ari Diana; Sediawan, Wahyudi Budi; Wirawan, Sang Kompiang; Budhijanto

2017-05-01

Utilization of valuable trace components in agriculture by product such as rice bran oil is interesting to be explored. Among the valuables, oryzanol, a healthy nutrition for cardiovascular prevention, is the most promising one. Literature studies suggest that adsorption-desorption is a prospective method for oryzanol isolation. Design of commercial scale adsorption-desorption system for oryzanol needs a quantitative description of the phenomena involved. In this study, quantitative modeling of the consecutive adsorption-desorption in packed column has been proposed and verified through experimental data. The offered model takes into account the intra-particle concentration gradient in the adsorbent particle. In this model, the rate of mass transfer from the bulk of the liquid to the surface of the adsorbent particle or vice versa is expressed by film theory. The mass transfer of oryzanol from the liquid in the pore of the particle to the adjacent pore surface is assumed to be instantaneous, so solid-liquid equilibrium on the surface of the pores is always attained. For simplicity, the adsorption equilibrium model applied was coefficient distribution approach. The values of the parameters implicated in the model were obtained by curve fitting to the experimental data. It verified that the model proposed works well to quantitatively describe the consecutive adsorption-desorption of oryzanol from rice bran oil in packed column.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Independence of reaction time and response force control during isometric leg extension.

PubMed

Fukushi, Tamami; Ohtsuki, Tatsuyuki

2004-04-01

In this study, we examined the relative control of reaction time and force in responses of the lower limb. Fourteen female participants (age 21.2 +/- 1.0 years, height 1.62 +/- 0.05 m, body mass 54.1 +/- 6.1 kg; mean +/- s) were instructed to exert their maximal isometric one-leg extension force as quickly as possible in response to an auditory stimulus presented after one of 13 foreperiod durations, ranging from 0.5 to 10.0 s. In the 'irregular condition' each foreperiod was presented in random order, while in the 'regular condition' each foreperiod was repeated consecutively. A significant interactive effect of foreperiod duration and regularity on reaction time was observed (P < 0.001 in two-way ANOVA with repeated measures). In the irregular condition the shorter foreperiod induced a longer reaction time, while in the regular condition the shorter foreperiod induced a shorter reaction time. Peak amplitude of isometric force was affected only by the regularity of foreperiod and there was a significant variation of changes in peak force across participants; nine participants were shown to significantly increase peak force for the regular condition (P < 0.001), three to decrease it (P < 0.05) and two showed no difference. These results indicate the independence of reaction time and response force control in the lower limb motor system. Variation of changes in peak force across participants may be due to the different attention to the bipolar nature of the task requirements such as maximal force and maximal speed.

Vasovagal Rates in Flouroscopically Guided Interventional Procedures: A Study of Over 8,000 Injections

PubMed Central

Kennedy, David J.; Schneider, Byron; Casey, Ellen; Rittenberg, Joshua; Conrad, Bryan; Smuck, Matthew; Plastaras, Christopher T.

2014-01-01

Objective To determine the rate of vasovagal (vv) complications in fluoroscopically guided interventional procedures. Design Retrospective case series analysis of prospectively collected data from March 8, 2004 to January 30, 2009. Setting A single academic medical center. Subjects Four thousand one hundred eighty-three subjects undergoing 8,010 consecutive injections. Outcome Measures Pearson's chi-square test was used to determine the relationship between categorical variables. Results A total of 8,010 injections, including epidural steroid injections, radiofrequency nerve ablations, medial branch blocks, hip injections, knee injections, and glenohumeral injections were performed. Overall vv reaction rate was 2.6%, with 0.8% of procedures resulting in early terminated due to vv reaction. Peripheral joint injections had a vv rate of 0.2%, all occurring in hip injections. Transforaminal epidural steroid injections had a vv rate of 3.5%. Diagnostic blocks of the medial branches had the highest rate of vv (5.1%). Other predictors of vv reactions were identified including preprocedure pain score visual analog scale <5 (P = 0.004), male gender (P < 0.001), and age less than 65 years old (P < 0.001). Conclusions vv reactions have an overall low occurrence rate (2.6%) in interventional procedures ranging from 0% in peripheral knee and shoulder injections to 5.1% in medial branch blocks. Conservative treatment of vv reaction and willingness to terminate procedures resulted in no serious adverse events related to vv reaction in 8,010 procedures. PMID:24118835

Recombinant methioninase effectively targets a Ewing's sarcoma in a patient-derived orthotopic xenograft (PDOX) nude-mouse model

PubMed Central

Murakami, Takashi; Li, Shukuan; Han, Qinghong; Tan, Yuying; Kiyuna, Tasuku; Igarashi, Kentaro; Kawaguchi, Kei; Hwang, Ho Kyoung; Miyake, Kentaro; Singh, Arun S.; Nelson, Scott D.; Dry, Sarah M.; Li, Yunfeng; Hiroshima, Yukihiko; Lwin, Thinzar M.; DeLong, Jonathan C.; Chishima, Takashi; Tanaka, Kuniya; Bouvet, Michael; Endo, Itaru; Eilber, Fritz C.; Hoffman, Robert M.

2017-01-01

Methionine dependence is due to the overuse of methionine for aberrant transmethylation reactions in cancer. Methionine dependence may be the only general metabolic defect in cancer. In order to exploit methionine dependence for therapy, our laboratory previously cloned L-methionine α-deamino-γ-mercaptomethane lyase [EC 4.4.1.11]). The cloned methioninase, termed recombinant methioninase, or rMETase, has been tested in mouse models of human cancer cell lines. Ewing's sarcoma is recalcitrant disease even though development of multimodal therapy has improved patients'outcome. Here we report efficacy of rMETase against Ewing's sarcoma in a patient-derived orthotopic xenograft (PDOX) model. The Ewing's sarcoma was implanted in the right chest wall of nude mice to establish a PDOX model. Eight Ewing's sarcoma PDOX mice were randomized into untreated control group (n = 4) and rMETase treatment group (n = 4). rMETase (100 units) was injected intraperitoneally (i.p.) every 24 hours for 14 consecutive days. All mice were sacrificed on day-15, 24 hours after the last rMETase administration. rMETase effectively reduced tumor growth compared to untreated control. The methionine level both of plasma and supernatants derived from sonicated tumors was lower in the rMETase group. Body weight did not significantly differ at any time points between the 2 groups. The present study is the first demonstrating rMETase efficacy in a PDOX model, suggesting potential clinical development, especially in recalcitrant cancers such as Ewing's sarcoma. PMID:28404944

Recombinant methioninase effectively targets a Ewing's sarcoma in a patient-derived orthotopic xenograft (PDOX) nude-mouse model.

PubMed

Murakami, Takashi; Li, Shukuan; Han, Qinghong; Tan, Yuying; Kiyuna, Tasuku; Igarashi, Kentaro; Kawaguchi, Kei; Hwang, Ho Kyoung; Miyake, Kentaro; Singh, Arun S; Nelson, Scott D; Dry, Sarah M; Li, Yunfeng; Hiroshima, Yukihiko; Lwin, Thinzar M; DeLong, Jonathan C; Chishima, Takashi; Tanaka, Kuniya; Bouvet, Michael; Endo, Itaru; Eilber, Fritz C; Hoffman, Robert M

2017-05-30

Methionine dependence is due to the overuse of methionine for aberrant transmethylation reactions in cancer. Methionine dependence may be the only general metabolic defect in cancer. In order to exploit methionine dependence for therapy, our laboratory previously cloned L-methionine α-deamino-γ-mercaptomethane lyase [EC 4.4.1.11]). The cloned methioninase, termed recombinant methioninase, or rMETase, has been tested in mouse models of human cancer cell lines. Ewing's sarcoma is recalcitrant disease even though development of multimodal therapy has improved patients'outcome. Here we report efficacy of rMETase against Ewing's sarcoma in a patient-derived orthotopic xenograft (PDOX) model. The Ewing's sarcoma was implanted in the right chest wall of nude mice to establish a PDOX model. Eight Ewing's sarcoma PDOX mice were randomized into untreated control group (n = 4) and rMETase treatment group (n = 4). rMETase (100 units) was injected intraperitoneally (i.p.) every 24 hours for 14 consecutive days. All mice were sacrificed on day-15, 24 hours after the last rMETase administration. rMETase effectively reduced tumor growth compared to untreated control. The methionine level both of plasma and supernatants derived from sonicated tumors was lower in the rMETase group. Body weight did not significantly differ at any time points between the 2 groups. The present study is the first demonstrating rMETase efficacy in a PDOX model, suggesting potential clinical development, especially in recalcitrant cancers such as Ewing's sarcoma.

Ocular Toxoplasmosis: Therapy-Related Adverse Drug Reactions and Their Management.

PubMed

Helfenstein, M; Zweifel, S; Barthelmes, D; Meier, F; Fehr, J; Böni, C

2017-04-01

Background There are different treatment options for ocular toxoplasmosis (OT). "Classic" therapy consists of pyrimethamine, sulfadiazine and folinic acid combined with systemic steroids and is still widely used. However, potentially severe side effects of this therapy have been reported. The aim of this retrospective study was to evaluate the incidence and types of adverse drug reactions in patients treated for OT. Clinical management of each adverse drug reaction was assessed. Patients and Methods In this retrospective analysis, we reviewed data of patients with OT, who were consecutively examined between December 2011 and December 2015 at the Department of Ophthalmology, University Hospital Zurich. Results In total, 49 patients had at least one episode of active OT. In 54 (83.0 %) of 65 treated episodes, the classic regimen was used. Of the 37 patients who received classic treatment, 9 (24.3 %) developed at least one adverse drug reaction which led to drug discontinuation, including elevated creatinine (5.4 %), elevated liver enzymes (5.4 %), vomiting (5.4 %), rash (5.4 %) and facial swelling (2.7 %). In 5 patients, treatment was switched to another drug, while in the other 4 patients, therapy was stopped. In these 9 patients, inflammation was well controlled 8 weeks after onset of therapy. No patient suffered from severe side effects, such as potentially life-threatening allergic reactions or pancytopenia. Conclusions In OT patients who were treated with classic therapy, adverse drug reactions are common. Therefore, clinical and laboratory monitoring is mandatory. Adverse drug reactions may require interdisciplinary management. Georg Thieme Verlag KG Stuttgart · New York.

From ketenimines to ketenes to quinolones: two consecutive pseudopericyclic events.

PubMed

Alajarín, Mateo; Ortín, María-Mar; Sánchez-Andrada, Pilar; Vidal, Angel; Bautista, Delia

2005-11-10

[reaction: see text] N-[2-(Alkyl- or arylthio)carbonyl]phenyl ketenimines undergo cyclization under mild thermal conditions to afford 2-alkyl(aryl)thio-3H-quinolin-4-ones by means of the 1,5-migration of the alkyl(aryl)thio group from the carbonyl carbon to the central carbon atom of the ketenimine fragment followed by the 6pi-electrocyclization of the resulting vinyliminoketene. These 1,5-migration and electrocyclization processes occur via transition states whose pseudopericyclic characteristics have been established on the basis of their magnetic properties, geometries, and NBO analyses.

Highly efficient and generalized asymmetric synthesis of quaternary stereogenic carbon-containing β-amino indanones/indanoles via Mannich-type additions between 1-indanones and N-tert-butanesulfinylketimines.

PubMed

Wu, Lingmin; Xie, Chen; Mei, Haibo; Soloshonok, Vadim A; Han, Jianlin; Pan, Yi

2014-07-14

Here we report that, unlike other ketones, 1-indanone and acetophenone derived enolates undergo Mannich-type addition reactions with N-tert-butanesulfinyl ketimines with excellent yields (up to 98%) and diastereoselectivity (>99/1). The resulting compounds represent a new type of biologically relevant β-aminoketone derivative bearing quaternary stereogenic carbon, which could be further converted into the corresponding β-amino ketones and β-amino alcohols, possessing three consecutive stereogenic centres.

Stable selones in glutathione-peroxidase-like catalytic cycle of selenonicotinamide derivative.

PubMed

Prabhu, Parashiva; Singh, Beena G; Noguchi, Masato; Phadnis, Prasad P; Jain, Vimal K; Iwaoka, Michio; Priyadarsini, K Indira

2014-04-21

Selenonicotinamide, 2,2'-diselenobis[3-amidopyridine] (NictSeSeNict) exhibits glutathione-peroxidase (GPx)-like activity, catalyzing the reduction of hydrogen peroxide (H2O2) by glutathione (GSH). Estimated reactivity parameters for the reaction of selenium species, according to the Dalziel kinetic model, towards GSH (ϕGSH) and H2O2 (ϕH2O2), indicated that the rate constant for the reaction of NictSeSeNict with GSH is higher as compared to that with H2O2, indicating that the activity is initiated by reduction. (77)Se NMR spectroscopy, HPLC analysis, mass spectrometry (MS) and absorption spectroscopy were employed to understand the nature of selenium intermediates responsible for the activity. The (77)Se NMR resonance at 525 ppm due to NictSeSeNict disappeared in the presence of GSH with the initial appearance of signals at δ 364 and 600 ppm, assigned to selone (NictC=Se) and selenenyl sulfide (NictSeSG), respectively. Reaction of H2O2 with NictSeSeNict produced a mixture of selenenic acid (NictSeOH) and seleninic acid (NictSeO2H) with (77)Se NMR resonances appearing at 1069 and 1165 ppm, respectively. Addition of three equivalents of GSH to this mixture produced a characteristic (77)Se NMR signal of NictSeSG. HPLC analysis of the product formed by the reaction of NictSeSeNict with GSH confirmed the formation of NictC=Se absorbing at 375 nm. Stopped-flow kinetic studies with global analysis revealed a bimolecular rate constant of 4.8 ± 0.5 × 10(3) M(-1) s(-1) and 1.7 ± 0.6 × 10(2) M(-1) s(-1) for the formation of NictC=Se produced in two consecutive reactions of NictSeSeNict and NictSeSG with GSH, respectively. Similarly the rate constant for the reaction of NictC=Se with H2O2 was estimated to be 18 ± 1.8 M(-1) s(-1). These studies clearly indicated that the GPx activity of NictSeSeNict is initiated by reduction to form NictSeSG and a stable selone, which is responsible for its efficient GPx activity.

Cutaneous hypersensitivity reactions to freshwater cyanobacteria – human volunteer studies

PubMed Central

Stewart, Ian; Robertson, Ivan M; Webb, Penelope M; Schluter, Philip J; Shaw, Glen R

2006-01-01

Background Pruritic skin rashes associated with exposure to freshwater cyanobacteria are infrequently reported in the medical and scientific literature, mostly as anecdotal and case reports. Diagnostic dermatological investigations in humans are also infrequently described. We sought to conduct a pilot volunteer study to explore the potential for cyanobacteria to elicit hypersensitivity reactions. Methods A consecutive series of adult patients presenting for diagnostic skin patch testing at a hospital outpatient clinic were invited to participate. A convenience sample of volunteers matched for age and sex was also enrolled. Patches containing aqueous suspensions of various cyanobacteria at three concentrations were applied for 48 hours; dermatological assessment was made 48 hours and 96 hours after application. Results 20 outpatients and 19 reference subjects were recruited into the study. A single outpatient produced unequivocal reactions to several cyanobacteria suspensions; this subject was also the only one of the outpatient group with a diagnosis of atopic dermatitis. No subjects in the reference group developed clinically detectable skin reactions to cyanobacteria. Conclusion This preliminary clinical study demonstrates that hypersensitivity reactions to cyanobacteria appear to be infrequent in both the general and dermatological outpatient populations. As cyanobacteria are widely distributed in aquatic environments, a better appreciation of risk factors, particularly with respect to allergic predisposition, may help to refine health advice given to people engaging in recreational activities where nuisance cyanobacteria are a problem. PMID:16584576

Clinical history as a predictor of penicillin skin test outcome.

PubMed

Wong, Benjamin B L; Keith, Paul K; Waserman, Susan

2006-08-01

Up to 10% of the population reports an "allergy" to penicillin, whereas approximately 1.1% has positive penicillin skin test results. Where penicillin skin tests are unavailable, some have advocated using history to decide whether to use a penicillin-related antibiotic. To determine if clinical history predicts penicillin skin test results. Retrospective medical record review of 94 consecutive patients who had previously taken penicillin referred for penicillin allergy. Case histories were taken, penicillin skin tests performed, and an oral challenge recommended if skin test results were negative. Of 91 cases studied, the average patient age was 27 years (range, 6 months to 82 years; 36% female). Fifty-two (57%) experienced hives as their main adverse reaction. Sixteen (18%) had at least 1 positive test result. Of this group, 9 had hives as their main symptom, whereas 1 had respiratory problems and 1 had angioedema. Most patients with positive skin test results had experienced their reaction at least 3 years ago. Regression analysis showed that age, sex, and clinical history, including type of reaction, time of reaction after penicillin ingestion, or time since the last reaction, were not associated with skin test positivity. Seventy-two (96%) of the 75 patients who had negative skin test results underwent oral challenge. Seventy had negative challenge results. The negative predictive value of a negative penicillin skin test result was 97%. Clinical history was not predictive of subsequent penicillin skin test results.

Patch testing with hydroxyisohexyl 3-cyclohexene carboxaldehyde (HICC) - a multicentre study of the Swedish Contact Dermatitis Research Group.

PubMed

Engfeldt, Malin; Hagvall, Lina; Isaksson, Marléne; Matura, Mihály; Mowitz, Martin; Ryberg, Kristina; Stenberg, Berndt; Svedman, Cecilia; Bruze, Magnus

2017-01-01

In 2014, the fragrance hydroxyisohexyl 3-cyclohexene carboxaldehyde (HICC) was excluded from the Swedish baseline series. To study (i) whether fragrance mix (FM) II with 5% HICC detects more positive reactions than usual FM II with 2.5% HICC, and (ii) the reproducibility of patch testing with HICC. Two thousand one hundred and eighteen dermatitis patients at five Swedish dermatology departments were consecutively tested with FM II 14% pet., FM II 16.5% pet., and duplicate preparations of HICC 5% pet. Of the patients, 3.2% reacted to FM II 14%, and 1.5% reacted to HICC. Separate testing with HICC detected 0.3% reactions without concomitant reactivity to FM II. FM II with 5% HICC did not give rise to more irritant reactions or signs of active sensitization than FM II with 2.5% HICC. Patch testing with duplicate applications of HICC increased the overall prevalence of HICC contact allergy to 1.9%. FM II with 5% HICC does not detect more positive reactions than FM II with 2.5% HICC. Separate testing with HICC does not detect a sufficient proportion of patients who react only to HICC, without concomitant reactions to FM II, to warrant its inclusion in a baseline series. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Models construction for acetone-butanol-ethanol fermentations with acetate/butyrate consecutively feeding by graph theory.

PubMed

Li, Zhigang; Shi, Zhongping; Li, Xin

2014-05-01

Several fermentations with consecutively feeding of acetate/butyrate were conducted in a 7 L fermentor and the results indicated that exogenous acetate/butyrate enhanced solvents productivities by 47.1% and 39.2% respectively, and changed butyrate/acetate ratios greatly. Then extracellular butyrate/acetate ratios were utilized for calculation of acids rates and the results revealed that acetate and butyrate formation pathways were almost blocked by corresponding acids feeding. In addition, models for acetate/butyrate feeding fermentations were constructed by graph theory based on calculation results and relevant reports. Solvents concentrations and butanol/acetone ratios of these fermentations were also calculated and the results of models calculation matched fermentation data accurately which demonstrated that models were constructed in a reasonable way. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

NASA Astrophysics Data System (ADS)

Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

2018-04-01

In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

C$sup 12$(n,p) B$sup 12$ CROSS SECTION FOR 14.9- TO 17.5-MEV NEUTRONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kreger, W.E.; Kern, B.D.

1958-09-23

The cross section for the C/sup 12/(n,p)B/sup 12/ reaction has been measured for 14.9- to 17.5-Mev nuetrons. The neutrons were obtained from the T(d,n)He/sup 4/ reaction and their flux density was determined by counting the recoil alpha particles or by counting the neutrons directly with a Li/sup 6/I(Eu) scintillation counter. A cylindrical plastic scintillator 5 inches in diameter and 3 inches in length served as the carbon-containing target and permitted the counting of the B/sup 12/ decay beta rays in nine consecutive 7-msec intervals during the beam-off period or a pulsed neutron beam cycle. The cross section rises from slightlymore » above the reaction threshold of 13.6-Mev to a value of 29.09 plus or minus 4.36 millibarns at 17.5 Mev. The B/sup 12/ beta decay half life has been redetermined as 18.87 plus or minus 0.50 milliseconds. (auth)« less

Hypersensitivity reactions to food colours with special reference to the natural colour annatto extract (butter colour).

PubMed

Mikkelsen, H; Larsen, J C; Tarding, F

1978-01-01

It is well known that synthetic food colours especially some azo dyes can provoke hypersensitivity reactions such as urticaria, angioneurotic oedema, and astma (Michaëlsson and Juhlin, 1973, Granholt and Thune, 1975). Natural food colours are scarcely investigated with respect to potential allergic properties. Annatto extract, a commonly used food colour in edible fats e.g. butter, has been tested in patients. Among 61 consecutive patients suffereing from chornic urticaria and/or angioneurotic oedema 56 patients were orally provoked by annatto extract during elimination diet. Challenge was performed with a dose equivalent to the amount used in 25 grammes of butter. Twentysix per cent of the patients reacted to this colour 4 hours (SD: 2,6) after intake. Similar challenges with synthetic dyes showed the following results: Tartrazine 11%, Sunset Yellow FCF 17%, Food Red 17 16%, Amaranth 9%, Ponceau 4 R 15%, Erythrosine 12% and Brillant Blue FCF 14%. The present study indicates that natural food colours may induce hypersensitivity reactions as frequent as synthetic dyes.

Burning mouth syndrome: the role of contact hypersensitivity.

PubMed

Marino, R; Capaccio, P; Pignataro, L; Spadari, F

2009-05-01

Burning mouth syndrome is a burning sensation or stinging disorder affecting the oral mucosa in the absence of any clinical signs or mucosal lesions. Some studies have suggested that burning mouth syndrome could be caused by the metals used in dental prostheses, as well as by acrylate monomers, additives and flavouring agents, although others have not found any aetiologic role for hypersensitivity to dental materials. To evaluate the extent and severity of adverse reactions to dental materials in a group of patients with burning mouth syndrome, and investigate the possible role of contact allergy in its pathogenesis. We prospectively studied 124 consecutive patients with burning mouth syndrome (108 males; mean age 57 years, range 41-83), all of whom underwent allergen patch testing between 2004 and 2007. Sixteen patients (13%) showed positive patch test reactions and were classified as having burning mouth syndrome type 3 or secondary burning mouth syndrome (Lamey's and Scala's classifications). Although we did not find any significant association between the patients and positive patch test reactions, it would be advisable to include hypersensitivity to dental components when evaluating patients experiencing intermittent oral burning without any clinical signs.

Simple model of inhibition of chain-branching combustion processes

NASA Astrophysics Data System (ADS)

Babushok, Valeri I.; Gubernov, Vladimir V.; Minaev, Sergei S.; Miroshnichenko, Taisia P.

2017-11-01

A simple kinetic model has been suggested to describe the inhibition and extinction of flame propagation in reaction systems with chain-branching reactions typical for hydrocarbon systems. The model is based on the generalised model of the combustion process with chain-branching reaction combined with the one-stage reaction describing the thermal mode of flame propagation with the addition of inhibition reaction steps. Inhibitor addition suppresses the radical overshoot in flame and leads to the change of reaction mode from the chain-branching reaction to a thermal mode of flame propagation. With the increase of inhibitor the transition of chain-branching mode of reaction to the reaction with straight-chains (non-branching chain reaction) is observed. The inhibition part of the model includes a block of three reactions to describe the influence of the inhibitor. The heat losses are incorporated into the model via Newton cooling. The flame extinction is the result of the decreased heat release of inhibited reaction processes and the suppression of radical overshoot with the further decrease of the reaction rate due to the temperature decrease and mixture dilution. A comparison of the results of modelling laminar premixed methane/air flames inhibited by potassium bicarbonate (gas phase model, detailed kinetic model) with the results obtained using the suggested simple model is presented. The calculations with the detailed kinetic model demonstrate the following modes of combustion process: (1) flame propagation with chain-branching reaction (with radical overshoot, inhibitor addition decreases the radical overshoot down to the equilibrium level); (2) saturation of chemical influence of inhibitor, and (3) transition to thermal mode of flame propagation (non-branching chain mode of reaction). The suggested simple kinetic model qualitatively reproduces the modes of flame propagation with the addition of the inhibitor observed using detailed kinetic models.

Modeling atmospheric mineral aerosol chemistry to predict heterogeneous photooxidation of SO2

NASA Astrophysics Data System (ADS)

Yu, Zechen; Jang, Myoseon; Park, Jiyeon

2017-08-01

The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the absorption-desorption kinetics of SO2 and NOx (partitioning between the gas phase and the multilayer coated dust). The reaction of absorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron-hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 55 % of total sulfate (56 ppb SO2, 290 µg m-3 ATD, and NOx less than 5 ppb). At high NOx ( > 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was suppressed by the competition between NO2 and SO2, which both consume the dust-surface oxidants (OH radicals or ozone).

Chronoamperometric study of the films formed by 4,4'-bipyridyl cation radical salts on mercury in the presence of iodide ions: consecutive two-dimensional phase transitions.

PubMed

Gómez, L; Ruiz, J J; Camacho, L; Rodríguez-Amaro, R

2005-01-04

This paper reports a new mathematical model for consecutive two-dimensional phase transitions that accounts for the chronoamperometric behavior observed in the formation of electrochemical phases by 4,4'-bipyridyl cation radical (BpyH(2)(*)(+)) on mercury in aqueous iodide solutions. Also, a new interpretation for the induction time is proposed.

Effects of water-management alternatives on streamflow in the Ipswich River basin, Massachusetts

USGS Publications Warehouse

Zarriello, Philip J.

2001-01-01

Management alternatives that could help mitigate the effects of water withdrawals on streamflow in the Ipswich River Basin were evaluated by simulation with a calibrated Hydrologic Simulation Program--Fortran (HSPF) model. The effects of management alternatives on streamflow were simulated for a 35-year period (196195). Most alternatives examined increased low flows compared to the base simulation of average 1989-93 withdrawals. Only the simulation of no septic-effluent inflow, and the simulation of a 20-percent increase in withdrawals, further lowered flows or caused the river to stop flowing for longer periods of time than the simulation of average 198993 withdrawals. Simulations of reduced seasonal withdrawals by 20 percent, and by 50 percent, resulted in a modest increase in low flow in a critical habitat reach (model reach 8 near the Reading town well field); log-Pearson Type III analysis of simulated daily-mean flow indicated that under these reduced withdrawals, model reach 8 would stop flowing for a period of seven consecutive days about every other year, whereas under average 198993 withdrawals this reach would stop flowing for a seven consecutive day period almost every year. Simulations of no seasonal withdrawals, and simulations that stopped streamflow depletion when flow in model reach 19 was below 22 cubic feet per second, indicated flow would be maintained in model reach 8 at all times. Simulations indicated wastewater-return flows would augment low flow in proportion to the rate of return flow. Simulations of a 1.5 million gallons per day return flow rate indicated model reach 8 would stop flowing for a period of seven consecutive days about once every 5 years; simulated return flow rates of 1.1 million gallons per day indicated that model reach 8 would stop flowing for a period of seven consecutive days about every other year. Simulation of reduced seasonal withdrawals, combined with no septic effluent return flow, indicated only a slight increase in low flow compared to low flows simulated under average 198993 withdrawals. Simulation of reduced seasonal withdrawal, combined with 2.6 million gallons per day wastewater-return flows, provided more flow in model reach 8 than that simulated under no withdrawals.

MRMer, an interactive open source and cross-platform system for data extraction and visualization of multiple reaction monitoring experiments.

PubMed

Martin, Daniel B; Holzman, Ted; May, Damon; Peterson, Amelia; Eastham, Ashley; Eng, Jimmy; McIntosh, Martin

2008-11-01

Multiple reaction monitoring (MRM) mass spectrometry identifies and quantifies specific peptides in a complex mixture with very high sensitivity and speed and thus has promise for the high throughput screening of clinical samples for candidate biomarkers. We have developed an interactive software platform, called MRMer, for managing highly complex MRM-MS experiments, including quantitative analyses using heavy/light isotopic peptide pairs. MRMer parses and extracts information from MS files encoded in the platform-independent mzXML data format. It extracts and infers precursor-product ion transition pairings, computes integrated ion intensities, and permits rapid visual curation for analyses exceeding 1000 precursor-product pairs. Results can be easily output for quantitative comparison of consecutive runs. Additionally MRMer incorporates features that permit the quantitative analysis experiments including heavy and light isotopic peptide pairs. MRMer is open source and provided under the Apache 2.0 license.

Chlorophyll degradation in a Chlamydomonas reinhardtii mutant: an accumulation of pyropheophorbide a by anaerobiosis.

PubMed

Doi, M; Inage, T; Shioi, Y

2001-05-01

Chlorophyll degradation was investigated in cells of a chlorophyll b-less mutant of Chlamydomonas reinhardtii under aerobic and anaerobic conditions. During degradation of chlorophyll under anaerobic conditions, chlorophyll catabolite P535, an open-tetrapyrrole, was not excreted, but pyropheophorbide a was accumulated as the end product with a transient accumulation of chlorophyllide a and pheophorbide a in cells, in contrast to the breakdown under aerobic conditions. It is likely that in the absence of oxygen, degradation of chlorophyll a proceeds to pyropheophorbide a by three consecutive reactions, dephytylation, metal-releasing and demethoxycarbonylation, and then stops due to a limitation of the oxygen that the monooxygenase reaction requires for bilin formation. A novel enzyme catalyzing demethoxycarbonylation of pheophorbide a was partially purified. The enzyme activity increased dependent on the age of cells, and its increase was completely suppressed by cycloheximide. Production of P535 was also dependent on cytoplasmic protein synthesis.

Can the epoxides of cinnamyl alcohol and cinnamal show new cases of contact allergy?

PubMed

Hagvall, Lina; Niklasson, Ida B; Luthman, Kristina; Karlberg, Ann-Therese

2018-06-01

Cinnamyl alcohol is considered to be a prohapten and prehapten with cinnamal as the main metabolite. However, many individuals who are allergic to cinnamyl alcohol do not react to cinnamal. Sensitizing epoxides of cinnamyl alcohol and cinnamal have been identified as metabolites and autoxidation products of cinnamyl alcohol. To investigate the clinical relevance of contact allergy to epoxycinnamyl alcohol and epoxycinnamal. Irritative effects of the epoxides were investigated in 12 dermatitis patients. Epoxycinnamyl alcohol and epoxycinnamal were patch tested in 393 and 390 consecutive patients, respectively. In parallel, cinnamyl alcohol and cinnamal were patch tested in 607 and 616 patients, respectively. Both epoxides were irritants, but no more positive reactions were detected than when testing was performed with cinnamyl alcohol and cinnamal. Late allergic reactions to epoxycinnamyl alcohol were observed. In general, patients with late reactions showed doubtful or positive reactions to cinnamal and fragrance mix I at regular patch testing. The investigated epoxides are not important haptens in contact allergy to cinnamon fragrance. The high frequency of fragrance allergy among patients included in the irritancy study showed the difficulty of suspecting fragrance allergy on the basis of history; patch testing broadly with fragrance compounds is therefore important. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Use of an instrument sandwiched between the hoof and shoe to measure vertical ground reaction forces and three-dimensional acceleration at the walk, trot, and canter in horses.

PubMed

Kai, M; Aoki, O; Hiraga, A; Oki, H; Tokuriki, M

2000-08-01

To develop an instrument that could be sandwiched between the hoof and shoe of horses and that would reliably measure vertical ground reaction forces and three-dimensional acceleration at the walk, trot, and canter. 5 clinically sound Thoroughbreds. The recording instrument (weight, 350 g) consisted of 2 metal plates, 2 bolts, 4 load cells, and 3 accelerometers. It was mounted to the hoof with a glue-on shoe and devised to support as much load exerted by a limb as possible. The load cells and accelerometers were wired to a 16-channel transmitter, and transmitted signals were received and amplified with a telemetry receiver. The recording instrument could measure in real time the 4 components of the ground reaction force or their resultant force along with acceleration in 3 dimensions as horses walked, trotted, or cantered on a treadmill. Patterns of force-time curves recorded for consecutive strides were similar to each other and to those previously reported, using a force plate. The recording instrument developed for use in the present study allowed us to record vertical ground reaction force and acceleration in 3 dimensions in horses at the walk, trot, and canter.

Cosmetic Contact Sensitivity in Patients with Melasma: Results of a Pilot Study

PubMed Central

Prabha, Neel; Mahajan, Vikram K.; Mehta, Karaninder S.; Chauhan, Pushpinder S.

2014-01-01

Background. Some of the patients with melasma perhaps have pigmented cosmetic dermatitis. However, cosmetic contact sensitivity in melasma remains poorly studied particularly in the Indian context. Objectives. To study cosmetic contact sensitivity in patients with melasma. Materials and Methods. 67 (F : M = 55 : 12) consecutive patients with melasma between 19 and 49 years of age were patch tested sequentially during January–December, 2012, with Indian Cosmetic and Fragrance Series, Indian Sunscreen Series, p-phenylenediamine, and patient's own cosmetic products. Results. 52 (78%) patients were in the age group of 20–40 years. The duration of melasma varied from 1 month to 20 years. Centrofacial, malar, and mandibular patterns were observed in 48 (72%), 18 (27%), and 1 (1%) patients, respectively. Indian Cosmetics and Fragrance Series elicited positive reactions in 29 (43.3%) patients. Cetrimide was the most common contact sensitizers eliciting positivity in 15 (52%) patients, followed by gallate mix in 9 (31%) patients and thiomersal in 7 (24%) patients. Only 2 of the 42 patients showed positive reaction from their own cosmetics while the other 5 patients had irritant reaction. Indian Sunscreen Series did not elicit any positive reaction. Conclusion. Cosmetics contact sensitivity appears as an important cause of melasma not associated with pregnancy, lactation, or hormone therapy. PMID:25132846

Modelling Students' Visualisation of Chemical Reaction

ERIC Educational Resources Information Center

Cheng, Maurice M. W.; Gilbert, John K.

2017-01-01

This paper proposes a model-based notion of "submicro representations of chemical reactions". Based on three structural models of matter (the simple particle model, the atomic model and the free electron model of metals), we suggest there are two major models of reaction in school chemistry curricula: (a) reactions that are simple…

Variability of vertical ground reaction forces collected with one and two force plates in healthy dogs.

PubMed

Stejskal, M; Torres, B T; Sandberg, G S; Sapora, J A; Dover, R K; Budsberg, S C

2015-01-01

To compare peak vertical force (PVF) and vertical impulse (VI) data collected with one and two force plates during the same collection time period in healthy dogs at a trot. Seventeen healthy client-owned adult dogs. Vertical ground reaction force (GRF) data were collected in a crossover study design, with four sessions on two consecutive days, and then two weeks apart (days 1, 2, 15, and 16) using both one and two force plates collection methods. A repeated measures model analysis of variance (ANOVA) was used to test for differences in force plate PVF, VI, and average time per trial (ATT) between days, weeks, and systems (1 plate versus 2 plates). Coefficients of variation for PVF and VI were also calculated separately by forelimbs and hindlimbs, plates, day, and week. The time required to obtain a valid trial was significantly longer using a single force plate when compared with two force plates. Comparing GRF data for all dogs, significant differences in PVF data were found between one and two force plates, however, these differences were diminutive in absolute magnitude, and of unknown clinical importance. Examination of the coefficients of variation for PVF and VI during the different collection periods yielded similar results. Use of two force plates decreased trial repetition and collection time. Vertical GRF data had a similar coefficient of variation with either one or two force plates collection techniques in healthy dogs.

Method of Breast Reconstruction Determines Venous Thromboembolism Risk Better Than Current Prediction Models

PubMed Central

Patel, Niyant V.; Wagner, Douglas S.

2015-01-01

Background: Venous thromboembolism (VTE) risk models including the Davison risk score and the 2005 Caprini risk assessment model have been validated in plastic surgery patients. However, their utility and predictive value in breast reconstruction has not been well described. We sought to determine the utility of current VTE risk models in this population and the VTE rate observed in various methods of breast reconstruction. Methods: A retrospective review of breast reconstructions by a single surgeon was performed. One hundred consecutive transverse rectus abdominis myocutaneous (TRAM) patients, 100 consecutive implant patients, and 100 consecutive latissimus dorsi patients were identified over a 10-year period. Patient demographics and presence of symptomatic VTE were collected. 2005 Caprini risk scores and Davison risk scores were calculated for each patient. Results: The TRAM reconstruction group was found to have a higher VTE rate (6%) than the implant (0%) and latissimus (0%) reconstruction groups (P < 0.01). Mean Davison risk scores and 2005 Caprini scores were similar across all reconstruction groups (P > 0.1). The vast majority of patients were stratified as high risk (87.3%) by the VTE risk models. However, only TRAM reconstruction patients demonstrated significant VTE risk. Conclusions: TRAM reconstruction appears to have a significantly higher risk of VTE than both implant and latissimus reconstruction. Current risk models do not effectively stratify breast reconstruction patients at risk for VTE. The method of breast reconstruction appears to have a significant role in patients’ VTE risk. PMID:26090287

Students' Visualisation of Chemical Reactions--Insights into the Particle Model and the Atomic Model

ERIC Educational Resources Information Center

Cheng, Maurice M. W.

2018-01-01

This paper reports on an interview study of 18 Grade 10-12 students' model-based reasoning of a chemical reaction: the reaction of magnesium and oxygen at the submicro level. It has been proposed that chemical reactions can be conceptualised using two models: (i) the "particle model," in which a reaction is regarded as the simple…

Allergy to oxidized limonene and linalool is frequent in the U.K.

PubMed

Audrain, H; Kenward, C; Lovell, C R; Green, C; Ormerod, A D; Sansom, J; Chowdhury, M M U; Cooper, S M; Johnston, G A; Wilkinson, M; King, C; Stone, N; Horne, H L; Holden, C R; Wakelin, S; Buckley, D A

2014-08-01

The oxidized forms of the fragrance terpenes limonene and linalool are known to cause allergic contact dermatitis. Significant rates of contact allergy to these fragrances have been reported in European studies and in a recent worldwide study. Patch testing to oxidized terpenes is not routinely carried out either in the U.K. or in other centres internationally. To investigate the prevalence of contact allergy to oxidized limonene and linalool in the U.K. Between 1 August 2011 and 31 December 2012, 4731 consecutive patients in 13 U.K. dermatology departments were tested for hydroperoxides of limonene 0·3% pet., hydroperoxides of linalool 1·0% pet., stabilized limonene 10·0% pet. and stabilized linalool 10·0% pet. Doubtful (?+) and equivocal (±) reactions were grouped together as irritant reactions. Two hundred and thirty-seven patients (5·0%) had a positive patch test reaction to hydroperoxides of limonene 0·3% pet. and 281 (5·9%) to hydroperoxides of linalool 1·0% pet. Irritant reactions to one or both oxidized terpenes were found in 242 patients (7·3%). Eleven patients (0·2%) had a positive patch test reaction to the stabilized terpenes alone. This large, multicentre U.K. audit shows a significant rate of allergy to the hydroperoxides of limonene and linalool plus a high rate of irritant reactions. Testing to the oxidized forms alone captures the majority (97·0%; 411 of 422) of positive reactions; testing to nonoxidized terpenes appears to be less useful. We recommend that the hydroperoxides of limonene and linalool be added to an extended baseline patch test series. © 2014 British Association of Dermatologists.

Integration of 3 Consecutive Years of Aqueous Geochemistry Monitoring Serpentinization at the Coast Range Ophiolite Microbial Observatory (CROMO), Northern California, USA

NASA Astrophysics Data System (ADS)

Cardace, D.; Hoehler, T. M.; McCollom, T. M.; Schrenk, M. O.; Kubo, M. D.

2014-12-01

In August 2011, a set of 8 groundwater monitoring wells were established in actively serpentinizing ultramafic rocks of the Coast Range Ophiolite near Lower Lake, CA, as a NASA Astrobiology Institute project (Cardace et al., 2013). These wells have enabled repeated sampling and analysis of aqueous geochemistry, which we now present in an integrated model of the progress of serpentinization at this locality. The Coast Range Ophiolite Microbial Observatory (CROMO) plumbs groundwaters percolating through a tectonic mélange of Jurassic-aged oceanic crust, with blocks of metabasalt and metagabbro, variably serpentinized ultramafics, Great Valley Sequence sedimentary rocks including the Jurassic Knoxville formation and the Cretaceous Crack Canyon formation, as well as rocks resulting from silica-carbonate alteration of serpentinites (marginal listvenites). All of these rock units are accessible in the McLaughlin Natural Reserve (administered by the University of California-Davis). In this work, we report on persistent geochemical trends in CROMO waters, which are gas-rich, high pH (11+), Ca2+-OH- type waters, contrast their characteristics with other continental sites of serpentinization and deep sea serpentinizing vent systems, and place the evolution of these waters in a water-rock reaction context based on geochemical modeling.

[Investigation of a new highly porous hydroxyapatite matrix for obliterating open mastoid cavities - application in guinea pigs bulla].

PubMed

Punke, C; Zehlicke, T; Boltze, C; Pau, H W

2009-04-01

Many different techniques for obliterating open mastoid cavity have been described. The results after the application of alloplastic materials like Hydroxyapatite and Tricalciumphosphate were poor due to long-lasting resorption. Extrusion of those materials has been described. We investigated the applicability of a new high-porosity ceramic for obliterating large open mastoid cavities and tested it in an animal model (bulla of guinea pig). A highly porous matrix (NanoBone) bone-inductor fabricated in a sol-gel-technique was administered unilaterally into the opened bullae of 30 guinea pigs. In each animal the opposite bulla was filled with Bio-Oss, a bone substitute consisting of a portion of mineral bovine bone. Histological evaluations were performed 1, 2, 3, 4, 5 and 12 weeks after the implantation. After the initial phase with an inflammatory reaction creating a loose granulation tissue, we observed the formation of trabeculare bone within the fourth week in both groups. From the fifth week on we found osteoclasts on the surface of NanoBone and Bio-Oss with consecutive degradation of both materials. In our animal model study we found beneficial properties of the used bone-inductors NanoBone and Bio-Oss for obliterating open mastoid cavities.

Simultaneous patch testing with fragrance mix I, fragrance mix II and their ingredients in southern Sweden between 2009 and 2015.

PubMed

Mowitz, Martin; Svedman, Cecilia; Zimerson, Erik; Isaksson, Marléne; Pontén, Ann; Bruze, Magnus

2017-11-01

Fragrance mix I (FM I) and fragrance mix II (FM II) are included in the European baseline series as screening substances for fragrance contact allergy. To investigate the frequency of allergic reactions to FM I, FM II and their ingredients in consecutively patch tested patients. A retrospective analysis of data from 4430 patients patch tested between 2009 and 2015 was performed. Of the patients, 6.5% were FM I-positive and 3.2% were FM II-positive. Forty-five per cent of FM I-positive patients did not have positive reactions to FM I ingredients. Thirty-five per cent of those who were FM II-positive did not have positive reactions to FM II ingredients. Twenty-seven per cent of those with positive reactions to one or more of the FM I ingredients were FM I-negative, and 36% of those who had positive reactions to one or more of the FM II ingredients were FM II-negative. The allergens with the highest pick-up rates were Evernia prunastri (1.8%), cinnamal (1.3%), citral (1.2%), and hydroxyisohexyl 3-cyclohexene carboxaldehyde (1.2%). Significant differences were observed in the proportions of positive reactions to FM I, FM II, eugenol, isoeugenol, and farnesol when results from patch testing with materials from different suppliers were compared. There is a risk of missing fragrance contact allergy when testing with only the fragrance mixes is performed. The use of preparations from different suppliers may affect the patch test results. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Subcritical carbon dioxide-water hydrolysis of sugarcane bagasse pith for reducing sugars production.

PubMed

Liang, Jiezhen; Chen, Xiaopeng; Wang, Linlin; Wei, Xiaojie; Wang, Huasheng; Lu, Songzhou; Li, Yunhua

2017-03-01

The aim of present study was to obtain total reducing sugars (TRS) by hydrolysis in subcritical CO 2 -water from sugarcane bagasse pith (SCBP), the fibrous residue remaining after papermaking from sugarcane bagasse. The optimum hydrolysis conditions were evaluated by L 16 (4 5 ) orthogonal experiments. The TRS yield achieved 45.8% at the optimal conditions: 200°C, 40min, 500rmin -1 , CO 2 initial pressure of 1MPa and liquid-to-solid ratio of 50:1. Fourier transform infrared spectrometry and two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance were used to characterize hydrolysis liquor, treated and untreated SCBP, resulting in the removal of hemicelluloses to mainly produce xylose, glucose and arabinose during hydrolysis. The severity factors had no correlation to TRS yield, indicating that the simple kinetic processes of biomass solubilisation cannot perfectly describe the SCBP hydrolysis. The first-order kinetic model based on consecutive reaction was used to obtain rate constants, activation energies and pre-exponential factors. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multi-technique approach for qualitative and quantitative characterization of furazidin degradation kinetics under alkaline conditions.

PubMed

Bērziņš, Kārlis; Kons, Artis; Grante, Ilze; Dzabijeva, Diana; Nakurte, Ilva; Actiņš, Andris

2016-09-10

Degradation of drug furazidin was studied under different conditions of environmental pH (11-13) and temperature (30-60°C). The novel approach of hybrid hard- and soft-multivariate curve resolution-alternating least squares (HS-MCR-ALS) method was applied to UV-vis spectral data to determine a valid kinetic model and kinetic parameters of the degradation process. The system was found to be comprised of three main species and best characterized by two consecutive first-order reactions. Furazidin degradation rate was found to be highly dependent on the applied environmental conditions, showing more prominent differences between both degradation steps towards higher pH and temperature. Complimentary qualitative analysis of the degradation process was carried out using HPLC-DAD-TOF-MS. Based on the obtained chromatographic and mass spectrometric results, as well as additional computational analysis of the species (theoretical UV-vis spectra calculations utilizing TD-DFT methodology), the operating degradation mechanism was proposed to include formation of a 5-hydroxyfuran derivative, followed by complete hydrolysis of furazidin hydantoin ring. Copyright © 2016 Elsevier B.V. All rights reserved.

cis-Prenyltransferase: New Insights into Protein Glycosylation, Rubber Synthesis, and Human Diseases.

PubMed

Grabińska, Kariona A; Park, Eon Joo; Sessa, William C

2016-08-26

cis-Prenyltransferases (cis-PTs) constitute a large family of enzymes conserved during evolution and present in all domains of life. cis-PTs catalyze consecutive condensation reactions of allylic diphosphate acceptor with isopentenyl diphosphate (IPP) in the cis (Z) configuration to generate linear polyprenyl diphosphate. The chain lengths of isoprenoid carbon skeletons vary widely from neryl pyrophosphate (C10) to natural rubber (C>10,000). The homo-dimeric bacterial enzyme, undecaprenyl diphosphate synthase (UPPS), has been structurally and mechanistically characterized in great detail and serves as a model for understanding the mode of action of eukaryotic cis-PTs. However, recent experiments have revealed that mammals, fungal, and long-chain plant cis-PTs are heteromeric enzymes composed of two distantly related subunits. In this review, the classification, function, and evolution of cis-PTs will be discussed with a special emphasis on the role of the newly described NgBR/Nus1 subunit and its plants' orthologs as essential, structural components of the cis-PTs activity. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Modelling Chemical Reasoning to Predict and Invent Reactions.

PubMed

Segler, Marwin H S; Waller, Mark P

2017-05-02

The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ethanol and other oxygenateds from low grade carbonaceous resources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joo, O.S.; Jung, K.D.; Han, S.H.

1995-12-31

Anhydrous ethanol and other oxygenates of C2 up can be produced quite competitively from low grade carbonaceous resources in high yield via gasification, methanol synthesis, carbonylation of methanol an hydrogenation consecutively. Gas phase carbonylation of methanol to form methyl acetate is the key step for the whole process. Methyl acetate can be produced very selectively in one step gas phase reaction on a fixed bed column reactor with GHSV over 5,000. The consecutive hydrogenation of methyl or ethyl acetate produce anhydrous ethanol in high purity. It is also attempted to co-produce methanol and DME in IGCC, in which low grademore » carbonaceous resources are used as energy sources, and the surplus power and pre-power gas can be stored in liquid form of methanol and DME during base load time. Further integration of C2 up oxygenate production with IGCC can improve its economics. The attempt of above extensive technology integration can generate significant industrial profitability as well as reduce the environmental complication related with massive energy consumption.« less

Facile consecutive solvothermal growth of highly fluorescent InP/ZnS core/shell quantum dots using a safer phosphorus source.

PubMed

Byun, Ho-June; Song, Woo-Seuk; Yang, Heesun

2011-06-10

The work presents a facile, stepwise synthetic approach for the production of highly fluorescent InP/ZnS core/shell quantum dots (QDs) by using a safer phosphorus (P) precursor. First, InP quantum dots (QDs) were solvothermally prepared at 180 °C for 24 h by using a P source of P(N(CH(3))(2))(3). The as-grown InP QDs were consecutively placed in another solvothermal condition for ZnS shell overcoating. In contrast to the almost non-fluorescent InP QDs, due to their highly defective surface states, the ZnS-coated InP QDs were highly fluorescent as a result of effective surface passivation. After the shell growth, the resulting InP/ZnS core/shell QDs were subjected to a size-sorting processing, by which red- to green-emitting QDs with quantum yields (QYs) of 24-60% were produced. Solvothermal shell growth parameters such as the reaction time and Zn/In solution concentration ratio were varied and optimized toward the highest QYs of core/shell QDs.

Facile consecutive solvothermal growth of highly fluorescent InP/ZnS core/shell quantum dots using a safer phosphorus source

NASA Astrophysics Data System (ADS)

Byun, Ho-June; Song, Woo-Seuk; Yang, Heesun

2011-06-01

The work presents a facile, stepwise synthetic approach for the production of highly fluorescent InP/ZnS core/shell quantum dots (QDs) by using a safer phosphorus (P) precursor. First, InP quantum dots (QDs) were solvothermally prepared at 180 °C for 24 h by using a P source of P(N(CH3)2)3. The as-grown InP QDs were consecutively placed in another solvothermal condition for ZnS shell overcoating. In contrast to the almost non-fluorescent InP QDs, due to their highly defective surface states, the ZnS-coated InP QDs were highly fluorescent as a result of effective surface passivation. After the shell growth, the resulting InP/ZnS core/shell QDs were subjected to a size-sorting processing, by which red- to green-emitting QDs with quantum yields (QYs) of 24-60% were produced. Solvothermal shell growth parameters such as the reaction time and Zn/In solution concentration ratio were varied and optimized toward the highest QYs of core/shell QDs.

PREFACE: Biomimetics, Artificial Muscles & Nano-Bio 2007: Scientists Meet Doctors

NASA Astrophysics Data System (ADS)

Fernández Otero, Toribio

2008-02-01

Science is one of the most robust conceptual constructs developed by human beings. Theoretical physical models have been developed involving the smallest and the largest systems over the full scale of the universe. At both extremes the models are predictive and include constant interactions between components. Life evolved from systems of intermediate size in relation to the extremes of universal scale. Life, biological organs and cells only develop functions under chemical driving conditions. Natural organs can be considered as biological devices which are very efficient at transforming chemical energy at constant temperature into functions, unlike machines' servitude to the Carnot cycle. Inside any living cell thousands of simultaneous reactions occur. Every reaction promotes changes from reactants to products with subsequent changes to hundreds of intramolecular and intermolecular interactions. Moreover, most of those reactions link conformational changes of biopolymers with ionic and electronic movement driving water flow. Chemical reactions, intermolecular and intramolecular interactions involving conformational movements are outside the possibilities of current theoretical models. Theoretical descriptions of any living cell and predictions of its behaviour when unhealthy are unavailable within our scientific models. Actuation of natural organs such as muscles involves, moreover, the chemical reaction ATP hydrolysis—simultaneous sensing processes which provide living creatures with a perfect consciousness of both the characteristics of their mechanical movements and their interactions with their environment: they are intelligent machines. This constitutes the proximity paradox. We have been able to develop good and predictive theoretical models for subatomic or galactic systems, far removed from our everyday surroundings. Nevertheless, we are unable to predict the behaviour of the cells and organs that constitute our life and everyday environment, when invaded by a new virus. A very expensive trial and error (still pseudo-alchemic) procedure has to be initiated to try to enable ill people to get better. Nowadays models from chemical kinetics do not include any quantification of either changes to the molecular interactions inside the system during reaction or structural information about the conformational changes brought about by enzymes or reactive proteins. From our point of view this is one the most important scientific challenges for the 21st century, involving responses to questions related to life, health and illness. Those responses, due to the magnitude of the challenge, can only be obtained by cooperative work involving chemists, physicist, engineers, biologists and clinicians. Figure Figure showing the full distance inside the universe. Small and large systems are submitted as `constant physical' interactions affording quite predictive models. Life is based on chemistry giving rise to simultaneous changes on all the molecular interactions included in the system: their interpretation is outside current chemical or physical models. Most technological advances developed by human beings are inspired by biological systems, organs, or mechanisms present in living creatures. The main difference between human technology and natural organs is the changes in chemical composition occurring inside the wet natural organ during actuation: they are reactive, soft and wet materials. Our artificial machines are constructed of dry materials that maintain a constant composition under actuation. This is the context proposed for the consecutive World Congresses on Biomimetics, Artificial Muscles & Nano-Bio and more specifically for the IVth Congress held in Torre Pacheco, Spain, 6-9 November 2007. The papers selected for this volume of Journal of Physics: Conference Series includes: dry and wet materials, chemically reactive or physically reactive materials, organic and inorganic materials, macroscopic films and nanoparticles. Different biomimicking devices: artificial muscles and actuators, sensors, electrochromic materials, and microscopic magnetic control of fluids are described under different experimental conditions. New models, including or avoiding chemical reactions are presented here. In this way new steps are being presented in an attempt to model biomimicking materials and devices. We expect that those biomimicking devices and models will, in the future, open the way to predict the behaviour of cells. Thanks are due to the editorial and production team of Journal of Physics: Conference Series for their continued support and management of the review and preparation process in an entirely efficient and professional manner. Thanks are due to those institutions that have contributed in different ways to the final success of the meeting: MEC, ISE, UPCT, IBERNAM and the Autonomous Government of the Murcia Region. Special thanks go to all the participants who have contributed to this volume of Journal of Physics: Conference Series who are at the forefront of progress towards the biomimetics of materials, properties and models. Toribio Fernández Otero

A new method for computing the reliability of consecutive k-out-of-n:F systems

NASA Astrophysics Data System (ADS)

Gökdere, Gökhan; Gürcan, Mehmet; Kılıç, Muhammet Burak

2016-01-01

In many physical systems, reliability evaluation, such as ones encountered in telecommunications, the design of integrated circuits, microwave relay stations, oil pipeline systems, vacuum systems in accelerators, computer ring networks, and spacecraft relay stations, have had applied consecutive k-out-of-n system models. These systems are characterized as logical connections among the components of the systems placed in lines or circles. In literature, a great deal of attention has been paid to the study of the reliability evaluation of consecutive k-out-of-n systems. In this paper, we propose a new method to compute the reliability of consecutive k-out-of-n:F systems, with n linearly and circularly arranged components. The proposed method provides a simple way for determining the system failure probability. Also, we write R-Project codes based on our proposed method to compute the reliability of the linear and circular systems which have a great number of components.

A dual-process model of reactions to perceived stigma.

PubMed

Pryor, John B; Reeder, Glenn D; Yeadon, Christopher; Hesson-McLnnis, Matthew

2004-10-01

The authors propose a theoretical model of individual psychological reactions to perceived stigma. This model suggests that 2 psychological systems may be involved in reactions to stigma across a variety of social contexts. One system is primarily reflexive, or associative, whereas the other is rule based, or reflective. This model assumes a temporal pattern of reactions to the stigmatized, such that initial reactions are governed by the reflexive system, whereas subsequent reactions or "adjustments" are governed by the rule-based system. Support for this model was found in 2 studies. Both studies examined participants' moment-by-moment approach-avoidance reactions to the stigmatized. The 1st involved participants' reactions to persons with HIV/AIDS, and the 2nd, participants' reactions to 15 different stigmatizing conditions. (c) 2004 APA, all rights reserved

Elective penicillin skin testing in a pediatric outpatient setting.

PubMed

Jost, Barbara Capes; Wedner, H James; Bloomberg, Gordon R

2006-12-01

Adverse reactions associated with penicillin-type antibiotics are common in pediatric practice, leading to the subsequent unnecessary use of alternative antibiotics. IgE-mediated penicillin allergy represents only a fraction of these adverse reactions. To examine (1) the trend of penicillin skin test reactivity during a recent 10-year interval, (2) the relative distribution of specific reagents related to a positive skin test result, and (3) skin test reactivity as a function of reaction history. Penicillin testing using 3 reagents--benzylpenicilloyl polylysine, penicillin G, and sodium penicilloate (penicillin A)--was conducted in a prospective study of 359 consecutive patients referred to an outpatient pediatric allergy clinic between January 1, 1993, and May 31, 2003. We also retrospectively reviewed penicillin skin test results for 562 children previously tested between January 1, 1979, and December 31, 1992. Between 1993 and 2003, the prevalence of penicillin skin test sensitivity markedly declined. Of all the positive skin test results between 1979 and 2002, either penicillin G or sodium penicilloate or both identified 34%, with sodium penicilloate alone responsible for 8.5%. The rate of positive skin test reactions was not significantly different between patients with vs without a history of suggestive IgE-mediated reactions. A marked decline in penicillin skin test sensitivity in the pediatric age group is identified. The minor determinant reagents penicillin G and sodium penicilloate are both necessary for determining potential penicillin allergy. Relating history alone to potential penicillin sensitivity is unreliable in predicting the presence or absence of a positive skin test result.

Understanding and Exploitation of Neighboring Heteroatom Effect for the Mild N-Arylation of Heterocycles with Diaryliodonium Salts under Aqueous Conditions: A Theoretical and Experimental Mechanistic Study.

PubMed

Bihari, Tamás; Babinszki, Bence; Gonda, Zsombor; Kovács, Szabolcs; Novák, Zoltán; Stirling, András

2016-07-01

The mechanism of arylation of N-heterocycles with unsymmetric diaryliodonium salts is elucidated. The fast and efficient N-arylation reaction is interpreted in terms of the bifunctionality of the substrate: The consecutive actions of properly oriented Lewis base and Brønsted acid centers in sufficient proximity result in the fast and efficient N-arylation. The mechanistic picture points to a promising synthetic strategy where suitably positioned nucleophilic and acidic centers enable functionalization, and it is tested experimentally.

Tetraethylene glycol promoted two-step, one-pot rapid synthesis of indole-3-[1- 11C]acetic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sojeong; Qu, Wenchao; Alexoff, David L.

2014-12-12

An operationally friendly, two-step, one-pot process has been developed for the rapid synthesis of carbon-11 labeled indole-3-acetic acid ([ 11]IAA or [ 11]auxin). By replacing an aprotic polar solvent with tetraethylene glycol, nucleophilic [ 11]cyanation and alkaline hydrolysis reactions were performed consecutively in a single pot without a time-consuming intermediate purification step. The entire production time for this updated procedure is 55 min, which dramatically simplifies the entire synthesis and reduces the starting radioactivity required for a whole plant imaging study.

Baseline Predictors of Missed Visits in the Look AHEAD Study

PubMed Central

Fitzpatrick, Stephanie L.; Jeffery, Robert; Johnson, Karen C.; Roche, Cathy C.; Van Dorsten, Brent; Gee, Molly; Johnson, Ruby Ann; Charleston, Jeanne; Dotson, Kathy; Walkup, Michael P.; Hill-Briggs, Felicia; Brancati, Frederick L.

2013-01-01

Objective To identify baseline attributes associated with consecutively missed data collection visits during the first 48 months of Look AHEAD—a randomized, controlled trial in 5145 overweight/obese adults with type 2 diabetes designed to determine the long-term health benefits of weight loss achieved by lifestyle change. Design and Methods The analyzed sample consisted of 5016 participants who were alive at month 48 and enrolled at Look AHEAD sites. Demographic, baseline behavior, psychosocial factors, and treatment randomization were included as predictors of missed consecutive visits in proportional hazard models. Results In multivariate Cox proportional hazard models, baseline attributes of participants who missed consecutive visits (n=222) included: younger age ( Hazard Ratio [HR] 1.18 per 5 years younger; 95% Confidence Interval 1.05, 1.30), higher depression score (HR 1.04; 1.01, 1.06), non-married status (HR 1.37; 1.04, 1.82), never self-weighing prior to enrollment (HR 2.01; 1.25, 3.23), and randomization to minimal vs. intensive lifestyle intervention (HR 1.46; 1.11, 1.91). Conclusions Younger age, symptoms of depression, non-married status, never self-weighing, and randomization to minimal intervention were associated with a higher likelihood of missing consecutive data collection visits, even in a high-retention trial like Look AHEAD. Whether modifications to screening or retention efforts targeted to these attributes might enhance long-term retention in behavioral trials requires further investigation. PMID:23996977

78 FR 71615 - Agency Forms Undergoing Paperwork Reduction Act Review

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-29

...TM Program (Hands-on, Online, Blended models). Trainee Reaction Survey-- 180 1 15/60 Hands-On Model. Trainee Reaction Survey-- 180 1 15/60 Online Model. Trainee Reaction Survey-- 180 1 15/60 Blended Model... Program (Train-the- Participant Survey. Trainer model). Trainee Reaction Survey-- 30 1 15/60 Train-the...

Synthesis and self-organization of zinc β-(dialkoxyphosphoryl)porphyrins in the solid state and in solution.

PubMed

Vinogradova, Ekaterina V; Enakieva, Yulia Y; Nefedov, Sergey E; Birin, Kirill P; Tsivadze, Aslan Y; Gorbunova, Yulia G; Bessmertnykh Lemeune, Alla G; Stern, Christine; Guilard, Roger

2012-11-19

The first synthesis and self-organization of zinc β-phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn(II) complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-β-(dialkoxyphosphoryl)porphyrins 1 Zn-3 Zn starting from the β-bromo-substituted zinc porphyrinate ZnTPPBr (TPP = tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)(2) (R = Et, iPr, nBu). The derivatives 1 Zn-3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72% yield. The use of a Pd-catalyzed C-P bond-forming reaction was further extended to the synthesis of β-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H(2)TPPBr(4) led to the formation of a mixture of the 2,12- and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H(2) and 6 H(2) in 81% total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic and spectroscopic studies of the [palladium(Ar-bian)]-catalyzed semi-hydrogenation of 4-octyne.

PubMed

Kluwer, Alexander M; Koblenz, Tehila S; Jonischkeit, Thorsten; Woelk, Klaus; Elsevier, Cornelis J

2005-11-09

The kinetics of the stereoselective semi-hydrogenation of 4-octyne in THF by the highly active catalyst [Pd{(m,m'-(CF(3))(2)C(6)H(3))-bian}(ma)] (2) (bian = bis(imino)acenaphthene; ma = maleic anhydride) has been investigated. The rate law under hydrogen-rich conditions is described by r = k[4-octyne](0.65)[Pd][H(2)], showing first order in palladium and dihydrogen and a broken order in substrate. Parahydrogen studies have shown that a pairwise transfer of hydrogen atoms occurs in the rate-limiting step. In agreement with recent theoretical results, the proposed mechanism consists of the consecutive steps: alkyne coordination, heterolytic dihydrogen activation (hydrogenolysis of one Pd-N bond), subsequent hydro-palladation of the alkyne, followed by addition of N-H to palladium, reductive coupling of vinyl and hydride and, finally, substitution of the product alkene by the alkyne substrate. Under hydrogen-limiting conditions, side reactions occur, that is, formation of catalytically inactive palladacycles by oxidative alkyne coupling. Furthermore, it has been shown that (Z)-oct-4-ene is the primary reaction product, from which the minor product (E)-oct-4-ene is formed by an H(2)-assisted, palladium-catalyzed isomerization reaction.

Real-Time Polymerase Chain Reaction for Detection of Schistosoma DNA in Small-Volume Urine Samples Reflects Focal Distribution of Urogenital Schistosomiasis in Primary School Girls in KwaZulu Natal, South Africa

PubMed Central

Pillay, Pavitra; Taylor, Myra; Zulu, Siphosenkosi G.; Gundersen, Svein G.; Verweij, Jaco J.; Hoekstra, Pytsje; Brienen, Eric A. T.; Kleppa, Elisabeth; Kjetland, Eyrun F.; van Lieshout, Lisette

2014-01-01

Schistosoma haematobium eggs and Schistosoma DNA levels were measured in urine samples from 708 girls recruited from 18 randomly sampled primary schools in South Africa. Microscopic analysis of two 10-mL urine subsamples collected on three consecutive days confirmed high day-to-day variation; 103 (14.5%) girls had positive results at all six examinations, and at least one positive sample was seen in 225 (31.8%) girls. Schistosoma-specific DNA, which was measured in a 200-μL urine subsample by using real-time polymerase chain reaction, was detected in 180 (25.4%) cases, and levels of DNA corresponded significantly with average urine egg excretion. In concordance with microscopic results, polymerase chain reaction results were significantly associated with history of gynecologic symptoms and confirmed highly focal distribution of urogenital schistosomiasis. Parasite-specific DNA detection has a sensitivity comparable to single urine microscopy and could be used as a standardized high-throughput procedure to assess distribution of urogenital schistosomiasis in relatively large study populations by using small sample volumes. PMID:24470560

Magnetically separable maghemite/montmorillonite composite as an efficient heterogeneous Fenton-like catalyst for phenol degradation.

PubMed

Jin, Mingjie; Long, Mingce; Su, Hanrui; Pan, Yue; Zhang, Qiuzhuo; Wang, Juan; Zhou, Baoxue; Zhang, Yanwu

2017-01-01

To develop highly efficient and conveniently separable iron containing catalysts is crucial to remove recalcitrant organic pollutants in wastewater through a heterogeneous Fenton-like reaction. A maghemite/montmorillonite composite was synthesized by a coprecipitation and calcination method. The physiochemical properties of catalysts were characterized by XRD, TEM, nitrogen physisorption, thermogravimetric analysis/differential scanning calorimetry (TG/DSC), zeta potential, and magnetite susceptibility measurements. The influence of calcination temperatures and reaction parameters was investigated. The calcined composites retain magnetism because the presence of montmorillonite inhibited the growth of γ-Fe 2 O 3 nanoparticles, as well as their phase transition. The catalytic activities for phenol degradation were significantly enhanced by calcinations, which strengthen the interaction between iron oxides and aluminosilicate framework and result in more negatively charged surface. The composite (73 m 2 /g) calcined at 350 °C had the highest catalytic activities, with more than 99 % phenol reduction after only 35 min reaction at pH 3.6. Simultaneously, this catalyst exhibited high stability, low iron leaching, and magnetically separable ability for consecutive usage, making it promising for the removal of recalcitrant organic pollutants in wastewater.

Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.

PubMed

Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere

2015-02-16

The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noise emitted from road, rail and air traffic and their effects on sleep

NASA Astrophysics Data System (ADS)

Griefahn, Barbara; Marks, Anke; Robens, Sibylle

2006-08-01

This study compared the effects of road, rail, and aircraft noise and tested the applicability of the equivalent noise level for the evaluation of sleep disturbances. Sixteen women and 16 men (19-28 years) slept during 3 consecutive weeks in the laboratory. Eight persons slept in quiet throughout. Twenty-four persons were exposed to road, rail, or aircraft noise with weekly permuted changes. Each week consisted of a random sequence of a quiet night (32 dBA) and 3 nights with equivalent noise levels of 39, 44, and 50 dBA and maximum levels of 50-62, 56-68, and 62-74 dBA, respectively. The polysomnogram was recorded during all nights, sleep quality was assessed and performance tests were completed in the morning. Subjectively evaluated sleep quality decreased and reaction time increased gradually with noise levels, whereas most physiological variables revealed the same reactions to both the lower and considerably stronger reactions to the highest noise load. Aircraft noise, rail and road traffic noise caused similar after-effects but physiological sleep parameters were most severely affected by rail noise. The equivalent noise level seems to be a suitable predictor for subjectively evaluated sleep quality but not for physiological sleep disturbances.

Mechanism of multinucleon transfer reaction based on the GRAZING model and DNS model

NASA Astrophysics Data System (ADS)

Wen, Pei-wei; Li, Cheng; Zhu, Long; Lin, Cheng-jian; Zhang, Feng-shou

2017-11-01

Multinucleon transfer (MNT) reactions have been studied by either the GRAZING model or dinuclear system (DNS) model before. MNT reactions in the grazing regime have been described quite well by the GRAZING model. The DNS model is able to deal with MNT reactions, which happen in the closer overlapped regime after contact of two colliding nuclei. Since MNT reactions can happen in both areas and cannot be distinguished in view of experimental work, it is beneficial to compare these two models to clarify mechanism of MNT reactions. In this study, the mechanism of the MNT reaction has been studied by comparing the GRAZING model and DNS model for the first time. Reaction systems 136Xe+208Pb at {E}{{c}.{{m}}.}=450 MeV and 64Ni+238U at {E}{{c}.{{m}}.}=307 MeV are taken as examples in this paper. It is found that the gradients of transfer cross sections with respect to the impact parameter of the GRAZING model and DNS model are mainly concentrated on two different areas, which represents two kinds of transfer mechanisms. The theoretical framework of these two models are exclusive according to whether capture happens, which guarantees that the theoretical results calculated by these two models have no overlap and can be added up. Results indicate that the description of experimental MNT reaction cross sections can be significantly improved if calculations of the GRAZING model and DNS model are both considered.

Viscoelastic substance in prefilled syringe as an etiology of Toxic Anterior Segment Syndrome.

PubMed

Althomali, Talal Abdulrahman

2016-09-01

Toxic Anterior Segment Syndrome (TASS) is an acute postoperative inflammatory reaction in which a noninfectious substance enters the anterior segment and induces toxic damage to the intraocular tissues. To present etiologic investigation of two consecutive clusters of TASS. TASS outbreak and investigation: This paper presents two consecutive clusters of TASS in 15 of the 24 uneventful surgeries and the investigation carried out to find the etiology. After the occurrence of first cluster of TASS, sterilization-related etiology was explored; however, we did not find any lacunae in the sterilization and cleaning process in the operating theater (OT). Nevertheless, multiple changes in cleaning process were implemented. Still a second cluster of TASS was encountered in the following session of OT. Several other factors which include preservatives, hand gloves, intraocular lenses, medications/solutions, intraocular penetration of topically administered drugs, and viscoelastics were investigated as the possible etiology of the second consecutive cluster of TASS; however, most of them were ruled out. The newly introduced viscoelastic I-visc® 1.4% sodium hyaluronate (I medical, i-Medical Ophthalmic International GmbH, Heidelberg, Germany) was thought to be the most likely cause and was replaced with previously in use sodium hyaluronate 1.5% and lidocaine hydrochloride 1% (Visthesia, CZ, Germany) in the following session of OT. No further TASS incident was encountered after replacing the viscoelastic. Investigation revealed that 1.4% sodium hyaluronate in prefilled syringe (PFS) (I-visc® 1.4%) was the etiologic factor of two consecutive clusters of TASS. While TASS due to residual denatured ophthalamic viscosurgical devices (OVDs) is a common knowledge, current study brings out that even disposable viscoelastic material supplied in PFSs can be an etiology of TASS. It is important to recognize that contamination of OVDs with endotoxins can occur at the time of manufacturing. Therefore, in the absence of appropriate guidelines for ophthalmic preparations, endotoxin limit for medical preparations (i.e. <0.5 endotoxin units/ml) must be considered during OVD manufacture.

Genetic parameters for stayability to consecutive calvings in Zebu cattle.

PubMed

Silva, D O; Santana, M L; Ayres, D R; Menezes, G R O; Silva, L O C; Nobre, P R C; Pereira, R J

2017-12-22

Longer-lived cows tend to be more profitable and the stayability trait is a selection criterion correlated to longevity. An alternative to the traditional approach to evaluate stayability is its definition based on consecutive calvings, whose main advantage is the more accurate evaluation of young bulls. However, no study using this alternative approach has been conducted for Zebu breeds. Therefore, the objective of this study was to compare linear random regression models to fit stayability to consecutive calvings of Guzerá, Nelore and Tabapuã cows and to estimate genetic parameters for this trait in the respective breeds. Data up to the eighth calving were used. The models included the fixed effects of age at first calving and year-season of birth of the cow and the random effects of contemporary group, additive genetic, permanent environmental and residual. Random regressions were modeled by orthogonal Legendre polynomials of order 1 to 4 (2 to 5 coefficients) for contemporary group, additive genetic and permanent environmental effects. Using Deviance Information Criterion as the selection criterion, the model with 4 regression coefficients for each effect was the most adequate for the Nelore and Tabapuã breeds and the model with 5 coefficients is recommended for the Guzerá breed. For Guzerá, heritabilities ranged from 0.05 to 0.08, showing a quadratic trend with a peak between the fourth and sixth calving. For the Nelore and Tabapuã breeds, the estimates ranged from 0.03 to 0.07 and from 0.03 to 0.08, respectively, and increased with increasing calving number. The additive genetic correlations exhibited a similar trend among breeds and were higher for stayability between closer calvings. Even between more distant calvings (second v. eighth), stayability showed a moderate to high genetic correlation, which was 0.77, 0.57 and 0.79 for the Guzerá, Nelore and Tabapuã breeds, respectively. For Guzerá, when the models with 4 or 5 regression coefficients were compared, the rank correlations between predicted breeding values for the intercept were always higher than 0.99, indicating the possibility of practical application of the least parameterized model. In conclusion, the model with 4 random regression coefficients is recommended for the genetic evaluation of stayability to consecutive calvings in Zebu cattle.

The consecutive dry days to trigger rainfall over West Africa

NASA Astrophysics Data System (ADS)

Lee, J. H.

2018-01-01

In order to resolve contradictions in addressing a soil moisture-precipitation feedback mechanism over West Africa and to clarify the impact of antecedent soil moisture on subsequent rainfall evolution, we first validated various data sets (SMOS satellite soil moisture observations, NOAH land surface model, TRMM rainfall, CMORPH rainfall and HadGEM climate models) with the Analyses Multidisciplinaires de la Mousson Africaine (AMMA) field campaign data. Based on this analysis, it was suggested that biases of data sets might cause contradictions in studying mechanisms. Thus, by taking into account uncertainties in data, it was found that the approach of consecutive dry days (i.e. a relative comparison of time-series) showed consistency across various data sets, while the direct comparison approach for soil moisture state and rainfall did not. Thus, it was discussed that it may be difficult to directly relate rain with soil moisture as the absolute value, however, it may be reasonable to compare a temporal progress of the variables. Based upon the results consistently showing a positive relationship between the consecutive dry days and rainfall, this study supports a negative feedback often neglected by climate model structure. This approach is less sensitive to interpretation errors arising from systematic errors in data sets, as this measures a temporal gradient of soil moisture state.

Water oxidation catalysed by manganese compounds: from complexes to 'biomimetic rocks'.

PubMed

Wiechen, Mathias; Berends, Hans-Martin; Kurz, Philipp

2012-01-07

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.

Contact allergy to common ingredients in hair dyes.

PubMed

Søsted, Heidi; Rustemeyer, Thomas; Gonçalo, Margarida; Bruze, Magnus; Goossens, An; Giménez-Arnau, Ana M; Le Coz, Christophe J; White, Ian R; Diepgen, Thomas L; Andersen, Klaus E; Agner, Tove; Maibach, Howard; Menné, Torkil; Johansen, Jeanne D

2013-07-01

p-Phenylenediamine (PPD) is the primary patch test screening agent for hair dye contact allergy, and approximately 100 different hair dye chemicals are allowed. To examine whether PPD is an optimal screening agent for diagnosing hair dye allergy or whether other clinically important sensitizers exist. Two thousand nine hundred and thirty-nine consecutive patients in 12 dermatology clinics were patch tested with five hair dyes available from patch test suppliers. Furthermore, 22 frequently used hair dye ingredients not available from patch test suppliers were tested in subgroups of ~500 patients each. A positive reaction to PPD was found in 4.5% of patients, and 2.8% reacted to toluene-2,5-diamine (PTD), 1.8% to p-aminophenol, 1% to m-aminophenol, and 0.1% to resorcinol; all together, 5.3% (n = 156). Dying hair was the most frequently reported cause of the allergy (55.4%); so-called 'temporary henna' tattoos were the cause in 8.5% of the cases. p-Methylaminophenol gave a reaction in 20 patients (2.2%), 3 of them with clinical relevance, and no co-reaction with the above five well-known hair dyes. Hair dyes are the prime cause of PPD allergy. PPD identifies the majority of positive reactions to PTD, p-aminophenol and m-aminophenol, but not all, which justifies additional testing with hair dye ingredients from the used product. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Monitoring contact sensitization to p-phenylenediamine (PPD) by patch testing with PPD 0.3% in petrolatum.

PubMed

Geier, Johannes; Ballmer-Weber, Barbara K; Dickel, Heinrich; Frosch, Peter J; Bircher, Andreas; Weisshaar, Elke; Hillen, Uwe

2013-07-01

Being a contact allergen of general relevance, p-phenylenediamine (PPD) is patch tested in the baseline series. However, PPD 1% in petrolatum may actively sensitize. Patch testing with PPD at 0.35% pet. proved to be safe, as far as active sensitization is concerned. To determine whether PPD 0.3% pet. reliably detects PPD sensitization. Patch testing with PPD 0.3% pet. and 1% pet. synchronously was performed in consecutive patients in a multicentre study within the Information Network of Departments of Dermatology. Altogether, 2042 patients were patch tested. PPD 1% pet. yielded 6.0% positive reactions (n = 123), and PPD 0.3% pet. yielded 4.7% (n = 95). The synchronous reproducibility of PPD reactions was similar as known from parallel patch tests with identical PPD concentrations. The diagnostic properties of PPD 0.3% pet. expressed as reaction index and positivity ratio were good. Of the 123 patients reacting to PPD 1% pet., 32 (26%) had no positive reaction to PPD 0.3% pet. In 22 of these 32 patients (69%), no clinical relevance could be found. As patch testing with PPD 0.3% pet. is reliable according to our results, we recommend replacing PPD 1% pet. in the baseline series with PPD 0.3% pet. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Further important sensitizers in patients sensitive to fragrances.

PubMed

Frosch, P J; Johansen, J D; Menné, T; Pirker, C; Rastogi, S C; Andersen, K E; Bruze, M; Goossens, A; Lepoittevin, J P; White, I R

2002-08-01

The aim of this study was to determine the frequency of responses to selected fragrance materials in consecutive patients patch tested in 6 dermatological centres in Europe. 1855 patients were evaluated with the 8% fragrance mix (FM) and 14 other frequently used well-defined fragrance chemicals (series I). Each patient was classified regarding a history of adverse reactions to fragrances: certain, probable, questionable, none. Reactions to FM occurred in 11.3% of the subjects. The 6 substances with the highest reactivity following FM were Lyral (2.7%), citral (1.1%), farnesol P (0.5%), citronellol (0.4%), hexyl cinnamic aldehyde (0.3%), and coumarin (0.3%). 41 (2.2%) of the patients reacted only to materials of series I and not to FM. 6.6% of 1855 patients gave a history of adverse reactions to fragrances which was classified as certain. This group reacted to FM only in 41.1%, to series I and FM in 12.0% and to series I only in 7.2%. 74.3% of the 39 patients reacting to both FM and 1 of the materials of series I had any type of positive fragrance history, which was significantly higher in comparison to those with isolated reactions to series I (53.6% of 41), p = 0.04. The study identified further sensitizers relevant for patch testing of patients with contact dermatitis, of which Lyral is the most important single chemical.

Ground reaction forces on stairs: effects of stair inclination and age.

PubMed

Stacoff, Alex; Diezi, Christian; Luder, Gerhard; Stüssi, Edgar; Kramers-de Quervain, Inès A

2005-01-01

The goals of the study were to compare data of vertical ground reaction force (GRF) parameters during level walking, stair ascent and descent on three different stair inclinations and three different age groups. Twenty healthy subjects of three age groups (young 33.7 years; middle 63.6 years; old 76.5 years) were tested during the seven test conditions with 8-10 repetitions. Vertical forces were measured during two consecutive steps with force plates embedded in the walkway and the staircase. The results showed that during level walking the vertical GRF curves were very regular and repetitive, the trail-to-trial variability and left-right asymmetry of defined test parameters being around 2-5% and 3-5%. During stair ascent the vertical GRF force pattern was found to change slightly compared to level gait, but considerably compared to stair descent. On the steep stair the average vertical load increased up to 1.6 BW, and variability (5-10%) and asymmetry (5-15%) were increased significantly. The steep stair descent condition was found to be the most demanding test showing the largest variability and asymmetry and thus, the least stable gait pattern. Age was found to be a factor which should be considered, because the young age group walked faster and produced larger vertical GRF maxima during level walking and on stair ascent than the middle and old age group. Differences between the middle and old age group were found to be small. The present investigation is the first to provide normative data of GRF parameters on gait variability and symmetry of two consecutive steps during level gait and stair ambulation. It is the intention that the results of this study may be used as a basis for comparison with patient data.

Determination of optimum processing temperature for transformation of glyceryl monostearate.

PubMed

Yajima, Toshio; Itai, Shigeru; Takeuchi, Hirofumi; Kawashima, Yoshiaki

2002-11-01

The purpose of this study was to clarify the mechanism of transformation from alpha-form to beta-form via beta'-form of glyceryl monostearate (GM) and to determine the optimum conditions of heat-treatment for physically stabilizing GM in a pharmaceutical formulation. Thermal analysis repeated twice using a differential scanning calorimeter (DSC) were performed on mixtures of two crystal forms. In the first run (enthalpy of melting: DeltaH1), two endothermic peaks of alpha-form and beta-form were observed. However, in the second run (enthalpy of melting: DeltaH2), only the endothermic peak of the alpha-form was observed. From a strong correlation observed between the beta-form content in the mixture of alpha-form and beta-form and the enthalpy change, (DeltaH1-DeltaH2)/DeltaH2, beta-form content was expressed as a function of the enthalpy change. Using this relation, the stable beta-form content during the heat-treatment could be determined, and the maximum beta-form content was obtained when the heat-treatment was carried out at 50 degrees C. An inflection point existed in the time course of transformation of alpha-form to beta-form. It was assumed that almost all of alpha-form transformed to beta'-form at this point, and that subsequently only transformation from beta'-form to beta-form occurred. Based on this aspect, the transformation rate equations were derived as consecutive reaction. Experimental data coincided well with the theoretical curve. In conclusion, GM was transformed in the consecutive reaction, and 50 degrees C was the optimum heat-treatment temperature for transforming GM from the alpha-form to the stable beta-form.

Indoor mold exposure associated with neurobehavioral and pulmonary impairment: a preliminary report.

PubMed

Kilburn, Kaye H

2003-07-01

Recently, patients who have been exposed indoors to mixed molds, spores, and mycotoxins have reported asthma, airway irritation and bleeding, dizziness, and impaired memory and concentration, all of which suggest the presence of pulmonary and neurobehavioral problems. The author evaluated whether such patients had measurable pulmonary and neurobehavioral impairments by comparing consecutive cases in a series vs. a referent group. Sixty-five consecutive outpatients exposed to mold in their respective homes in Arizona, California, and Texas were compared with 202 community subjects who had no known mold or chemical exposures. Balance, choice reaction time, color discrimination, blink reflex, visual fields, grip, hearing, problem-solving, verbal recall, perceptual motor speed, and memory were measured. Medical histories, mood states, and symptom frequencies were recorded with checklists, and spirometry was used to measure various pulmonary volumes and flows. Neurobehavioral comparisons were made after individual measurements were adjusted for age, educational attainment, and sex. Significant differences between groups were assessed by analysis of variance; a p value of less than 0.05 was used for all statistical tests. The mold-exposed group exhibited decreased function for balance, reaction time, blink-reflex latency, color discrimination, visual fields, and grip, compared with referents. The exposed group's scores were reduced for the following tests: digit-symbol substitution, peg placement, trail making, verbal recall, and picture completion. Twenty-one of 26 functions tested were abnormal. Airway obstructions were found, and vital capacities were reduced. Mood state scores and symptom frequencies were elevated. The author concluded that indoor mold exposures were associated with neurobehavioral and pulmonary impairments that likely resulted from the presence of mycotoxins, such as trichothecenes.

How accurate is automated gap filling of metabolic models?

PubMed

Karp, Peter D; Weaver, Daniel; Latendresse, Mario

2018-06-19

Reaction gap filling is a computational technique for proposing the addition of reactions to genome-scale metabolic models to permit those models to run correctly. Gap filling completes what are otherwise incomplete models that lack fully connected metabolic networks. The models are incomplete because they are derived from annotated genomes in which not all enzymes have been identified. Here we compare the results of applying an automated likelihood-based gap filler within the Pathway Tools software with the results of manually gap filling the same metabolic model. Both gap-filling exercises were applied to the same genome-derived qualitative metabolic reconstruction for Bifidobacterium longum subsp. longum JCM 1217, and to the same modeling conditions - anaerobic growth under four nutrients producing 53 biomass metabolites. The solution computed by the gap-filling program GenDev contained 12 reactions, but closer examination showed that solution was not minimal; two of the twelve reactions can be removed to yield a set of ten reactions that enable model growth. The manually curated solution contained 13 reactions, eight of which were shared with the 12-reaction computed solution. Thus, GenDev achieved recall of 61.5% and precision of 66.6%. These results suggest that although computational gap fillers are populating metabolic models with significant numbers of correct reactions, automatically gap-filled metabolic models also contain significant numbers of incorrect reactions. Our conclusion is that manual curation of gap-filler results is needed to obtain high-accuracy models. Many of the differences between the manual and automatic solutions resulted from using expert biological knowledge to direct the choice of reactions within the curated solution, such as reactions specific to the anaerobic lifestyle of B. longum.

Structure of Naegleria Tet-like dioxygenase (NgTet1) in complexes with a reaction intermediate 5-hydroxymethylcytosine DNA

DOE PAGES

Hashimoto, Hideharu; Pais, June E.; Dai, Nan; ...

2015-08-31

The family of ten-eleven translocation (Tet) dioxygenases is widely distributed across the eukaryotic tree of life, from mammals to the amoeboflagellate Naegleria gruberi. Like mammalian Tet proteins, the Naegleria Tet-like protein, NgTet1, acts on 5-methylcytosine (5mC) and generates 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC) and 5-carboxylcytosine (5caC) in three consecutive, Fe(II)- and α-ketoglutarate-dependent oxidation reactions. The two intermediates, 5hmC and 5fC, could be considered either as the reaction product of the previous enzymatic cycle or the substrate for the next cycle. Here we present a new crystal structure of NgTet1 in complex with DNA containing a 5hmC. Along with the previously solvedmore » NgTet1–5mC structure, the two complexes offer a detailed picture of the active site at individual stages of the reaction cycle. In the crystal, the hydroxymethyl (OH-CH 2-) moiety of 5hmC points to the metal center, representing the reaction product of 5mC hydroxylation. The hydroxyl oxygen atom could be rotated away from the metal center, to a hydrophobic pocket formed by Ala212, Val293 and Phe295. Such rotation turns the hydroxyl oxygen atom away from the product conformation, and exposes the target CH 2 towards the metal-ligand water molecule, where a dioxygen O 2 molecule would occupy to initiate the next round of reaction by abstracting a hydrogen atom from the substrate. The Ala212-to-Val (A212V) mutant profoundly limits the product to 5hmC, probably due to the reduced hydrophobic pocket size restricts the binding of 5hmC as a substrate.« less

The cortisol awakening response is associated with performance of a serial sequence reaction time task.

PubMed

Hodyl, Nicolette A; Schneider, Luke; Vallence, Ann-Maree; Clow, Angela; Ridding, Michael C; Pitcher, Julia B

2016-02-01

There is emerging evidence of a relationship between the cortisol awakening response (CAR) and the neural mechanisms underlying learning and memory. The aim of this study was to determine whether the CAR is associated with acquisition, retention and overnight consolidation or improvement of a serial sequence reaction time task. Salivary samples were collected at 0, 15, 30 and 45 min after awakening in 39 healthy adults on 2 consecutive days. The serial sequence reaction time task was repeated each afternoon. Participants completed the perceived stress scale and provided salivary samples prior to testing for cortisol assessment. While the magnitude of the CAR (Z score) was not associated with either baseline performance or the timed improvement during task acquisition of the serial sequence task, a positive correlation was observed with reaction times during the stable performance phase on day 1 (r=0.373, p=0.019). Residuals derived from the relationship between baseline and stable phase reaction times on day 1 were used as a surrogate for the degree of learning: these residuals were also correlated with the CAR mean increase on day 1 (r=0.357, p=0.048). Task performance on day 2 was not associated with the CAR obtained on this same day. No association was observed between the perceived stress score, cortisol at testing or task performance. These data indicate that a smaller CAR in healthy adults is associated with a greater degree of learning and faster performance of a serial sequence reaction time task. These results support recognition of the CAR as an important factor contributing to cognitive performance throughout the day. Copyright © 2015 Elsevier B.V. All rights reserved.

Limonene and its ozone-initiated reaction products attenuate allergic lung inflammation in mice.

PubMed

Hansen, Jitka S; Nørgaard, Asger W; Koponen, Ismo K; Sørli, Jorid B; Paidi, Maya D; Hansen, Søren W K; Clausen, Per Axel; Nielsen, Gunnar D; Wolkoff, Peder; Larsen, Søren Thor

2016-11-01

Inhalation of indoor air pollutants may cause airway irritation and inflammation and is suspected to worsen allergic reactions. Inflammation may be due to mucosal damage, upper (sensory) and lower (pulmonary) airway irritation due to activation of the trigeminal and vagal nerves, respectively, and to neurogenic inflammation. The terpene, d-limonene, is used as a fragrance in numerous consumer products. When limonene reacts with the pulmonary irritant ozone, a complex mixture of gas and particle phase products is formed, which causes sensory irritation. This study investigated whether limonene, ozone or the reaction mixture can exacerbate allergic lung inflammation and whether airway irritation is enhanced in allergic BALB/cJ mice. Naïve and allergic (ovalbumin sensitized) mice were exposed via inhalation for three consecutive days to clean air, ozone, limonene or an ozone-limonene reaction mixture. Sensory and pulmonary irritation was investigated in addition to ovalbumin-specific antibodies, inflammatory cells, total protein and surfactant protein D in bronchoalveolar lavage fluid and hemeoxygenase-1 and cytokines in lung tissue. Overall, airway allergy was not exacerbated by any of the exposures. In contrast, it was found that limonene and the ozone-limonene reaction mixture reduced allergic inflammation possibly due to antioxidant properties. Ozone induced sensory irritation in both naïve and allergic mice. However, allergic but not naïve mice were protected from pulmonary irritation induced by ozone. This study showed that irritation responses might be modulated by airway allergy. However, aggravation of allergic symptoms was observed by neither exposure to ozone nor exposure to ozone-initiated limonene reaction products. In contrast, anti-inflammatory properties of the tested limonene-containing pollutants might attenuate airway allergy.

Multinational experience with hypersensitivity drug reactions in Latin America.

PubMed

Jares, Edgardo José; Sánchez-Borges, Mario; Cardona-Villa, Ricardo; Ensina, Luis Felipe; Arias-Cruz, Alfredo; Gómez, Maximiliano; Barayazarra, Susana; Bernstein, Jonathan A; Serrano, Carlos D; Cuello, Mabel Noemi; Morfin-Maciel, Blanca María; De Falco, Alicia; Cherrez-Ojeda, Iván

2014-09-01

Epidemiologic drug allergy data from Latin America are scarce, and there are no studies on specific procedures focusing on this topic in Latin America. To assess the clinical characteristics and management of hypersensitivity drug reactions in different Latin American countries. An European Network of Drug Allergy questionnaire survey was implemented in 22 allergy units in 11 Latin American countries to report on consecutive patients who presented with a suspected hypersensitivity drug reaction. Each unit used its own protocols to investigate patients. Included were 868 hypersensitivity drug reactions in 862 patients (71% of adults and elderly patients were women and 51% of children were girls, P = .0001). Children presented with less severe reactions than adults and elderly patients (P < .0001). Urticaria and angioedema accounted for the most frequent clinical presentations (71%), whereas anaphylaxis was present in 27.3% of cases. There were no deaths reported. Nonsteroidal anti-inflammatory drugs (52.3%), β-lactam antibiotics (13.8%), and other antibiotics (10.1%) were the drugs used most frequently. Skin prick tests (16.7%) and provocation tests (34.2%) were the study procedures most commonly used. A large proportion of patients were treated in the emergency department (62%) with antihistamines (68%) and/or corticosteroids (53%). Only 22.8% of patients presenting with anaphylaxis received epinephrine. Nonsteroidal anti-inflammatory drugs and antibiotics were the drugs used in at least 75% of patients. More than half the reactions were treated in the emergency department, whereas epinephrine was administered in fewer than 25% of patients with anaphylaxis. Dissemination of guidelines for anaphylaxis among primary and emergency department physicians should be encouraged. Copyright © 2014 American College of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meemken, Fabian; Müller, Philipp; Hungerbühler, Konrad

Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the usemore » of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated.« less

Acute Versus Chronic Partial Sleep Deprivation in Middle-Aged People: Differential Effect on Performance and Sleepiness

PubMed Central

Philip, Pierre; Sagaspe, Patricia; Prague, Mélanie; Tassi, Patricia; Capelli, Aurore; Bioulac, Bernard; Commenges, Daniel; Taillard, Jacques

2012-01-01

Study Objective: To evaluate the effects of acute sleep deprivation and chronic sleep restriction on vigilance, performance, and self-perception of sleepiness. Design: Habitual night followed by 1 night of total sleep loss (acute sleep deprivation) or 5 consecutive nights of 4 hr of sleep (chronic sleep restriction) and recovery night. Participants: Eighteen healthy middle-aged male participants (age [(± standard deviation] = 49.7 ± 2.6 yr, range 46-55 yr). Measurements: Multiple sleep latency test trials, Karolinska Sleepiness Scale scores, simple reaction time test (lapses and 10% fastest reaction times), and nocturnal polysomnography data were recorded. Results: Objective and subjective sleepiness increased immediately in response to sleep restriction. Sleep latencies after the second and third nights of sleep restriction reached levels equivalent to those observed after acute sleep deprivation, whereas Karolinska Sleepiness Scale scores did not reach these levels. Lapse occurrence increased after the second day of sleep restriction and reached levels equivalent to those observed after acute sleep deprivation. A statistical model revealed that sleepiness and lapses did not progressively worsen across days of sleep restriction. Ten percent fastest reaction times (i.e., optimal alertness) were not affected by acute or chronic sleep deprivation. Recovery to baseline levels of alertness and performance occurred after 8-hr recovery night. Conclusions: In middle-aged study participants, sleep restriction induced a high increase in sleep propensity but adaptation to chronic sleep restriction occurred beyond day 3 of restriction. This sleepiness attenuation was underestimated by the participants. One recovery night restores daytime sleepiness and cognitive performance deficits induced by acute or chronic sleep deprivation. Citation: Philip P; Sagaspe P; Prague M; Tassi P; Capelli A; Bioulac B; Commenges D; Taillard J. Acute versus chronic partial sleep deprivation in middle-aged people: differential effect on performance and sleepiness. SLEEP 2012;35(7):997–1002. PMID:22754046

DNA Bipedal Motor Achieves a Large Number of Steps Due to Operation Using Microfluidics-Based Interface.

PubMed

Tomov, Toma E; Tsukanov, Roman; Glick, Yair; Berger, Yaron; Liber, Miran; Avrahami, Dorit; Gerber, Doron; Nir, Eyal

2017-04-25

Realization of bioinspired molecular machines that can perform many and diverse operations in response to external chemical commands is a major goal in nanotechnology, but current molecular machines respond to only a few sequential commands. Lack of effective methods for introduction and removal of command compounds and low efficiencies of the reactions involved are major reasons for the limited performance. We introduce here a user interface based on a microfluidics device and single-molecule fluorescence spectroscopy that allows efficient introduction and removal of chemical commands and enables detailed study of the reaction mechanisms involved in the operation of synthetic molecular machines. The microfluidics provided 64 consecutive DNA strand commands to a DNA-based motor system immobilized inside the microfluidics, driving a bipedal walker to perform 32 steps on a DNA origami track. The microfluidics enabled removal of redundant strands, resulting in a 6-fold increase in processivity relative to an identical motor operated without strand removal and significantly more operations than previously reported for user-controlled DNA nanomachines. In the motor operated without strand removal, redundant strands interfere with motor operation and reduce its performance. The microfluidics also enabled computer control of motor direction and speed. Furthermore, analysis of the reaction kinetics and motor performance in the absence of redundant strands, made possible by the microfluidics, enabled accurate modeling of the walker processivity. This enabled identification of dynamic boundaries and provided an explanation, based on the "trap state" mechanism, for why the motor did not perform an even larger number of steps. This understanding is very important for the development of future motors with significantly improved performance. Our universal interface enables two-way communication between user and molecular machine and, relying on concepts similar to that of solid-phase synthesis, removes limitations on the number of external stimuli. This interface, therefore, is an important step toward realization of reliable, processive, reproducible, and useful externally controlled DNA nanomachines.

mRNA expression pattern of selected candidate genes differs in bovine oviductal epithelial cells in vitro compared with the in vivo state and during cell culture passages.

PubMed

Danesh Mesgaran, Sadjad; Sharbati, Jutta; Einspanier, Ralf; Gabler, Christoph

2016-08-15

The mammalian oviduct provides the optimal environment for gamete maturation including sperm capacitation, fertilization, and development of the early embryo. Various cell culture models for primary bovine oviductal epithelial cells (BOEC) were established to reveal such physiological events. The aim of this study was to evaluate 17 candidate mRNA expression patterns in oviductal epithelial cells (1) in transition from in vivo cells to in vitro cells; (2) during three consecutive cell culture passages; (3) affected by the impact of LOW or HIGH glucose content media; and (4) influenced by different phases of the estrous cycle in vivo and in vitro. In addition, the release of a metabolite and proteins from BOEC at two distinct cell culture passage numbers was estimated to monitor the functionality. BOEC from 8 animals were isolated and cultured for three consecutive passages. Total RNA was extracted from in vivo and in vitro samples and subjected to reverse transcription quantitative polymerase chain reaction to reveal mRNA expression of selected candidate genes. The release of prostaglandin E2 (PGE2), oviduct-specific glycoprotein 1 (OVGP1) and interleukin 8 (IL8) by BOEC was measured by EIA or ELISA after 24 h. Almost all candidate genes (prostaglandin synthases, enzymes of cellular metabolism and mucins) mRNA expression pattern differed compared in vivo with in vitro state. In addition, transcription of most candidate genes was influenced by the number of cell culture passages. Different glucose medium content did not affect mRNA expression of most candidate genes. The phase of the estrous cycle altered some candidate mRNA expression in BOEC in vitro at later passages. The release of PGE2 and OVGP1 between passages did not differ. However, BOEC in passage 3 released significantly higher amount of IL8 compared with cells in passage 0. This study supports the hypothesis that candidate mRNA expression in BOEC was influenced by transition from the in vivo situation to the new in vitro environment and during consecutive passages. The consequence of cell culture passaging on BOEC ability to release bioactive compounds should be considered.

Immobilization of 5-aminopyridine-2-tetrazole on cross-linked polystyrene for the preparation of a new adsorbent to remove heavy metal ions from aqueous solution.

PubMed

Zhang, Yu; Chen, Youning; Wang, Chaozhan; Wei, Yinmao

2014-07-15

Novel 5-aminopyridine-2-tetrazole-functionalized polystyrene resin (APTZ-PS) was prepared by anchoring 5-aminopyridine-2-carbonitrile onto chloromethylated polystyrene beads (CMPS) and subsequently using the cyano-tetrazole conversion reaction. The APTZ-PS resin was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and specific surface area and pore size analyses. The adsorption experiments of the prepared resin for heavy metal ions were conducted by batch methods. The effects of the experimental conditions, such as pH, contact time and initial metal ion concentration on the adsorption properties of Cu(II), Pb(II) and Hg(II) were investigated. The results showed that the resin possessed perfect adsorption capacities for Cu(II), Pb(II) and Hg(II), and the selectivity was different from the commonly used iminodiacetic acid-chelating resin. The sorption kinetics of the three metal ions followed the pseudo-second-order equation. The adsorption isotherms for Cu(II) and Pb(II) could be better fitted by the Langmuir model than the Freundlich model, whereas the Freundlich model was the best for the Hg(II) ion. Even after five consecutive adsorption-desorption cycles, no obvious change in the adsorption capacity of the resin was found, which implied that the APTZ-PS resin was suitable for the efficient removal of heavy metal ions from aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Stainless steel corrosion scale formed in reclaimed water: Characteristics, model for scale growth and metal element release.

PubMed

Cui, Yong; Liu, Shuming; Smith, Kate; Hu, Hongying; Tang, Fusheng; Li, Yuhong; Yu, Kanghua

2016-10-01

Stainless steels generally have extremely good corrosion resistance, but are still susceptible to pitting corrosion. As a result, corrosion scales can form on the surface of stainless steel after extended exposure to aggressive aqueous environments. Corrosion scales play an important role in affecting water quality. These research results showed that interior regions of stainless steel corrosion scales have a high percentage of chromium phases. We reveal the morphology, micro-structure and physicochemical characteristics of stainless steel corrosion scales. Stainless steel corrosion scale is identified as a podiform chromite deposit according to these characteristics, which is unlike deposit formed during iron corrosion. A conceptual model to explain the formation and growth of stainless steel corrosion scale is proposed based on its composition and structure. The scale growth process involves pitting corrosion on the stainless steel surface and the consecutive generation and homogeneous deposition of corrosion products, which is governed by a series of chemical and electrochemical reactions. This model shows the role of corrosion scales in the mechanism of iron and chromium release from pitting corroded stainless steel materials. The formation of corrosion scale is strongly related to water quality parameters. The presence of HClO results in higher ferric content inside the scales. Cl - and SO 4 2- ions in reclaimed water play an important role in corrosion pitting of stainless steel and promote the formation of scales. Copyright © 2016. Published by Elsevier B.V.

Dynamic routing and spectrum assignment based on multilayer virtual topology and ant colony optimization in elastic software-defined optical networks

NASA Astrophysics Data System (ADS)

Wang, Fu; Liu, Bo; Zhang, Lijia; Zhang, Qi; Tian, Qinghua; Tian, Feng; Rao, Lan; Xin, Xiangjun

2017-07-01

Elastic software-defined optical networks greatly improve the flexibility of the optical switching network while it has brought challenges to the routing and spectrum assignment (RSA). A multilayer virtual topology model is proposed to solve RSA problems. Two RSA algorithms based on the virtual topology are proposed, which are the ant colony optimization (ACO) algorithm of minimum consecutiveness loss and the ACO algorithm of maximum spectrum consecutiveness. Due to the computing power of the control layer in the software-defined network, the routing algorithm avoids the frequent link-state information between routers. Based on the effect of the spectrum consecutiveness loss on the pheromone in the ACO, the path and spectrum of the minimal impact on the network are selected for the service request. The proposed algorithms have been compared with other algorithms. The results show that the proposed algorithms can reduce the blocking rate by at least 5% and perform better in spectrum efficiency. Moreover, the proposed algorithms can effectively decrease spectrum fragmentation and enhance available spectrum consecutiveness.

Analysis of dental arch relationships in Swedish unilateral cleft lip and palate subjects: 20-year longitudinal consecutive series treated with delayed hard palate closure.

PubMed

Lilja, Jan; Mars, Michael; Elander, Anna; Enocson, Lars; Hagberg, Catharina; Worrell, Emma; Batra, Puneet; Friede, Hans

2006-09-01

To evaluate the dental arch relationships for a consecutive series from Goteborg, Sweden, who had delayed hard palate closure. Retrospective study. Sahlgrenska University Hospital, Goteborg, Sweden. The dental study models of 104 consecutive unilateral cleft lip and palate subjects. The study cohort was born between 1979 and 1994. Longitudinal records were available at ages 5 (n = 94), 10 (n = 97), 16 (n = 59), and 19 years (n = 46). Five assessors rated models according to the GOSLON Yardstick on two separate occasions each. These patients had been operated upon according to the Goteborg protocol of delayed hard palate closure (at age 8 years). 85% of subjects were rated in groups 1 and 2 (excellent or very good outcome), 12% were rated in group 3 (satisfactory), and 3% were assigned to group 4 (poor). No patients presented in Group 5 (very poor). Weighted kappa statistics for double determination of Yardstick allocation for five assessors demonstrated values between .65 and .90 for interrater agreement (good/very good) and between .70 and .90 for intrarater agreement (very good). Delayed hard palate closure as practiced in Goteborg since 1979 has produced the best GOSLON Yardstick ratings in a consecutive series of patients ever recorded worldwide, since the Yardstick was first used in 1983. However, it is noteworthy that a new protocol has been introduced in Goteborg since 1994, in which hard palate closure is done at 3 years due to concerns regarding speech.

Exploring Organic Mechanistic Puzzles with Molecular Modeling

ERIC Educational Resources Information Center

Horowitz, Gail; Schwartz, Gary

2004-01-01

The molecular modeling was used to reinforce more general skills such as deducing and drawing reaction mechanisms, analyzing reaction kinetics and thermodynamics and drawing reaction coordinate energy diagrams. This modeling was done through the design of mechanistic puzzles, involving reactions not familiar to the students.

For t 2 DNA vaccine prevents Forcipomyia taiwana (biting midge) allergy in a mouse model.

PubMed

Lee, M-F; Song, P-P; Lin, T-M; Chiu, Y-T; Chen, Y-H

2016-04-01

Forcipomyia taiwana (biting midge) is the most prevalent allergenic biting insect in Taiwan, and 60% of the exposed subjects develop allergic reactions. Subjects with insect allergy frequently limit their outdoor activities to avoid the annoyingly intense itchy allergic reactions, leading to significant worsening of their quality of life. Allergen-specific immunotherapy is the only known therapy that provides long-term host immune tolerance to the allergen, but is time-consuming and cumbersome. This study tested whether the For t 2 DNA vaccine can prevent allergic symptoms in For t 2-sensitized mice. Two consecutive shots of For t 2 DNA vaccine were given to mice with a 7-day interval before sensitization with recombinant For t 2 proteins, using the two-step sensitization protocol reported previously. The For t 2 DNA vaccine at 50 μg prevented the production of For t 2-specific IgE (P < 0.05), as well as midge allergen-challenge-induced scratch bouts, midge allergen-induced IL-13 and IL-4 production from splenocytes, and inflammatory cell infiltrations in the lesions 48 h after intradermal challenge. This study is the first to demonstrate that DNA vaccine encoding midge allergen is effective in preventing allergic skin inflammation induced by biting midge. Immunotherapy using For t 2 DNA vaccine can protect mice from being sensitized by midge allergen and may be a promising treatment for biting midge allergy in the future. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Concepts, challenges, and successes in modeling thermodynamics of metabolism.

PubMed

Cannon, William R

2014-01-01

The modeling of the chemical reactions involved in metabolism is a daunting task. Ideally, the modeling of metabolism would use kinetic simulations, but these simulations require knowledge of the thousands of rate constants involved in the reactions. The measurement of rate constants is very labor intensive, and hence rate constants for most enzymatic reactions are not available. Consequently, constraint-based flux modeling has been the method of choice because it does not require the use of the rate constants of the law of mass action. However, this convenience also limits the predictive power of constraint-based approaches in that the law of mass action is used only as a constraint, making it difficult to predict metabolite levels or energy requirements of pathways. An alternative to both of these approaches is to model metabolism using simulations of states rather than simulations of reactions, in which the state is defined as the set of all metabolite counts or concentrations. While kinetic simulations model reactions based on the likelihood of the reaction derived from the law of mass action, states are modeled based on likelihood ratios of mass action. Both approaches provide information on the energy requirements of metabolic reactions and pathways. However, modeling states rather than reactions has the advantage that the parameters needed to model states (chemical potentials) are much easier to determine than the parameters needed to model reactions (rate constants). Herein, we discuss recent results, assumptions, and issues in using simulations of state to model metabolism.

Poor short term outcome with a metal-on-metal total hip arthroplasty.

PubMed

Levy, Yadin D; Ezzet, Kace A

2013-08-01

Metal-on-metal (MoM) bearings for total hip arthroplasty (THA) have come under scrutiny with reports of high failure rates. Clinical outcome studies with several commercially available MoM THA bearings remain unreported. We evaluated 78 consecutive MoM THAs from a single manufacturer in 68 patients. Sixty-six received cobalt-chrome (CoCr) monoblock and 12 received modular titanium acetabular cups with internal CoCr liners. Femoral components were titanium with modular necks. At average 2.1 years postoperatively, 12 THAs (15.4%) demonstrated aseptic failure (10 revisions, 2 revision recommended). All revised hips demonstrated capsular necrosis with positive histology reaction for aseptic lymphocytic vasculitis-associated lesions/adverse local tissue reactions. Prosthetic instability following revision surgery was relatively common. Female gender was a strong risk factor for failure, though smaller cups were not. Both monoblock and modular components fared poorly. Corrosion was frequently observed around the proximal and distal end of the modular femoral necks. Copyright © 2013 Elsevier Inc. All rights reserved.

Anethum graveolens Linn. (dill) extract enhances the mounting frequency and level of testicular tyrosine protein phosphorylation in rats*

PubMed Central

Iamsaard, Sitthichai; Prabsattroo, Thawatchai; Sukhorum, Wannisa; Muchimapura, Supaporn; Srisaard, Panee; Uabundit, Nongnut; Thukhammee, Wipawee; Wattanathorn, Jintanaporn

2013-01-01

Objective: To investigate the effect of Anethum graveolens (AG) extracts on the mounting frequency, histology of testis and epididymis, and sperm physiology. Methods: Male rats induced by cold immobilization before treating with vehicle or AG extracts [50, 150, and 450 mg/kg body weight (BW)] via gastric tube for consecutive 1, 7, and 14 d were examined for mounting frequency, testicular phosphorylation level by immunoblotting, sperm concentration, sperm acrosome reaction, and histological structures of testis and epididymis, respectively. Results: AG (50 mg/kg BW) significantly increased the mounting frequency on Days 1 and 7 compared to the control group. Additionally, rat testis treated with 50 mg/kg BW AG showed high levels of phosphorylated proteins as compared with the control group. In histological analyses, AG extract did not affect the sperm concentration, acrosome reaction, and histological structures of testis and epididymis. Conclusions: AG extract enhances the aphrodisiac activity and is not harmful to sperm and male reproductive organs. PMID:23463768

Anethum graveolens Linn. (dill) extract enhances the mounting frequency and level of testicular tyrosine protein phosphorylation in rats.

PubMed

Iamsaard, Sitthichai; Prabsattroo, Thawatchai; Sukhorum, Wannisa; Muchimapura, Supaporn; Srisaard, Panee; Uabundit, Nongnut; Thukhammee, Wipawee; Wattanathorn, Jintanaporn

2013-03-01

To investigate the effect of Anethum graveolens (AG) extracts on the mounting frequency, histology of testis and epididymis, and sperm physiology. Male rats induced by cold immobilization before treating with vehicle or AG extracts [50, 150, and 450 mg/kg body weight (BW)] via gastric tube for consecutive 1, 7, and 14 d were examined for mounting frequency, testicular phosphorylation level by immunoblotting, sperm concentration, sperm acrosome reaction, and histological structures of testis and epididymis, respectively. AG (50 mg/kg BW) significantly increased the mounting frequency on Days 1 and 7 compared to the control group. Additionally, rat testis treated with 50 mg/kg BW AG showed high levels of phosphorylated proteins as compared with the control group. In histological analyses, AG extract did not affect the sperm concentration, acrosome reaction, and histological structures of testis and epididymis. AG extract enhances the aphrodisiac activity and is not harmful to sperm and male reproductive organs.

Effect of stance position on kick performance in taekwondo.

PubMed

Estevan, Isaac; Jandacka, Daniel; Falco, Coral

2013-01-01

In taekwondo, the stance position can potentially affect kick performance. The aim of this study was to analyse mechanical variables in the roundhouse kick in taekwondo according to three stance positions (0°, 45°, 90°). Nine experienced taekwondo athletes performed consecutive kicking trials in a random order according to these three relative positions of the feet on the ground. Measurements for the mechanical analysis were performed using two 3D force plates and an eight-camera motion capture system. The taekwondo athletes' reaction and execution times were shorter when starting from the 0° and 45° stance positions than from the 90° position (P < 0.05). Moreover, the ground reaction force was negatively correlated with execution time and positively with velocity of thigh and shank. Our results suggest that the stance position affects the execution technique of taekwondo athletes' kicks. It is suggested that athletes should not adopt the 90° stance position because it will not enable them to achieve the best performance in the roundhouse kick.

Extraction of microalgal lipids and the influence of polar lipids on biodiesel production by lipase-catalyzed transesterification.

PubMed

Navarro López, Elvira; Robles Medina, Alfonso; González Moreno, Pedro Antonio; Esteban Cerdán, Luis; Molina Grima, Emilio

2016-09-01

In order to obtain microalgal saponifiable lipids (SLs) fractions containing different polar lipid (glycolipids and phospholipids) contents, SLs were extracted from wet Nannochloropsis gaditana microalgal biomass using seven extraction systems, and the polar lipid contents of some fractions were reduced by low temperature acetone crystallization. We observed that the polar lipid content in the extracted lipids depended on the polarity of the first solvent used in the extraction system. Lipid fractions with polar lipid contents between 75.1% and 15.3% were obtained. Some of these fractions were transformed into fatty acid methyl esters (FAMEs, biodiesel) by methanolysis, catalyzed by the lipases Novozym 435 and Rhizopus oryzae in tert-butanol medium. We observed that the reaction velocity was higher the lower the polar lipid content, and that the final FAME conversions achieved after using the same lipase batch to catalyze consecutive reactions decreased in relation to an increase in the polar lipid content. Copyright © 2016 Elsevier Ltd. All rights reserved.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

NASA Astrophysics Data System (ADS)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

Evaluation of laboratory tests for dengue diagnosis in clinical specimens from consecutive patients with suspected dengue in Belo Horizonte, Brazil.

PubMed

Ferraz, Fernanda Oliveira; Bomfim, Maria Rosa Quaresma; Totola, Antônio Helvécio; Ávila, Thiago Vinícius; Cisalpino, Daniel; Pessanha, José Eduardo Marques; da Glória de Souza, Danielle; Teixeira Júnior, Antônio Lúcio; Nogueira, Maurício Lacerda; Bruna-Romero, Oscar; Teixeira, Mauro Martins

2013-09-01

Dengue is a widely spread arboviral disease in tropical and subtropical regions of the world. Dengue fever presents clinical characteristics similar to other febrile illness. Thus laboratory diagnosis is important for adequate management of the disease. The present study was designed to evaluate the diagnostic performance of real-time PCR and serological methods for dengue in a real epidemic context. Clinical data and blood samples were collected from consecutive patients with suspected dengue who attended a primary health care unit in Belo Horizonte, Brazil. Serologic methods and real-time PCR were performed in serum samples to confirm dengue diagnosis. Among the 181 consecutive patients enrolled in this study with suspected dengue, 146 were considered positive by serological criteria (positive NS1 ELISA and/or anti-dengue IgM ELISA) and 138 were positive by real-time PCR. Clinical criteria were not sufficient for distinguishing between dengue and non-dengue febrile illness. The PCR reaction was pre-optimized using samples from patients with known viral infection. It had similar sensitivity compared to NS1 ELISA (88% and 89%, respectively). We also evaluated three commercial lateral flow immunochromatographic tests for NS1 detection (BIOEASY, BIORAD and PANBIO). All three tests showed high sensitivity (94%, 91% and 81%, respectively) for dengue diagnosis. According to our results it can be suggested that lateral flow tests for NS1 detection are the most feasible methods for early diagnosis of dengue. Copyright © 2013 Elsevier B.V. All rights reserved.

Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol.

PubMed

Azofra, Luis Miguel; Alkorta, Ibon; Toro-Labbé, Alejandro; Elguero, José

2013-09-07

The mechanism of the S(N)2 model glycosylation reaction between ethanol, 1,2-ethanediol and methoxymethanol has been studied theoretically at the B3LYP/6-311+G(d,p) computational level. Three different types of reactions have been explored: (i) the exchange of hydroxyl groups between these model systems; (ii) the basic catalysis reactions by combination of the substrates as glycosyl donors (neutral species) and acceptors (enolate species); and (iii) the effect on the reaction profile of an explicit H2O molecule in the reactions considered in (ii). The reaction force, the electronic chemical potential and the reaction electronic flux have been characterized for the reaction path in each case. Energy calculations show that methoxymethanol is the worst glycosyl donor model among the ones studied here, while 1,2-ethanediol is the best, having the lowest activation barrier of 74.7 kJ mol(-1) for the reaction between this one and the ethanolate as the glycosyl acceptor model. In general, the presence of direct interactions between the atoms involved in the penta-coordinated TS increases the activation energies of the processes.

Incidence of infusion reactions to anti-neoplastic agents in early phase clinical trials: The MD Anderson Cancer Center experience.

PubMed

Bupathi, Manojkumar; Hajjar, Joud; Bean, Stacie; Fu, Siqing; Hong, David; Karp, Daniel; Stephen, Bettzy; Hess, Kenneth; Meric-Bernstam, Funda; Naing, Aung

2017-02-01

Infusion reactions (IRs) to anti-neoplastic agents require prompt recognition and immediate treatment to avert significant complications. We conducted a retrospective review of the medical records of consecutive patients who received anti-neoplastic therapy in the outpatient treatment center of the Department of Investigational Cancer Therapeutics from January 1, 2013 to November 30, 2013. Of the 597 patients who received treatment, 9 (1.5 %) had IRs (all ≤ grade 2). The most common IRs observed on first occurrence were chills (n = 5), itching, rash, and facial flushing (n = 3 each). There were no IR-related deaths. All the IRs were reversible with appropriate symptomatic treatment and the therapy was completed after temporary cessation of infusion in 7 of the 9 patients. The infusion was stopped in 2 patients due to symptoms suggestive of IgE-mediated allergic reaction and cytokine storm. Five of the 8 patients who were re-challenged with the same therapy developed a similar reaction. However, the infusion was completed in 4 of the 5 patients after administration of intravenous diphenhydramine and/or hydrocortisone, or slowing the rate of infusion. And, subsequent cycles with the same agents were uneventful. IRs to anti-neoplastic agents are rare. Though the clinical presentations are overlapping, most IRs are not IgE-mediated allergic reactions. Appropriate premedication and slow rate of infusion facilitates uneventful administration of the anti-neoplastic agents in subsequent cycles. Further study in a larger cohort of patients to identify biomarkers of hypersensitivity is warranted.

Mark R. Nimlos | NREL

Science.gov Websites

, reaction kinetics, computational modeling, photochemistry, and molecular spectroscopy. Nimlos has served as Chemical reaction energetics and kinetics Biomass pyrolysis and gasification Heterogeneous catalysis in zeolites Quantum modeling and kinetic modeling of reaction Molecular dynamics modeling

Ozone impacts of gas-aerosol uptake in global chemistry transport models

NASA Astrophysics Data System (ADS)

Stadtler, Scarlet; Simpson, David; Schröder, Sabine; Taraborrelli, Domenico; Bott, Andreas; Schultz, Martin

2018-03-01

The impact of six heterogeneous gas-aerosol uptake reactions on tropospheric ozone and nitrogen species was studied using two chemical transport models, the Meteorological Synthesizing Centre-West of the European Monitoring and Evaluation Programme (EMEP MSC-W) and the European Centre Hamburg general circulation model combined with versions of the Hamburg Aerosol Model and Model for Ozone and Related chemical Tracers (ECHAM-HAMMOZ). Species undergoing heterogeneous reactions in both models include N2O5, NO3, NO2, O3, HNO3, and HO2. Since heterogeneous reactions take place at the aerosol surface area, the modelled surface area density (Sa) of both models was compared to a satellite product retrieving the surface area. This comparison shows a good agreement in global pattern and especially the capability of both models to capture the extreme aerosol loadings in east Asia. The impact of the heterogeneous reactions was evaluated by the simulation of a reference run containing all heterogeneous reactions and several sensitivity runs. One reaction was turned off in each sensitivity run to compare it with the reference run. The analysis of the sensitivity runs confirms that the globally most important heterogeneous reaction is the one of N2O5. Nevertheless, NO2, HNO3, and HO2 heterogeneous reactions gain relevance particularly in east Asia due to the presence of high NOx concentrations and high Sa in the same region. The heterogeneous reaction of O3 itself on dust is of minor relevance compared to the other heterogeneous reactions. The impacts of the N2O5 reactions show strong seasonal variations, with the biggest impacts on O3 in springtime when photochemical reactions are active and N2O5 levels still high. Evaluation of the models with northern hemispheric ozone surface observations yields a better agreement of the models with observations in terms of concentration levels, variability, and temporal correlations at most sites when the heterogeneous reactions are incorporated. Our results are loosely consistent with results from earlier studies, although the magnitude of changes induced by N2O5 reaction is at the low end of estimates, which seems to fit a trend, whereby the more recent the study the lower the impacts of these reactions.

Generalized Pseudo-Reaction Zone Model for Non-Ideal Explosives

NASA Astrophysics Data System (ADS)

Wescott, Bradley

2007-06-01

The pseudo-reaction zone model was proposed to improve engineering scale simulations when using Detonation Shock Dynamics with high explosives that have a slow reaction component. In this work an extension of the pseudo-reaction zone model is developed for non-ideal explosives that propagate well below their steady-planar Chapman-Jouguet velocity. A programmed burn method utilizing Detonation Shock Dynamics and a detonation velocity dependent pseudo-reaction rate has been developed for non-ideal explosives and applied to the explosive mixture of ammonium nitrate and fuel oil (ANFO). The pseudo-reaction rate is calibrated to the experimentally obtained normal detonation velocity---shock curvature relation. The generalized pseudo-reaction zone model proposed here predicts the cylinder expansion to within 1% by accounting for the slow reaction in ANFO.

Sleep Detriments Associated With Quick Returns in Rotating Shift Work: A Diary Study.

PubMed

Vedaa, Øystein; Mørland, Erik; Larsen, Marit; Harris, Anette; Erevik, Eilin; Sivertsen, Børge; Bjorvatn, Bjørn; Waage, Siri; Pallesen, Ståle

2017-06-01

We aimed to compared sleep characteristics associated with quick returns (QRs, <11 hours between shift intervals) with those associated with other common shift transitions. Sixty-seven nurses completed a 2-week work and sleep diary (94.0% female, mean age 47.7 years). A multilevel fixed effects model was used to examine the sleep in QRs compared with two consecutive night shifts, two consecutive evening shifts, and two consecutive day shifts, respectively. None of the other shift transitions studied encumbered as many detriments as QRs, which included short sleep duration (5.6 hours), slightly prolonged sleep onset latency, more abrupt ending of main sleep period, increased sleepiness, and higher level of perceived stress on the following shift. The study emphasizes the need for sufficient time for rest and recuperation between shifts.

Why the predictions for monsoon rainfall fail?

NASA Astrophysics Data System (ADS)

Lee, J.

2016-12-01

To be in line with the Global Land/Atmosphere System Study (GLASS) of the Global Energy and Water Cycle Experiment (GEWEX) international research scheme, this study discusses classical arguments about the feedback mechanisms between land surface and precipitation to improve the predictions of African monsoon rainfall. In order to clarify the impact of antecedent soil moisture on subsequent rainfall evolution, several data sets will be presented. First, in-situ soil moisture field measurements acquired by the AMMA field campaign will be shown together with rain gauge data. This data set will validate various model and satellite data sets such as NOAH land surface model, TRMM rainfall, CMORPH rainfall and HadGEM climate models, SMOS soil moisture. To relate soil moisture with precipitation, two approaches are employed: one approach makes a direct comparison between the spatial distributions of soil moisture as an absolute value and rainfall, while the other measures a temporal evolution of the consecutive dry days (i.e. a relative change within the same soil moisture data set over time) and rainfall occurrences. Consecutive dry days shows consistent results of a negative feedback between soil moisture and rainfall across various data sets, contrary to the direct comparison of soil moisture state. This negative mechanism needs attention, as most climate models usually focus on a positive feedback only. The approach of consecutive dry days takes into account the systematic errors in satellite observations, reminding us that it may cause the misinterpretation to directly compare model with satellite data, due to their difference in data retrievals. This finding is significant, as the climate indices employed by the Intergovernmental Panel on Climate Change (IPCC) modelling archive are based on the atmospheric variable rathr than land.

Evaluation of effect of atorvastatin on left ventricular systolic function in rats with myocardial infarction via 2D-STI technique.

PubMed

Hua, Yan; Xie, Manying; Yin, Jiabao; Wang, Yu; Gan, Ling; Sang, Ming; Sun, Xiaodong; Li, Mingyang; Liu, Shanjun; Xu, Jinzhi

2018-05-01

This report aims to evaluate the effect of atorvastatin (Ator) on left ventricular systolic function in myocardial infarction (MI) rats. Forty healthy adult Sprague-Dawley rats were randomly divided into four groups: Ator group, MI group, sham-operation group and normal group. The left anterior descending coronary arteries were ligated to establish the MI model; after modeling, the Ator group was treated with Ator for 4 consecutive weeks. The echocardiographic detection was performed; the left ventricular myocardial systolic peak velocities, strain and strain rates were analyzed using the 2D-STI technique. After 4 weeks, myocardial tissues were taken from all rats and received the pathological examination. Left ventricular end-diastolic diameter (LVEDD) and left ventricular end-systolic diameter (LVESD) in Ator group and MI group were increased after operation, but left ventricular ejection fraction (LVEF) and left ventricular fractional shortening (LVFS) were decreased; myocardial function were decreased significantly (p<0.05). After Ator treatment, myocardial function at the 3rd and 4th week after operation increased significantly (p<0.05). After Ator treatment, LVEDD and LVESD decreased while LVEF and LVFS increased in Ator group at the 3rd and 4th week after operation compared with MI group (p<0.05). At the 4th week after operation, LVEDD and LVESD in Ator group were decreased compared with those at the 1st and 2nd week after operation, but LVEF and LVFS were increased compared with those at the 1st, 2nd and 3rd week after operation (p<0.05). Pathological examination showed that necrosis and fibrosis of myocardial cells and inflammatory reaction were obvious in MI group. The inflammatory reaction of myocardial cells and myocardial fibrosis were lighter in Ator group. Ator can effectively improve the left ventricular systolic function in MI rats, which could be related to the reduction of response to inflammation and fibrosis.

Optimizing Chemical Reactions with Deep Reinforcement Learning.

PubMed

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Analysis of noise-induced temporal correlations in neuronal spike sequences

NASA Astrophysics Data System (ADS)

Reinoso, José A.; Torrent, M. C.; Masoller, Cristina

2016-11-01

We investigate temporal correlations in sequences of noise-induced neuronal spikes, using a symbolic method of time-series analysis. We focus on the sequence of time-intervals between consecutive spikes (inter-spike-intervals, ISIs). The analysis method, known as ordinal analysis, transforms the ISI sequence into a sequence of ordinal patterns (OPs), which are defined in terms of the relative ordering of consecutive ISIs. The ISI sequences are obtained from extensive simulations of two neuron models (FitzHugh-Nagumo, FHN, and integrate-and-fire, IF), with correlated noise. We find that, as the noise strength increases, temporal order gradually emerges, revealed by the existence of more frequent ordinal patterns in the ISI sequence. While in the FHN model the most frequent OP depends on the noise strength, in the IF model it is independent of the noise strength. In both models, the correlation time of the noise affects the OP probabilities but does not modify the most probable pattern.

Force modeling for incisions into various tissues with MRF haptic master

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa; Kim, Soomin; Park, Young-Dai; Choi, Seung-Bok

2016-03-01

This study proposes a new model to predict the reaction force that occurs in incisions during robot-assisted minimally invasive surgery. The reaction force is fed back to the manipulator by a magneto-rheological fluid (MRF) haptic master, which is featured by a bi-directional clutch actuator. The reaction force feedback provides similar sensations to laparotomy that cannot be provided by a conventional master for surgery. This advantage shortens the training period for robot-assisted minimally invasive surgery and can improve the accuracy of operations. The reaction force modeling of incisions can be utilized in a surgical simulator that provides a virtual reaction force. In this work, in order to model the reaction force during incisions, the energy aspect of the incision process is adopted and analyzed. Each mode of the incision process is classified by the tendency of the energy change, and modeled for realistic real-time application. The reaction force model uses actual reaction force information with three types of actual tissues: hard tissue, medium tissue, and soft tissue. This modeled force is realized by the MRF haptic master through an algorithm based on the position and velocity of a scalpel using two different control methods: an open-loop algorithm and a closed-loop algorithm. The reaction forces obtained from the proposed model are compared with a desired force in time domain.

Interlaboratory study for the assessment of potential irritative properties of hygiene products on the hamster cheek pouch.

PubMed

Bourrinet, P; Conduzorgues, J P; Dutertre, H; Macabies, J; Masson, P; Maurin, J; Mercier, O

1995-02-01

An interlaboratory study was carried out to determine the feasibility and reliability of a method using the hamster cheek pouch as a model for assessing the potential irritative properties of substances intended to be applied to the lips or other mucous membranes. The test substances were applied once daily to both pouches for 14 consecutive days. Local and general tolerances were appraised throughout the study. At the end of the study, histologic examination of the pouches and the main organs was performed. Results of the feasibility study, conducted on various types of commercial products, indicated that this model is suitable for preparations of various consistence and composition. Results of the reliability study, carried out on gel-type preparations containing various concentrations of a known irritant, sodium lauryl sulfate, indicated that the method elicits a dose-dependent reaction for this compound. This hamster cheek pouch method was reproducible for the various parameters under consideration: local tolerance, general tolerance, histologic examination. For all products, results were in good agreement among the various laboratories participating in the study. The French regulatory authorities of the Fraud Repression Department have accepted it as an official method for the evaluation of the potential irritative properties of cosmetics and hygiene products intended to be applied to the lips or other mucous membranes.

Role of -675 4G/5G in the plasminogen activator inhibitor-1 gene and -308G/A tumor necrosis factor-α gene polymorphisms in obese Argentinean patients.

PubMed

Wingeyer, Silvia D Perés; Graffigna, Mabel N; Belli, Susana H; Benetucci, Jorge; de Larrañaga, Gabriela F

2012-05-01

Plasminogen activator inhibitor-1 (PAI-1) and tumor necrosis factor-α (TNF-α) are increased in the circulation of obese persons. Because a direct link between PAI-1 and TNF-α in obesity has been observed, they are candidate genes for the development of obesity. We sought to evaluate the relation between the genotypic and allelic frequencies of the -675 4G/5G PAI-1 and -308 G/A TNF-α polymorphisms and their association with the risk for obesity in an Argentinean population. A group of 110 consecutive obese persons and a group of 111 lean controls were recruited. Polymerase chain reaction was used to determine the frequency of PAI-1 and TNF-α polymorphisms; serum fasting glucose, insulin, and lipid levels were measured by standard methods. Insulin sensitivity was evaluated by using homeostasis model assessment. The -308 TNF-α and -675 4G/5G PAI-1 genotype distribution did not significantly differ between the groups (p=0.544 and p=0.327, respectively). Homeostasis model assessment was the only positive independent determinant of body mass index (R(2)=0.493; p<0.001). The -675 4G/5G PAI-1 and the -308 TNF-α polymorphism variants tested in this study, individually or combined, were not associated with obesity in an Argentinean population.

Multifaceted Quadruplet of Low-Lying Spin-Zero States in 66Ni: Emergence of Shape Isomerism in Light Nuclei

NASA Astrophysics Data System (ADS)

Leoni, S.; Fornal, B.; Mǎrginean, N.; Sferrazza, M.; Tsunoda, Y.; Otsuka, T.; Bocchi, G.; Crespi, F. C. L.; Bracco, A.; Aydin, S.; Boromiza, M.; Bucurescu, D.; Cieplicka-Oryǹczak, N.; Costache, C.; Cǎlinescu, S.; Florea, N.; GhiÅ£ǎ, D. G.; Glodariu, T.; Ionescu, A.; Iskra, Ł. W.; Krzysiek, M.; Mǎrginean, R.; Mihai, C.; Mihai, R. E.; Mitu, A.; NegreÅ£, A.; NiÅ£ǎ, C. R.; Olǎcel, A.; Oprea, A.; Pascu, S.; Petkov, P.; Petrone, C.; Porzio, G.; Şerban, A.; Sotty, C.; Stan, L.; Ştiru, I.; Stroe, L.; Şuvǎilǎ, R.; Toma, S.; Turturicǎ, A.; Ujeniuc, S.; Ur, C. A.

2017-04-01

A search for shape isomers in the 66Ni nucleus was performed, following old suggestions of various mean-field models and recent ones, based on state-of-the-art Monte Carlo shell model (MCSM), all considering 66Ni as the lightest nuclear system with shape isomerism. By employing the two-neutron transfer reaction induced by an 18O beam on a 64Ni target, at the sub-Coulomb barrier energy of 39 MeV, all three lowest-excited 0+ states in 66Ni were populated and their γ decay was observed by γ -coincidence technique. The 0+ states lifetimes were assessed with the plunger method, yielding for the 02+, 03+, and 04+ decay to the 21+ state the B (E 2 ) values of 4.3, 0.1, and 0.2 Weisskopf units (W.u.), respectively. MCSM calculations correctly predict the existence of all three excited 0+ states, pointing to the oblate, spherical, and prolate nature of the consecutive excitations. In addition, they account for the hindrance of the E 2 decay from the prolate 04+ to the spherical 21+ state, although overestimating its value. This result makes 66Ni a unique nuclear system, apart from U,238236 , in which a retarded γ transition from a 0+ deformed state to a spherical configuration is observed, resembling a shape-isomerlike behavior.

Kinetic modeling of electro-Fenton reaction in aqueous solution.

PubMed

Liu, H; Li, X Z; Leng, Y J; Wang, C

2007-03-01

To well describe the electro-Fenton (E-Fenton) reaction in aqueous solution, a new kinetic model was established according to the generally accepted mechanism of E-Fenton reaction. The model has special consideration on the rates of hydrogen peroxide (H(2)O(2)) generation and consumption in the reaction solution. The model also embraces three key operating factors affecting the organic degradation in the E-Fenton reaction, including current density, dissolved oxygen concentration and initial ferrous ion concentration. This analytical model was then validated by the experiments of phenol degradation in aqueous solution. The experiments demonstrated that the H(2)O(2) gradually built up with time and eventually approached its maximum value in the reaction solution. The experiments also showed that phenol was degraded at a slow rate at the early stage of the reaction, a faster rate during the middle stage, and a slow rate again at the final stage. It was confirmed in all experiments that the curves of phenol degradation (concentration vs. time) appeared to be an inverted "S" shape. The experimental data were fitted using both the normal first-order model and our new model, respectively. The goodness of fittings demonstrated that the new model could better fit the experimental data than the first-order model appreciably, which indicates that this analytical model can better describe the kinetics of the E-Fenton reaction mathematically and also chemically.

Relationship between Immunological Abnormalities in Rat Models of Diabetes Mellitus and the Amplification Circuits for Diabetes.

PubMed

Takeda, Yuji; Shimomura, Tomoko; Asao, Hironobu; Wakabayashi, Ichiro

2017-01-01

A better understanding of pathogenic mechanisms is required in order to treat diseases. However, the mechanisms of diabetes mellitus and diabetic complications are extremely complex. Immune reactions are involved in the pathogenesis of diabetes and its complications, while diabetes influences immune reactions. Furthermore, both diabetes and immune reactions are influenced by genetic and environmental factors. To address these issues, animal models are useful tools. So far, various animal models of diabetes have been developed in rats, which have advantages over mice models in terms of the larger volume of tissue samples and the variety of type 2 diabetes models. In this review, we introduce rat models of diabetes and summarize the immune reactions in diabetic rat models. Finally, we speculate on the relationship between immune reactions and diabetic episodes. For example, diabetes-prone Biobreeding rats, type 1 diabetes model rats, exhibit increased autoreactive cellular and inflammatory immune reactions, while Goto-Kakizaki rats, type 2 diabetes model rats, exhibit increased Th2 reactions and attenuation of phagocytic activity. Investigation of immunological abnormalities in various diabetic rat models is useful for elucidating complicated mechanisms in the pathophysiology of diabetes. Studying immunological alterations, such as predominance of Th1/17 or Th2 cells, humoral immunity, and innate immune reactions, may improve understanding the structure of amplification circuits for diabetes in future studies.

ReactionPredictor: prediction of complex chemical reactions at the mechanistic level using machine learning.

PubMed

Kayala, Matthew A; Baldi, Pierre

2012-10-22

Proposing reasonable mechanisms and predicting the course of chemical reactions is important to the practice of organic chemistry. Approaches to reaction prediction have historically used obfuscating representations and manually encoded patterns or rules. Here we present ReactionPredictor, a machine learning approach to reaction prediction that models elementary, mechanistic reactions as interactions between approximate molecular orbitals (MOs). A training data set of productive reactions known to occur at reasonable rates and yields and verified by inclusion in the literature or textbooks is derived from an existing rule-based system and expanded upon with manual curation from graduate level textbooks. Using this training data set of complex polar, hypervalent, radical, and pericyclic reactions, a two-stage machine learning prediction framework is trained and validated. In the first stage, filtering models trained at the level of individual MOs are used to reduce the space of possible reactions to consider. In the second stage, ranking models over the filtered space of possible reactions are used to order the reactions such that the productive reactions are the top ranked. The resulting model, ReactionPredictor, perfectly ranks polar reactions 78.1% of the time and recovers all productive reactions 95.7% of the time when allowing for small numbers of errors. Pericyclic and radical reactions are perfectly ranked 85.8% and 77.0% of the time, respectively, rising to >93% recovery for both reaction types with a small number of allowed errors. Decisions about which of the polar, pericyclic, or radical reaction type ranking models to use can be made with >99% accuracy. Finally, for multistep reaction pathways, we implement the first mechanistic pathway predictor using constrained tree-search to discover a set of reasonable mechanistic steps from given reactants to given products. Webserver implementations of both the single step and pathway versions of ReactionPredictor are available via the chemoinformatics portal http://cdb.ics.uci.edu/.

Sunlight-assisted Fenton reaction catalyzed by gold supported on diamond nanoparticles as pretreatment for biological degradation of aqueous phenol solutions.

PubMed

Navalon, Sergio; Martin, Roberto; Alvaro, Mercedes; Garcia, Hermenegildo

2011-05-23

Gold nanoparticles supported on Fenton-treated diamond nanoparticles (Au/DNPs) have been reported as one of the most efficient solid catalysts effecting the Fenton reaction, achieving a turnover number (TON) as high as 321,000. However, at room temperature the main limitation for the catalytic activity of Au/DNPs is the pH of the solution, which should be less than 5. In this paper, we report that exposure of Au/DNPs to sunlight enhances the catalytic activity of Au/DNPs up to the point that it can promote the Fenton reaction at room temperature even at slightly basic pH values. Also, in addition to performing a deep Fenton treatment and considering that the excess of H(2)O(2) used in the process should be minimized, we have achieved in our study, using a mild Fenton reaction promoted by Au/DNPs under sunlight irradiation, an optimum in the biodegradability, a minimum in the ecotoxicity, and no toxicity for the Vibrio fischeri test. The results have shown that, by using an H(2)O(2) -to-phenol molar ratio of 5.5 or higher, it is possible to achieve a high biodegradability as well as a complete lack of ecotoxicity and of Vibrio fischeri toxicity. The stability of Au/DNPs was confirmed by analyzing the gold leached to the solution and by performing four consecutive reuses of the catalyst with initial pH values ranging from 4 to 8. It was observed that, after finishing the reaction and exhaustive washings with basic aqueous solutions, the initial reaction rate of the used catalyst is recovered to the value exhibited by the fresh solid. Overall, our study shows that the synergism between catalysis and photocatalysis can overcome the limitations found for dark catalytic reactions and that the reaction parameters can be optimized to effect mild Fenton reactions aimed at increasing biodegradability in biorecalcitrant waste waters. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Systematic assignment of thermodynamic constraints in metabolic network models

PubMed Central

Kümmel, Anne; Panke, Sven; Heinemann, Matthias

2006-01-01

Background The availability of genome sequences for many organisms enabled the reconstruction of several genome-scale metabolic network models. Currently, significant efforts are put into the automated reconstruction of such models. For this, several computational tools have been developed that particularly assist in identifying and compiling the organism-specific lists of metabolic reactions. In contrast, the last step of the model reconstruction process, which is the definition of the thermodynamic constraints in terms of reaction directionalities, still needs to be done manually. No computational method exists that allows for an automated and systematic assignment of reaction directions in genome-scale models. Results We present an algorithm that – based on thermodynamics, network topology and heuristic rules – automatically assigns reaction directions in metabolic models such that the reaction network is thermodynamically feasible with respect to the production of energy equivalents. It first exploits all available experimentally derived Gibbs energies of formation to identify irreversible reactions. As these thermodynamic data are not available for all metabolites, in a next step, further reaction directions are assigned on the basis of network topology considerations and thermodynamics-based heuristic rules. Briefly, the algorithm identifies reaction subsets from the metabolic network that are able to convert low-energy co-substrates into their high-energy counterparts and thus net produce energy. Our algorithm aims at disabling such thermodynamically infeasible cyclic operation of reaction subnetworks by assigning reaction directions based on a set of thermodynamics-derived heuristic rules. We demonstrate our algorithm on a genome-scale metabolic model of E. coli. The introduced systematic direction assignment yielded 130 irreversible reactions (out of 920 total reactions), which corresponds to about 70% of all irreversible reactions that are required to disable thermodynamically infeasible energy production. Conclusion Although not being fully comprehensive, our algorithm for systematic reaction direction assignment could define a significant number of irreversible reactions automatically with low computational effort. We envision that the presented algorithm is a valuable part of a computational framework that assists the automated reconstruction of genome-scale metabolic models. PMID:17123434

Optimizing Chemical Reactions with Deep Reinforcement Learning

PubMed Central

2017-01-01

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability. PMID:29296675

Evaluation and linking of effective parameters in particle-based models and continuum models for mixing-limited bimolecular reactions

NASA Astrophysics Data System (ADS)

Zhang, Yong; Papelis, Charalambos; Sun, Pengtao; Yu, Zhongbo

2013-08-01

Particle-based models and continuum models have been developed to quantify mixing-limited bimolecular reactions for decades. Effective model parameters control reaction kinetics, but the relationship between the particle-based model parameter (such as the interaction radius R) and the continuum model parameter (i.e., the effective rate coefficient Kf) remains obscure. This study attempts to evaluate and link R and Kf for the second-order bimolecular reaction in both the bulk and the sharp-concentration-gradient (SCG) systems. First, in the bulk system, the agent-based method reveals that R remains constant for irreversible reactions and decreases nonlinearly in time for a reversible reaction, while mathematical analysis shows that Kf transitions from an exponential to a power-law function. Qualitative link between R and Kf can then be built for the irreversible reaction with equal initial reactant concentrations. Second, in the SCG system with a reaction interface, numerical experiments show that when R and Kf decline as t-1/2 (for example, to account for the reactant front expansion), the two models capture the transient power-law growth of product mass, and their effective parameters have the same functional form. Finally, revisiting of laboratory experiments further shows that the best fit factor in R and Kf is on the same order, and both models can efficiently describe chemical kinetics observed in the SCG system. Effective model parameters used to describe reaction kinetics therefore may be linked directly, where the exact linkage may depend on the chemical and physical properties of the system.

Minimum reaction network necessary to describe Ar/CF4 plasma etch

NASA Astrophysics Data System (ADS)

Helpert, Sofia; Chopra, Meghali; Bonnecaze, Roger T.

2018-03-01

Predicting the etch and deposition profiles created using plasma processes is challenging due to the complexity of plasma discharges and plasma-surface interactions. Volume-averaged global models allow for efficient prediction of important processing parameters and provide a means to quickly determine the effect of a variety of process inputs on the plasma discharge. However, global models are limited based on simplifying assumptions to describe the chemical reaction network. Here a database of 128 reactions is compiled and their corresponding rate constants collected from 24 sources for an Ar/CF4 plasma using the platform RODEo (Recipe Optimization for Deposition and Etching). Six different reaction sets were tested which employed anywhere from 12 to all 128 reactions to evaluate the impact of the reaction database on particle species densities and electron temperature. Because many the reactions used in our database had conflicting rate constants as reported in literature, we also present a method to deal with those uncertainties when constructing the model which includes weighting each reaction rate and filtering outliers. By analyzing the link between a reaction's rate constant and its impact on the predicted plasma densities and electron temperatures, we determine the conditions at which a reaction is deemed necessary to the plasma model. The results of this study provide a foundation for determining which minimal set of reactions must be included in the reaction set of the plasma model.

Reaction time for trimolecular reactions in compartment-based reaction-diffusion models

NASA Astrophysics Data System (ADS)

Li, Fei; Chen, Minghan; Erban, Radek; Cao, Yang

2018-05-01

Trimolecular reaction models are investigated in the compartment-based (lattice-based) framework for stochastic reaction-diffusion modeling. The formulae for the first collision time and the mean reaction time are derived for the case where three molecules are present in the solution under periodic boundary conditions. For the case of reflecting boundary conditions, similar formulae are obtained using a computer-assisted approach. The accuracy of these formulae is further verified through comparison with numerical results. The presented derivation is based on the first passage time analysis of Montroll [J. Math. Phys. 10, 753 (1969)]. Montroll's results for two-dimensional lattice-based random walks are adapted and applied to compartment-based models of trimolecular reactions, which are studied in one-dimensional or pseudo one-dimensional domains.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; Crowhurst, Jonathan C.; Rose, Timothy P.; Koroglu, Batikan; Radousky, Harry B.; Armstrong, Michael R.

2017-12-01

In this work, we present a newly constructed U x O y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. The global model is used to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.

Saving a Drug Poisoning Victim: A Kinetics Simulation

NASA Astrophysics Data System (ADS)

Selco, Jodye I.; Beery, Janet

2002-05-01

In this project, students, posing as hospital emergency room physicians, must save the life of a child who has accidentally overdosed on the asthma medication, theophylline. The progress of the drug through the child's body can be modeled as a chemical kinetics problem involving first-order consecutive reactions. Students begin by setting up a system of linear first-order differential equations describing the medication's absorption into and elimination from the child's bloodstream using half-lives obtained from the Physician's Desk Reference. By using a computer to solve the differential equations numerically, students discover that the child will almost certainly die if they, as physicians, do not intervene. The students then determine by how much they need to increase the drug's elimination rate in order to save the child. This dictates the appropriate medical action. Students discover that they need to use the more drastic treatment of extracorporeal filtering of the blood through charcoal, rather than simply administering oral doses of charcoal. We've found that this project appeals to a broad range of students; many students are interested in careers in the health professions and all are intrigued by the child's grave situation.

The cumulative analgesic effect of repeated electroacupuncture involves synaptic remodeling in the hippocampal CA3 region☆

PubMed Central

Xu, Qiuling; Liu, Tao; Chen, Shuping; Gao, Yonghui; Wang, Junying; Qiao, Lina; Liu, Junling

2012-01-01

In the present study, we examined the analgesic effect of repeated electroacupuncture at bilateral Zusanli (ST36) and Yanglingquan (GB34) once a day for 14 consecutive days in a rat model of chronic sciatic nerve constriction injury-induced neuropathic pain. In addition, concomitant changes in calcium/calmodulin-dependent protein kinase II expression and synaptic ultrastructure of neurons in the hippocampal CA3 region were examined. The thermal pain threshold (paw withdrawal latency) was increased significantly in both groups at 2 weeks after electroacupuncture intervention compared with 2 days of electroacupuncture. In ovariectomized rats with chronic constriction injury, the analgesic effect was significantly reduced. Electroacupuncture for 2 weeks significantly diminished the injury-induced increase in synaptic cleft width and thinning of the postsynaptic density, and it significantly suppressed the down-regulation of intracellular calcium/calmodulin-dependent protein kinase II expression in the hippocampal CA3 region. Repeated electroacupuncture intervention had a cumulative analgesic effect on injury-induced neuropathic pain reactions, and it led to synaptic remodeling of hippocampal neurons and upregulated calcium/calmodulin-dependent protein kinase II expression in the hippocampal CA3 region. PMID:25657670

Negative methylation status of Vimentin predicts improved prognosis in pancreatic carcinoma

PubMed Central

Zhou, Yi-Feng; Xu, Wei; Wang, Xia; Sun, Jin-Shan; Xiang, Jing-Jing; Li, Zhao-Shen; Zhang, Xiao-Feng

2014-01-01

AIM: To determine the existence of a potential relationship between the methylation state of the Vimentin gene and its prognostic value in pancreatic cancer. METHODS: Sixty-four primary tumor specimens and normal tissues were collected consecutively from pancreatic cancer patients during surgery at Hangzhou First People’s Hospital and Affiliated Hospital of the Logistics University of the Chinese People’s Armed Police Force. DNA was extracted from the samples and subsequently quantitative methylation-specific polymerase chain reaction was used to detect the Vimentin methylation status of the samples. All of the patients were followed up to December 2012. χ2 test, Kaplan-Meier survival and Cox regression statistical models were used. RESULTS: Out of 64 pancreatic cancer tissues, 21 were marked as Vimentin methylation-positive, and 43 were marked as Vimentin methylation-negative. The location of pancreatic carcinoma was related to the Vimentin methylation state. The pathological T staging (P < 0.001), adjuvant chemotherapy (P = 0.003) and the Vimentin methylation state (P = 0.037) were independent prognostic factors. CONCLUSION: In our study, Vimentin methylation status can predict the prognosis of pancreatic cancer patients. However, additional experiments and clinical trials are needed to accurately validate this observation. PMID:25278713

Cutting the Wires: Modularization of Cellular Networks for Experimental Design

PubMed Central

Lang, Moritz; Summers, Sean; Stelling, Jörg

2014-01-01

Understanding naturally evolved cellular networks requires the consecutive identification and revision of the interactions between relevant molecular species. In this process, initially often simplified and incomplete networks are extended by integrating new reactions or whole subnetworks to increase consistency between model predictions and new measurement data. However, increased consistency with experimental data alone is not sufficient to show the existence of biomolecular interactions, because the interplay of different potential extensions might lead to overall similar dynamics. Here, we present a graph-based modularization approach to facilitate the design of experiments targeted at independently validating the existence of several potential network extensions. Our method is based on selecting the outputs to measure during an experiment, such that each potential network extension becomes virtually insulated from all others during data analysis. Each output defines a module that only depends on one hypothetical network extension, and all other outputs act as virtual inputs to achieve insulation. Given appropriate experimental time-series measurements of the outputs, our modules can be analyzed, simulated, and compared to the experimental data separately. Our approach exemplifies the close relationship between structural systems identification and modularization, an interplay that promises development of related approaches in the future. PMID:24411264

Enzyme-assisted growth of nacreous CaCO3/polymer hybrid nanolaminates via the formation of mineral bridges

NASA Astrophysics Data System (ADS)

Yeom, Bongjun; Char, Kookheon

2016-06-01

Laminated nanostructures in nacre have been adopted as models in the fabrication of strong, tough synthetic nanocomposites. However, the utilization of CaCO3 biominerals in these composites is limited by the complexity of the synthesis method for nanosized biominerals. In this study, we use the enzymatic reaction of urease to generate a nanoscale CaCO3 thin film to prepare CaCO3/polymer hybrid nanolaminates. Additional layers of CaCO3 thin film are consecutively grown over the base CaCO3 layer with the intercalation of organic layers. The morphology and crystallinity of the added CaCO3 layers depend strongly on the thickness of the organic layer coated on the underlying CaCO3 layer. When the organic layer is less than 20 nm thick, the amorphous CaCO3 layer is spontaneously transformed into crystalline calcite layer during the growth process. We also observe crystalline continuity between adjacent CaCO3 layers through interconnecting mineral bridges. The formation of these mineral bridges is crucial to the epitaxial growth of CaCO3 layers, similar to the formation of natural nacre.

Blueberry polyphenol oxidase: Characterization and the kinetics of thermal and high pressure activation and inactivation.

PubMed

Terefe, Netsanet Shiferaw; Delon, Antoine; Buckow, Roman; Versteeg, Cornelis

2015-12-01

Partially purified blueberry polyphenol oxidase (PPO) in Mcllvaine buffer (pH=3.6, typical pH of blueberry juice) was subjected to processing at isothermal-isobaric conditions at temperatures from 30 to 80 °C and pressure from 0.1 to 700 MPa. High pressure processing at 30-50 °C at all pressures studied caused irreversible PPO activity increase with a maximum of 6.1 fold increase at 500 MPa and 30 °C. Treatments at mild pressure-mild temperature conditions (0.1-400 MPa, 60 °C) also caused up to 3 fold PPO activity increase. Initial activity increase followed by a decrease occurred at relatively high pressure-mild temperature (400-600 MPa, 60 °C) and mild pressure-high temperature (0.1-400 MPa, 70-80 °C) combinations. At temperatures higher than 76 °C, monotonic decrease in PPO activity occurred at 0.1 MPa and pressures higher than 500 MPa. The activation/inactivation kinetics of the enzyme was successfully modelled assuming consecutive reactions in series with activation followed by inactivation. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

POD experiments using real and simulated time-sharing observations for GEO satellites in C-band transfer ranging system

NASA Astrophysics Data System (ADS)

Fen, Cao; XuHai, Yang; ZhiGang, Li; ChuGang, Feng

2016-08-01

The normal consecutive observing model in Chinese Area Positioning System (CAPS) can only supply observations of one GEO satellite in 1 day from one station. However, this can't satisfy the project need for observing many GEO satellites in 1 day. In order to obtain observations of several GEO satellites in 1 day like GPS/GLONASS/Galileo/BeiDou, the time-sharing observing model for GEO satellites in CAPS needs research. The principle of time-sharing observing model is illuminated with subsequent Precise Orbit Determination (POD) experiments using simulated time-sharing observations in 2005 and the real time-sharing observations in 2015. From time-sharing simulation experiments before 2014, the time-sharing observing 6 GEO satellites every 2 h has nearly the same orbit precision with the consecutive observing model. From POD experiments using the real time-sharing observations, POD precision for ZX12# and Yatai7# are about 3.234 m and 2.570 m, respectively, which indicates the time-sharing observing model is appropriate for CBTR system and can realize observing many GEO satellites in 1 day.

Does hormone therapy affect attention and memory in sleep-deprived women?

PubMed

Alhola, P; Kylmälä, M; Urrila, A Sofia; Karakorpi, M; Portin, R; Kalleinen, N; Polo-Kantola, P

2008-06-01

To evaluate whether hormone therapy (HT) modifies cognitive performance during sleep deprivation in postmenopausal women. Comparison was made with a group of young women. Participants included 26 postmenopausal women (age 58-72 years, 16 HT users, 10 non-users), 11 young women (age 20-26 years). They spent four consecutive nights in the sleep laboratory. Cognitive tests of attention, working memory, and verbal episodic memory were carried out after the baseline night, 25-h sleep deprivation, and recovery night. Sleep deprivation impaired performance in all groups. It was manifested either as delayed practice effect or deteriorated performance (p < 0.05). In simple reaction time and 10-choice reaction time, non-users and young maintained their performance, whereas HT users suffered a minor impairment (p < 0.01). In other measurements, there was no interaction of group and condition. In 10-choice reaction time and vigilance, postmenopausal women made fewer errors and omissions than the young (p < 0.05). For most tasks, all groups showed improvement after one recovery night. HT had a minor adverse effect on cognitive performance during sleep deprivation. Attention and memory deteriorated similarly in postmenopausal and young women, despite the lower initial performance level of postmenopausal women. One night of sleep ensured recovery in most tasks.

Hydroxyacetone: A Glycerol-Based Platform for Electrocatalytic Hydrogenation and Hydrodeoxygenation Processes.

PubMed

Sauter, Waldemar; Bergmann, Olaf L; Schröder, Uwe

2017-08-10

Here, we propose the use of hydroxyacetone, a dehydration product of glycerol, as a platform for the electrocatalytic synthesis of acetone, 1,2-propanediol, and 2-propanol. 11 non-noble metals were investigated as electrode materials in combination with three different electrolyte compositions toward the selectivity, Coulombic efficiency (CE), and reaction rates of the electrocatalytic hydrogenation (formation of 1,2-propanediol) and hydrodeoxygenation (formation of acetone and propanol) of hydroxyacetone. With a selectivity of 84.5 %, a reaction rate of 782 mmol h -1  m -2 and a CE of 32 % (for 0.09 m hydroxyacetone), iron electrodes, in a chloride electrolyte, yielded the best 1,2 propanediol formation. A further enhancement of the performance can be achieved upon increasing the educt concentration to 0.5 m, yielding a reaction rate of 2248.1 mmol h -1  m -2 and a CE of 64.5 %. Acetone formation was optimal at copper and lead electrodes in chloride solution, with lead showing the lowest tendency of side product formation. 2-propanol formation can be achieved using a consecutive oxidation of the formed acetone (at iron electrodes). 1-propanol formation was observed only in traces. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

Gas-phase ion chemistry and organic chemistry-the story of a hybrid six sector mass spectrometer--the "AutoSpec 6F".

PubMed

Gerbaux, Pascal; Lamote, Luc; Van Haverbeke, Yves; Flammang, Robert; Brown, Jeffrey M

2012-01-01

The AutoSpec 6F mass spectrometer is a large, floor standing instrument comprising a pair of commercial EBE geometry (AutoSpec) mass spectrometers coupled in series to provide an hybrid EBE-EBE configuration, (E and B being respectively electrostatic and magnetic sectors.) It was designed in close collaboration between Professor R. Flammang and VG Analytical in Manchester, UK. It was equipped with five collision cells and allowed the recording of high energy CID (collision induced dissociation), MIKES (mass analyzed ion kinetic energy spectrometry) and NRMS (neutralization re-ionization mass spectrometry) data as well as consecutive MSn analyses. The field-free regions between sectors allowed the study of unimolecular decomposition products from long-lived metastable ions. The mass spectrometer became even more versatile when an RF-only quadrupole collision cell was installed between the second and the third electric sector. This allowed the study of associative ion/molecule reactions in the low kinetic energy regime. Bimolecular chemical reactions were performed inside the quadrupole cell when a neutral reagent was introduced and the reaction products were analyzed by high energy CID in the downstream sectors. This paper tells the history and summarizes the capabilities of this versatile instrument.

A thermophilic cyanobacterium Synechococcus elongatus has three different Class I prenyltransferase genes.

PubMed

Ohto, C; Ishida, C; Nakane, H; Muramatsu, M; Nishino, T; Obata, S

1999-05-01

Prenyltransferases (prenyl diphosphate synthases), which are a broad group of enzymes that catalyze the consecutive condensation of homoallylic diphosphate of isopentenyl diphosphates (IPP, C5) with allylic diphosphates to synthesize prenyl diphosphates of various chain lengths, have highly conserved regions in their amino acid sequences. Based on the above information, three prenyltransferase homologue genes were cloned from a thermophilic cyanobacterium, Synechococcus elongatus. Through analyses of the reaction products of the enzymes encoded by these genes, it was revealed that one encodes a thermolabile geranylgeranyl (C20) diphosphate synthase, another encodes a farnesyl (C15) diphosphate synthase whose optimal reaction temperature is 60 degrees C, and the third one encodes a prenyltransferase whose optimal reaction temperature is 75 degrees C. The last enzyme could catalyze the synthesis of five prenyl diphosphates of farnesyl, geranylgeranyl, geranylfarnesyl (C25), hexaprenyl (C30), and heptaprenyl (C35) diphosphates from dimethylallyl (C5) diphosphate, geranyl (C10) diphosphate, or farnesyl diphosphate as the allylic substrates. The product specificity of this novel kind of enzyme varied according to the ratio of the allylic and homoallylic substrates. The situations of these three S. elongatus enzymes in a phylogenetic tree of prenyltransferases are discussed in comparison with a mesophilic cyanobacterium of Synechocystis PCC6803, whose complete genome has been reported by Kaneko et al. (1996).

Treatment of cyanide wastewater by bulk liquid membrane using tricaprylamine as a carrier.

PubMed

Li, Guoping; Xue, Juanqin; Liu, Nina; Yu, Lihua

2016-01-01

The transport of cyanide from wastewater through a bulk liquid membrane (BLM) containing tricaprylamine (TOA) as a carrier was studied. The effect of cyanide concentration in the feed solution, TOA concentration in the organic phase, the stirring speed, NaOH concentration in the stripping solution and temperature on cyanide transport was determined through BLM. Mass transfer of cyanide through BLM was analyzed by following the kinetic laws of two consecutive irreversible first-order reactions, and the kinetic parameters (k(1), k(2), R(m)(max), t(max), J(a)(max), J(d)(max)) were also calculated. Apparently, increase in membrane entrance (k(1)) and exit rate (k(2)) constants was accompanied by a rise in temperature. The values of activation energies were obtained as 35.6 kJ/mol and 18.2 kJ/mol for removal and recovery, respectively. These values showed that both removal and recovery steps in cyanide transport is controlled by the rate of the chemical complexation reaction. The optimal reaction conditions were determined by BLM using trioctylamine as the carrier: feed phase: pH 4, carrier TOA possession ratio in organic phase: 2% (V/V), stripping phase concentration of NaOH: 1% (W/V), reaction time: 60 min, stirring speed: 250 r/min. Under the above conditions, the removal rate was up to 92.96%. The experiments demonstrated that TOA was a good carrier for cyanide transport through BLM in this study.

Synthesis, properties, and application in peptide chemistry of a magnetically separable and reusable biocatalyst

NASA Astrophysics Data System (ADS)

Liria, Cleber W.; Ungaro, Vitor A.; Fernandes, Raphaella M.; Costa, Natália J. S.; Marana, Sandro R.; Rossi, Liane M.; Machini, M. Teresa

2014-11-01

Enzyme-catalyzed chemical processes are selective, very productive, and generate little waste. Nevertheless, they may be optimized using enzymes bound to solid supports, which are particularly important for protease-mediated reactions since proteases undergo fast autolysis in solution. Magnetic nanoparticles are suitable supports for this purpose owing to their high specific surface area and to be easily separated from reaction media. Here we describe the immobilization of bovine α-chymotrypsin (αCT) on silica-coated superparamagnetic nanoparticles (Fe3O4@silica) and the characterization of the enzyme-nanoparticle hybrid (Fe3O4@silica-αCT) in terms of protein content, properties, recovery from reaction media, application, and reuse in enzyme-catalyzed peptide synthesis. The results revealed that (i) full acid hydrolysis of the immobilized protease followed by amino acid analysis of the hydrolyzate is a reliable method to determine immobilization yield; (ii) despite showing lower amidase activity and a lower K cat/ K m value for a specific substrate than free αCT, the immobilized enzyme is chemically and thermally more stable, magnetically recoverable from reaction media, and can be consecutively reused for ten cycles to catalyze the amide bond hydrolysis and ester hydrolysis of the protected dipeptide Z-Ala-Phe-OMe. Altogether, these properties indicate the potential of Fe3O4@silica-αCT to act as an efficient, suitably stable, and reusable catalyst in amino acid, peptide, and protein chemistry as well as in proteomic studies.

An introduction to multidimensional measurement using Rasch models.

PubMed

Briggs, Derek C; Wilson, Mark

2003-01-01

The act of constructing a measure requires a number of important assumptions. Principle among these assumptions is that the construct is unidimensional. In practice there are many instances when the assumption of unidimensionality does not hold, and where the application of a multidimensional measurement model is both technically appropriate and substantively advantageous. In this paper we illustrate the usefulness of a multidimensional approach to measurement with the Multidimensional Random Coefficient Multinomial Logit (MRCML) model, an extension of the unidimensional Rasch model. An empirical example is taken from a collection of embedded assessments administered to 541 students enrolled in middle school science classes with a hands-on science curriculum. Student achievement on these assessments are multidimensional in nature, but can also be treated as consecutive unidimensional estimates, or as is most common, as a composite unidimensional estimate. Structural parameters are estimated for each model using ConQuest, and model fit is compared. Student achievement in science is also compared across models. The multidimensional approach has the best fit to the data, and provides more reliable estimates of student achievement than under the consecutive unidimensional approach. Finally, at an interpretational level, the multidimensional approach may well provide richer information to the classroom teacher about the nature of student achievement.

Neonatal intensive care unit: predictive models for length of stay.

PubMed

Bender, G J; Koestler, D; Ombao, H; McCourt, M; Alskinis, B; Rubin, L P; Padbury, J F

2013-02-01

Hospital length of stay (LOS) is important to administrators and families of neonates admitted to the neonatal intensive care unit (NICU). A prediction model for NICU LOS was developed using predictors birth weight, gestational age and two severity of illness tools, the score for neonatal acute physiology, perinatal extension (SNAPPE) and the morbidity assessment index for newborns (MAIN). Consecutive admissions (n=293) to a New England regional level III NICU were retrospectively collected. Multiple predictive models were compared for complexity and goodness-of-fit, coefficient of determination (R (2)) and predictive error. The optimal model was validated prospectively with consecutive admissions (n=615). Observed and expected LOS was compared. The MAIN models had best Akaike's information criterion, highest R (2) (0.786) and lowest predictive error. The best SNAPPE model underestimated LOS, with substantial variability, yet was fairly well calibrated by birthweight category. LOS was longer in the prospective cohort than the retrospective cohort, without differences in birth weight, gestational age, MAIN or SNAPPE. LOS prediction is improved by accounting for severity of illness in the first week of life, beyond factors known at birth. Prospective validation of both MAIN and SNAPPE models is warranted.

Coupled enzyme reactions performed in heterogeneous reaction media: experiments and modeling for glucose oxidase and horseradish peroxidase in a PEG/citrate aqueous two-phase system.

PubMed

Aumiller, William M; Davis, Bradley W; Hashemian, Negar; Maranas, Costas; Armaou, Antonios; Keating, Christine D

2014-03-06

The intracellular environment in which biological reactions occur is crowded with macromolecules and subdivided into microenvironments that differ in both physical properties and chemical composition. The work described here combines experimental and computational model systems to help understand the consequences of this heterogeneous reaction media on the outcome of coupled enzyme reactions. Our experimental model system for solution heterogeneity is a biphasic polyethylene glycol (PEG)/sodium citrate aqueous mixture that provides coexisting PEG-rich and citrate-rich phases. Reaction kinetics for the coupled enzyme reaction between glucose oxidase (GOX) and horseradish peroxidase (HRP) were measured in the PEG/citrate aqueous two-phase system (ATPS). Enzyme kinetics differed between the two phases, particularly for the HRP. Both enzymes, as well as the substrates glucose and H2O2, partitioned to the citrate-rich phase; however, the Amplex Red substrate necessary to complete the sequential reaction partitioned strongly to the PEG-rich phase. Reactions in ATPS were quantitatively described by a mathematical model that incorporated measured partitioning and kinetic parameters. The model was then extended to new reaction conditions, i.e., higher enzyme concentration. Both experimental and computational results suggest mass transfer across the interface is vital to maintain the observed rate of product formation, which may be a means of metabolic regulation in vivo. Although outcomes for a specific system will depend on the particulars of the enzyme reactions and the microenvironments, this work demonstrates how coupled enzymatic reactions in complex, heterogeneous media can be understood in terms of a mathematical model.

Development Of Simulation Model For Fluid Catalytic Cracking

NASA Astrophysics Data System (ADS)

Ghosh, Sobhan

2010-10-01

Fluid Catalytic Cracking (FCC) is the most widely used secondary conversion process in the refining industry, for producing gasoline, olefins, and middle distillate from heavier petroleum fractions. There are more than 500 units in the world with a total processing capacity of about 17 to 20% of the crude capacity. FCC catalyst is the highest consumed catalyst in the process industry. On one hand, FCC is quite flexible with respect to it's ability to process wide variety of crudes with a flexible product yield pattern, and on the other hand, the interdependence of the major operating parameters makes the process extremely complex. An operating unit is self balancing and some fluctuations in the independent parameters are automatically adjusted by changing the temperatures and flow rates at different sections. However, a good simulation model is very useful to the refiner to get the best out of the process, in terms of selection of the best catalyst, to cope up with the day to day changing of the feed quality and the demands of different products from FCC unit. In addition, a good model is of great help in designing the process units and peripherals. A simple empirical model is often adequate to monitor the day to day operations, but they are not of any use in handling the other problems such as, catalyst selection or, design / modification of the plant. For this, a kinetic based rigorous model is required. Considering the complexity of the process, large number of chemical species undergoing "n" number of parallel and consecutive reactions, it is virtually impossible to develop a simulation model based on the kinetic parameters. The most common approach is to settle for a semi empirical model. We shall take up the key issues for developing a FCC model and the contribution of such models in the optimum operation of the plant.

Structure-reactivity modeling using mixture-based representation of chemical reactions.

PubMed

Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre

2017-09-01

We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

Teacher Spillover Effects across Four Subjects in Middle Schools

ERIC Educational Resources Information Center

Yuan, Kun

2014-01-01

Value-added modeling (VAM), one class of statistical models used to estimate individual teacher's or school's contribution to student achievement based on student test score growth between consecutive years, has become increasingly popular in the last decades. Despite the increasing popularity of VAM, many researchers are concerned about the…

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE PAGES

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; ...

2017-10-12

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

NASA Astrophysics Data System (ADS)

Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

2017-10-01

In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

Reframed Genome-Scale Metabolic Model to Facilitate Genetic Design and Integration with Expression Data.

PubMed

Gu, Deqing; Jian, Xingxing; Zhang, Cheng; Hua, Qiang

2017-01-01

Genome-scale metabolic network models (GEMs) have played important roles in the design of genetically engineered strains and helped biologists to decipher metabolism. However, due to the complex gene-reaction relationships that exist in model systems, most algorithms have limited capabilities with respect to directly predicting accurate genetic design for metabolic engineering. In particular, methods that predict reaction knockout strategies leading to overproduction are often impractical in terms of gene manipulations. Recently, we proposed a method named logical transformation of model (LTM) to simplify the gene-reaction associations by introducing intermediate pseudo reactions, which makes it possible to generate genetic design. Here, we propose an alternative method to relieve researchers from deciphering complex gene-reactions by adding pseudo gene controlling reactions. In comparison to LTM, this new method introduces fewer pseudo reactions and generates a much smaller model system named as gModel. We showed that gModel allows two seldom reported applications: identification of minimal genomes and design of minimal cell factories within a modified OptKnock framework. In addition, gModel could be used to integrate expression data directly and improve the performance of the E-Fmin method for predicting fluxes. In conclusion, the model transformation procedure will facilitate genetic research based on GEMs, extending their applications.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Foy, E.; Ronan, G.; Chinitz, W.

1982-01-01

A principal element to be derived from modeling turbulent reacting flows is an expression for the reaction rates of the various species involved in any particular combustion process under consideration. A temperature-derived most-likely probability density function (pdf) was used to describe the effects of temperature fluctuations on the Arrhenius reaction rate constant. A most-likely bivariate pdf described the effects of temperature and species concentrations fluctuations on the reaction rate. A criterion is developed for the use of an "appropriate" temperature pdf. The formulation of models to calculate the mean turbulent Arrhenius reaction rate constant and the mean turbulent reaction rate is considered and the results of calculations using these models are presented.

Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

ERIC Educational Resources Information Center

Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

2016-01-01

A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

A more robust model of the biodiesel reaction, allowing identification of process conditions for significantly enhanced rate and water tolerance.

PubMed

Eze, Valentine C; Phan, Anh N; Harvey, Adam P

2014-03-01

A more robust kinetic model of base-catalysed transesterification than the conventional reaction scheme has been developed. All the relevant reactions in the base-catalysed transesterification of rapeseed oil (RSO) to fatty acid methyl ester (FAME) were investigated experimentally, and validated numerically in a model implemented using MATLAB. It was found that including the saponification of RSO and FAME side reactions and hydroxide-methoxide equilibrium data explained various effects that are not captured by simpler conventional models. Both the experiment and modelling showed that the "biodiesel reaction" can reach the desired level of conversion (>95%) in less than 2min. Given the right set of conditions, the transesterification can reach over 95% conversion, before the saponification losses become significant. This means that the reaction must be performed in a reactor exhibiting good mixing and good control of residence time, and the reaction mixture must be quenched rapidly as it leaves the reactor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dynamic modeling of reversible methanolysis of Jatropha curcas oil to biodiesel.

PubMed

Syam, Azhari M; Hamid, Hamidah A; Yunus, Robiah; Rashid, Umer

2013-01-01

Many kinetics studies on methanolysis assumed the reactions to be irreversible. The aim of the present work was to study the dynamic modeling of reversible methanolysis of Jatropha curcas oil (JCO) to biodiesel. The experimental data were collected under the optimal reaction conditions: molar ratio of methanol to JCO at 6 : 1, reaction temperature of 60°C, 60 min of reaction time, and 1% w/w of catalyst concentration. The dynamic modeling involved the derivation of differential equations for rates of three stepwise reactions. The simulation study was then performed on the resulting equations using MATLAB. The newly developed reversible models were fitted with various rate constants and compared with the experimental data for fitting purposes. In addition, analysis of variance was done statistically to evaluate the adequacy and quality of model parameters. The kinetics study revealed that the reverse reactions were significantly slower than forward reactions. The activation energies ranged from 6.5 to 44.4 KJ mol⁻¹.

Dynamic Modeling of Reversible Methanolysis of Jatropha curcas Oil to Biodiesel

PubMed Central

Syam, Azhari M.; Hamid, Hamidah A.; Yunus, Robiah; Rashid, Umer

2013-01-01

Many kinetics studies on methanolysis assumed the reactions to be irreversible. The aim of the present work was to study the dynamic modeling of reversible methanolysis of Jatropha curcas oil (JCO) to biodiesel. The experimental data were collected under the optimal reaction conditions: molar ratio of methanol to JCO at 6 : 1, reaction temperature of 60°C, 60 min of reaction time, and 1% w/w of catalyst concentration. The dynamic modeling involved the derivation of differential equations for rates of three stepwise reactions. The simulation study was then performed on the resulting equations using MATLAB. The newly developed reversible models were fitted with various rate constants and compared with the experimental data for fitting purposes. In addition, analysis of variance was done statistically to evaluate the adequacy and quality of model parameters. The kinetics study revealed that the reverse reactions were significantly slower than forward reactions. The activation energies ranged from 6.5 to 44.4 KJ mol−1. PMID:24363616

Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

NASA Astrophysics Data System (ADS)

Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

2013-11-01

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Safety, reactogenicity and immunogenicity of a booster dose of the 10-valent pneumococcal non-typeable Haemophilus influenzae protein D conjugate vaccine (PHiD-CV) in Malian children.

PubMed

Dicko, Alassane; Santara, Gaoussou; Mahamar, Almahamoudou; Sidibe, Youssoufa; Barry, Amadou; Dicko, Yahia; Diallo, Aminata; Dolo, Amagana; Doumbo, Ogobara; Shafi, Fakrudeen; François, Nancy; Strezova, Ana; Borys, Dorota; Schuerman, Lode

2013-02-01

Primary vaccination with the 10-valent pneumococcal non-typeable Haemophilus influenzae protein D conjugate vaccine (PHiD-CV) was previously shown to be immunogenic and well tolerated in Malian children. Data on booster vaccination with a fourth consecutive dose of PHiD-CV are available for Europe, Asia and Latin America but are lacking for Africa. The present study evaluated further the safety, reactogenicity and immunogenicity of a fourth consecutive (booster) dose of PHiD-CV. Low incidences of AEs with grade 3 intensity (2.1% of subjects) were observed. There were no reports of large swelling reactions and serious adverse events. One month post-booster vaccination, for each vaccine pneumococcal serotype, at least 97.8% of subjects had antibody concentrations ≥ 0.2 μg/ml, and at least 97.1% of subjects had opsonophagocytic activity ≥ 8. From pre- to post-booster, a 12.3-fold increase in anti-protein D geometric mean concentration was observed. This phase III, open-label study was conducted in Ouelessebougou, Mali, between November 2009 and June 2010. The study population consisted of Malian children previously primed (3 doses) with PHiD-CV in study NCT00678301 receiving a fourth consecutive (booster) dose of PHiD-CV in the second year of life. The incidences of adverse events (AEs) with grade 3 intensity (primary objective) or of any intensity (secondary objective), and the immunogenicity (secondary objective) of the PHiD-CV booster dose were assessed. A booster dose of PHiD-CV was well tolerated when administered to Malian children in the second year of life and was highly immunogenic for all 10 vaccine pneumococcal serotypes and NTHi protein D. (ClinicalTrials.gov identifier: NCT00985465).

Comparison of LAMP and PCR for molecular mass screening of sand flies for Leishmania martiniquensis infection.

PubMed

Tiwananthagorn, Saruda; Kato, Hirotomo; Yeewa, Ranchana; Muengpan, Amontip; Polseela, Raxsina; Leelayoova, Saovanee

2017-02-01

Leishmaniasis caused by Leishmania martiniquensis infection has been reported in human and domestic animals of Martinique Island, Germany, Switzerland, USA, Myanmar and Thailand. The peculiar clinical features of disseminated cutaneous and visceral forms co-existence render the urgent need of specific diagnostic tool to identify the natural sand fly vectors for effective prevention and control strategies. Loop-mediated isothermal amplification (LAMP) of 18S rRNA gene as well as polymerase chain reaction (PCR) of minicircle kinetoplast DNA gene (PCR-mkDNA) have never been applied to detect L. martiniquensis and L. siamensis in sand fly vectors. The present study was aimed to validate malachite green-LAMP (MG-LAMP) and PCR-mkDNA techniques to detect L. martiniquensis in sand fly vectors, compared with the conventional PCR of internal transcribed spacer 1 (PCR-ITS1). We compared the validity of LAMP of 18S rRNA gene and PCR-mkDNA, to PCR-ITS1 in simulation model of L. martiniquensis infection in Sergentomyia gemmea sand flies. Attributable to the sensitivity and specificity, PCR-mkDNA was consecutively applied to detect L. martiniquensis in 380 female sand fly individuals captured in the newly identified affected region of Lamphun Province, Thailand. Results showed that PCR-mkDNA could detect at least one promastigote per sand fly, which was 10-time superior to LAMP and PCR-ITS1. In addition, PCR-mkDNA was more specific, able to differentiate L. martiniquensis from other viscerotropic Leishmania species, such as L. siamensis, L. (L.) donovani, and L. (L.) infantum. Consecutively, mass screening of L. martiniquensis in 380 female sand fly individuals by PCR-mkDNA was implemented in a new affected area of Thailand where a patient with leishmaniasis/HIV co-infection resides; however Leishmania DNA was undetected. In conclusion, PCR-mkDNA is a promising tool for molecular mass screening of L. martiniquensis infection in outbreak areas where several species of Leishmania and sand flies co-exist.

PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

USGS Publications Warehouse

Parkhurst, David L.; Wissmeier, Laurin

2015-01-01

PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst–Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants.PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

Introducing improved structural properties and salt dependence into a coarse-grained model of DNA

NASA Astrophysics Data System (ADS)

Snodin, Benedict E. K.; Randisi, Ferdinando; Mosayebi, Majid; Šulc, Petr; Schreck, John S.; Romano, Flavio; Ouldridge, Thomas E.; Tsukanov, Roman; Nir, Eyal; Louis, Ard A.; Doye, Jonathan P. K.

2015-06-01

We introduce an extended version of oxDNA, a coarse-grained model of deoxyribonucleic acid (DNA) designed to capture the thermodynamic, structural, and mechanical properties of single- and double-stranded DNA. By including explicit major and minor grooves and by slightly modifying the coaxial stacking and backbone-backbone interactions, we improve the ability of the model to treat large (kilobase-pair) structures, such as DNA origami, which are sensitive to these geometric features. Further, we extend the model, which was previously parameterised to just one salt concentration ([Na+] = 0.5M), so that it can be used for a range of salt concentrations including those corresponding to physiological conditions. Finally, we use new experimental data to parameterise the oxDNA potential so that consecutive adenine bases stack with a different strength to consecutive thymine bases, a feature which allows a more accurate treatment of systems where the flexibility of single-stranded regions is important. We illustrate the new possibilities opened up by the updated model, oxDNA2, by presenting results from simulations of the structure of large DNA objects and by using the model to investigate some salt-dependent properties of DNA.

Introducing improved structural properties and salt dependence into a coarse-grained model of DNA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snodin, Benedict E. K., E-mail: benedict.snodin@chem.ox.ac.uk; Mosayebi, Majid; Schreck, John S.

2015-06-21

We introduce an extended version of oxDNA, a coarse-grained model of deoxyribonucleic acid (DNA) designed to capture the thermodynamic, structural, and mechanical properties of single- and double-stranded DNA. By including explicit major and minor grooves and by slightly modifying the coaxial stacking and backbone-backbone interactions, we improve the ability of the model to treat large (kilobase-pair) structures, such as DNA origami, which are sensitive to these geometric features. Further, we extend the model, which was previously parameterised to just one salt concentration ([Na{sup +}] = 0.5M), so that it can be used for a range of salt concentrations including thosemore » corresponding to physiological conditions. Finally, we use new experimental data to parameterise the oxDNA potential so that consecutive adenine bases stack with a different strength to consecutive thymine bases, a feature which allows a more accurate treatment of systems where the flexibility of single-stranded regions is important. We illustrate the new possibilities opened up by the updated model, oxDNA2, by presenting results from simulations of the structure of large DNA objects and by using the model to investigate some salt-dependent properties of DNA.« less

Anomalous Impact in Reaction-Diffusion Financial Models

NASA Astrophysics Data System (ADS)

Mastromatteo, I.; Tóth, B.; Bouchaud, J.-P.

2014-12-01

We generalize the reaction-diffusion model A +B → /0 in order to study the impact of an excess of A (or B ) at the reaction front. We provide an exact solution of the model, which shows that the linear response breaks down: the average displacement of the reaction front grows as the square root of the imbalance. We argue that this model provides a highly simplified but generic framework to understand the square-root impact of large orders in financial markets.

Anomalous diffusion with linear reaction dynamics: from continuous time random walks to fractional reaction-diffusion equations.

PubMed

Henry, B I; Langlands, T A M; Wearne, S L

2006-09-01

We have revisited the problem of anomalously diffusing species, modeled at the mesoscopic level using continuous time random walks, to include linear reaction dynamics. If a constant proportion of walkers are added or removed instantaneously at the start of each step then the long time asymptotic limit yields a fractional reaction-diffusion equation with a fractional order temporal derivative operating on both the standard diffusion term and a linear reaction kinetics term. If the walkers are added or removed at a constant per capita rate during the waiting time between steps then the long time asymptotic limit has a standard linear reaction kinetics term but a fractional order temporal derivative operating on a nonstandard diffusion term. Results from the above two models are compared with a phenomenological model with standard linear reaction kinetics and a fractional order temporal derivative operating on a standard diffusion term. We have also developed further extensions of the CTRW model to include more general reaction dynamics.

Charge-dependent non-bonded interaction methods for use in quantum mechanical modeling of condensed phase reactions

NASA Astrophysics Data System (ADS)

Kuechler, Erich R.

Molecular modeling and computer simulation techniques can provide detailed insight into biochemical phenomena. This dissertation describes the development, implementation and parameterization of two methods for the accurate modeling of chemical reactions in aqueous environments, with a concerted scientific effort towards the inclusion of charge-dependent non-bonded non-electrostatic interactions into currently used computational frameworks. The first of these models, QXD, modifies interactions in a hybrid quantum mechanical/molecular (QM/MM) mechanical framework to overcome the current limitations of 'atom typing' QM atoms; an inaccurate and non-intuitive practice for chemically active species as these static atom types are dictated by the local bonding and electrostatic environment of the atoms they represent, which will change over the course of the simulation. The efficacy QXD model is demonstrated using a specific reaction parameterization (SRP) of the Austin Model 1 (AM1) Hamiltonian by simultaneously capturing the reaction barrier for chloride ion attack on methylchloride in solution and the solvation free energies of a series of compounds including the reagents of the reaction. The second, VRSCOSMO, is an implicit solvation model for use with the DFTB3/3OB Hamiltonian for biochemical reactions; allowing for accurate modeling of ionic compound solvation properties while overcoming the discontinuous nature of conventional PCM models when chemical reaction coordinates. The VRSCOSMO model is shown to accurately model the solvation properties of over 200 chemical compounds while also providing smooth, continuous reaction surfaces for a series of biologically motivated phosphoryl transesterification reactions. Both of these methods incorporate charge-dependent behavior into the non-bonded interactions variationally, allowing the 'size' of atoms to change in meaningful ways with respect to changes in local charge state, as to provide an accurate, predictive and transferable models for the interactions between the quantum mechanical system and their solvated surroundings.

Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method.

PubMed

Xie, Hai-Yang; Liu, Qian; Li, Jia-Hao; Fan, Liu-Yin; Cao, Cheng-Xi

2013-02-21

A novel moving redox reaction boundary (MRRB) model was developed for studying electrophoretic behaviors of analytes involving redox reaction on the principle of moving reaction boundary (MRB). Traditional potassium permanganate method was used to create the boundary model in agarose gel electrophoresis because of the rapid reaction rate associated with MnO(4)(-) ions and Fe(2+) ions. MRB velocity equation was proposed to describe the general functional relationship between velocity of moving redox reaction boundary (V(MRRB)) and concentration of reactant, and can be extrapolated to similar MRB techniques. Parameters affecting the redox reaction boundary were investigated in detail. Under the selected conditions, good linear relationship between boundary movement distance and time were obtained. The potential application of MRRB in electromigration redox reaction titration was performed in two different concentration levels. The precision of the V(MRRB) was studied and the relative standard deviations were below 8.1%, illustrating the good repeatability achieved in this experiment. The proposed MRRB model enriches the MRB theory and also provides a feasible realization of manual control of redox reaction process in electrophoretic analysis.

Hydrolysis of Nerve Agents by Model Nucleophiles: A Computational Study

PubMed Central

Beck, Jeremy M.

2008-01-01

Density functional theory calculations were employed to study the reaction of five nerve agents with model nucleophiles, including EtX− and EtXH (X = O, S, Se) for serine, cysteine and selenocysteine, respectively. Calculations at the B3LYP/6-311++G(2d,p) level of theory predict an exothermic reaction between ethoxide and all of the nerve agents studied. As compared to EtO− as a nucleophile, these reactions become ~30 kcal/mol more endothermic for EtS−, and by ~40 kcal/mol for EtSe−. The equivalent reactions with the neutral nucleophiles (EtXH) were more endothermic. The effect of solvation on the reaction thermochemistry was determined using a polarizable continuum model simulating the dielectric constant of chloroform. While there was a large exothermic shift for reactions involving charged nucleophiles with solvation modeling, the corresponding shift was minimal for the reaction with neutral nucleophiles. PMID:18538754

The influence of the "cage" effect on the mechanism of reversible bimolecular multistage chemical reactions proceeding from different sites in solutions.

PubMed

Doktorov, Alexander B

2016-08-28

Manifestations of the "cage" effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the "cage complex," just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of the "cage" effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.

ECUT: Energy Conversion and Utilization Technologies program. Heterogeneous catalysis modeling program concept

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1983-01-01

Insufficient theoretical definition of heterogeneous catalysts is the major difficulty confronting industrial suppliers who seek catalyst systems which are more active, selective, and stable than those currently available. In contrast, progress was made in tailoring homogeneous catalysts to specific reactions because more is known about the reaction intermediates promoted and/or stabilized by these catalysts during the course of reaction. However, modeling heterogeneous catalysts on a microscopic scale requires compiling and verifying complex information on reaction intermediates and pathways. This can be achieved by adapting homogeneous catalyzed reaction intermediate species, applying theoretical quantum chemistry and computer technology, and developing a better understanding of heterogeneous catalyst system environments. Research in microscopic reaction modeling is now at a stage where computer modeling, supported by physical experimental verification, could provide information about the dynamics of the reactions that will lead to designing supported catalysts with improved selectivity and stability.

Reaction rates for mesoscopic reaction-diffusion kinetics

DOE PAGES

Hellander, Stefan; Hellander, Andreas; Petzold, Linda

2015-02-23

The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In thismore » paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.« less

Reaction rates for mesoscopic reaction-diffusion kinetics

PubMed Central

Hellander, Stefan; Hellander, Andreas; Petzold, Linda

2016-01-01

The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results. PMID:25768640

Treatment of palmoplantar warts with a diphencyprone and salicylic acid ointment.

PubMed

Armour, Katherine; Orchard, David

2006-08-01

We report on 50 consecutive suitable patients with one or more palmoplantar warts who were treated with a patient-applied ointment comprising 0.1% diphencyprone and 15% salicylic acid in white soft paraffin. All patients sensitized to diphencyprone were followed up clinically and assessed by patient questionnaire. The intention to treat success rate in this series was 88%. The time to wart clearance ranged from less than 4 weeks to 4 months. In our patient group, 90% rated their treatment as 'excellent' or 'good', whereas 10% stated that the reaction induced by diphencyprone was 'too severe'. Our results are compared with those previously published using diphencyprone in the treatment of palmoplantar warts.

Ingenol Mebutate for Recalcitrant Chronic Actinic Cheilitis.

PubMed

Tzika, Evangelia; Masouyé, Isabelle; Mühlstädt, Michael; Laffitte, Emmanuel

2016-01-01

We present the case of a healthy 76-year-old man with a whitish, hyperkeratotic lesion of the lower lip diagnosed as actinic cheilitis (AC) previously treated with classic red light photodynamic therapy 5 years ago. Initial treatment with 5% imiquimod cream - also with intensified application - failed. After 2 cycles thrice daily, consecutive applications of 150 μg/g ingenol mebutate gel at 3 weeks' interval, the lesions cleared completely. Surprisingly, no pustular or crusting reaction or other side effect occurred contrary to expectation. Remission was stable for 10 months, when recurrence occurred. Ingenol mebutate proved to be a feasible and safe treatment in this otherwise refractory case of AC. © 2016 S. Karger AG, Basel.

A programmable microfluidic static droplet array for droplet generation, transportation, fusion, storage, and retrieval.

PubMed

Jin, Si Hyung; Jeong, Heon-Ho; Lee, Byungjin; Lee, Sung Sik; Lee, Chang-Soo

2015-01-01

We present a programmable microfluidic static droplet array (SDA) device that can perform user-defined multistep combinatorial protocols. It combines the passive storage of aqueous droplets without any external control with integrated microvalves for discrete sample dispensing and dispersion-free unit operation. The addressable picoliter-volume reaction is systematically achieved by consecutively merging programmable sequences of reagent droplets. The SDA device is remarkably reusable and able to perform identical enzyme kinetic experiments at least 30 times via automated cross-contamination-free removal of droplets from individual hydrodynamic traps. Taking all these features together, this programmable and reusable universal SDA device will be a general microfluidic platform that can be reprogrammed for multiple applications.

Mathematics in chemistry: indeterminate forms and their meaning

NASA Astrophysics Data System (ADS)

Segurado, Manuel A. P.; Silva, Margarida F. B.; Castro, Rita

2011-07-01

The mathematical language and its tools are complementary to the formalism in chemistry, in particular at an advanced level. It is thus crucial, for its understanding, that students acquire a solid knowledge in Calculus and that they know how to apply it. The frequent occurrence of indeterminate forms in multiple areas, particularly in Physical Chemistry, justifies the need to properly understand the limiting process in such cases. This article emphasizes the importance of the L'Hôpital's rule as a practical tool, although often neglected, to obtain the more common indeterminate limits, through the use of some specific examples as the radioactive decay, spectrophotometric error, Planck's radiation law, second-order kinetics, or consecutive reactions.

One-pot syntheses of blue-luminescent 4-aryl-1H-benzo[f]isoindole-1,3(2H)-diones by T3P® activation of 3-arylpropiolic acids.

PubMed

Denißen, Melanie; Kraus, Alexander; Reiss, Guido J; Müller, Thomas J J

2017-01-01

In situ activation of 3-arylpropiolic acids with T3P ® ( n -propylphosphonic acid anhydride) initiates a domino reaction furnishing 4-arylnaphtho[2,3- c ]furan-1,3-diones in excellent yields. Upon employing these anhydrides as reactive intermediates blue-luminescent 4-aryl-1 H -benzo[ f ]isoindole-1,3(2 H )-diones are formed by consecutive pseudo three-component syntheses in a one-pot fashion. The Stokes shifts correlate excellently with the Hammett-Taft σ R parameter indicating an extended degree of resonance stabilization in the vibrationally relaxed excited singlet state.

One-pot syntheses of blue-luminescent 4-aryl-1H-benzo[f]isoindole-1,3(2H)-diones by T3P® activation of 3-arylpropiolic acids

PubMed Central

Denißen, Melanie; Kraus, Alexander; Reiss, Guido J

2017-01-01

In situ activation of 3-arylpropiolic acids with T3P® (n-propylphosphonic acid anhydride) initiates a domino reaction furnishing 4-arylnaphtho[2,3-c]furan-1,3-diones in excellent yields. Upon employing these anhydrides as reactive intermediates blue-luminescent 4-aryl-1H-benzo[f]isoindole-1,3(2H)-diones are formed by consecutive pseudo three-component syntheses in a one-pot fashion. The Stokes shifts correlate excellently with the Hammett–Taft σR parameter indicating an extended degree of resonance stabilization in the vibrationally relaxed excited singlet state. PMID:29181114

Serial crystallography captures enzyme catalysis in copper nitrite reductase at atomic resolution from one crystal.

PubMed

Horrell, Sam; Antonyuk, Svetlana V; Eady, Robert R; Hasnain, S Samar; Hough, Michael A; Strange, Richard W

2016-07-01

Relating individual protein crystal structures to an enzyme mechanism remains a major and challenging goal for structural biology. Serial crystallography using multiple crystals has recently been reported in both synchrotron-radiation and X-ray free-electron laser experiments. In this work, serial crystallography was used to obtain multiple structures serially from one crystal (MSOX) to study in crystallo enzyme catalysis. Rapid, shutterless X-ray detector technology on a synchrotron MX beamline was exploited to perform low-dose serial crystallography on a single copper nitrite reductase crystal, which survived long enough for 45 consecutive 100 K X-ray structures to be collected at 1.07-1.62 Å resolution, all sampled from the same crystal volume. This serial crystallography approach revealed the gradual conversion of the substrate bound at the catalytic type 2 Cu centre from nitrite to nitric oxide, following reduction of the type 1 Cu electron-transfer centre by X-ray-generated solvated electrons. Significant, well defined structural rearrangements in the active site are evident in the series as the enzyme moves through its catalytic cycle, namely nitrite reduction, which is a vital step in the global denitrification process. It is proposed that such a serial crystallography approach is widely applicable for studying any redox or electron-driven enzyme reactions from a single protein crystal. It can provide a 'catalytic reaction movie' highlighting the structural changes that occur during enzyme catalysis. The anticipated developments in the automation of data analysis and modelling are likely to allow seamless and near-real-time analysis of such data on-site at some of the powerful synchrotron crystallographic beamlines.

Titanite-bearing calc-silicate rocks constrain timing, duration and magnitude of metamorphic CO2 degassing in the Himalayan belt

NASA Astrophysics Data System (ADS)

Rapa, Giulia; Groppo, Chiara; Rolfo, Franco; Petrelli, Maurizio; Mosca, Pietro; Perugini, Diego

2017-11-01

The pressure, temperature, and timing (P-T-t) conditions at which CO2 was produced during the Himalayan prograde metamorphism have been constrained, focusing on the most abundant calc-silicate rock type in the Himalaya. A detailed petrological modeling of a clinopyroxene + scapolite + K-feldspar + plagioclase + quartz ± calcite calc-silicate rock allowed the identification and full characterization - for the first time - of different metamorphic reactions leading to the simultaneous growth of titanite and CO2 production. The results of thermometric determinations (Zr-in-Ttn thermometry) and U-Pb geochronological analyses suggest that, in the studied lithology, most titanite grains grew during two nearly consecutive episodes of titanite formation: a near-peak event at 730-740 °C, 10 kbar, 30-26 Ma, and a peak event at 740-765 °C, 10.5 kbar, 25-20 Ma. Both episodes of titanite growth are correlated with specific CO2-producing reactions and constrain the timing, duration and P-T conditions of the main CO2-producing events, as well as the amounts of CO2 produced (1.4-1.8 wt% of CO2). A first-order extrapolation of such CO2 amounts to the orogen scale provides metamorphic CO2 fluxes ranging between 1.4 and 19.4 Mt/yr; these values are of the same order of magnitude as the present-day CO2 fluxes degassed from spring waters located along the Main Central Thrust. We suggest that these metamorphic CO2 fluxes should be considered in any future attempts of estimating the global budget of non-volcanic carbon fluxes from the lithosphere.

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

USGS Publications Warehouse

Lorah, Michelle M.; Herman, Janet S.

1988-01-01

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO2outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO2, outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO2 along the entire 5.2-km flow path. Outgassing of CO2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO2. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Modeling Individual Differences in Within-Person Variation of Negative and Positive Affect in a Mixed Effects Location Scale Model Using BUGS/JAGS

ERIC Educational Resources Information Center

Rast, Philippe; Hofer, Scott M.; Sparks, Catharine

2012-01-01

A mixed effects location scale model was used to model and explain individual differences in within-person variability of negative and positive affect across 7 days (N=178) within a measurement burst design. The data come from undergraduate university students and are pooled from a study that was repeated at two consecutive years. Individual…

Unveiling Singlet Fission Mediating States in TIPS-pentacene and its Aza Derivatives.

PubMed

Herz, Julia; Buckup, Tiago; Paulus, Fabian; Engelhart, Jens U; Bunz, Uwe H F; Motzkus, Marcus

2015-06-25

Femtosecond pump-depletion-probe experiments were carried out in order to shed light on the ultrafast excited-state dynamics of triisopropylsilylethynyl (TIPS)-pentacene and two nitrogen-containing derivatives, namely, diaza-TIPS-pentacene and tetraaza-TIPS-pentacene. Measurements performed in the visible and near-infrared spectral range in combination with rate model simulations reveal that singlet fission proceeds via the extremely short-lived intermediate (1)TT state, which absorbs in the near-infrared spectral region only. The T1 → T3 transition probed in the visible region shows a rise time that comprises two components according to a consecutive reaction (S1 → (1)TT → T1). The incorporation of nitrogen atoms into the acene structure leads to shorter dynamics, but the overall triplet formation follows the same kinetic model. This is of particular importance, since experiments on tetraaza-TIPS-pentacene allow for investigation of the triplet state in the visible range without an overlapping singlet contribution. In addition, the pump-depletion-probe experiments show that the triplet absorption in the visible (T1 → T3) and near-infrared (T1 → T2) regions occurs from the same initial state, which was questioned in previous studies. Furthermore, an additional ultrafast transfer between the excited triplet states (T3 → T2) is identified, which is also in agreement with the rate model simulation. By applying depletion pulses, which are resonant with higher vibrational levels, we gain insight into internal vibrational energy redistribution processes within the triplet manifold. This additional information is of great relevance regarding the study of loss channels within these materials.

Generalized Pseudo-Reaction Zone Model for Non-Ideal Explosives

NASA Astrophysics Data System (ADS)

Wescott, B. L.

2007-12-01

The pseudo-reaction zone model was proposed to improve engineering scale simulations with high explosives that have a slow reaction component. In this work an extension of the pseudo-reaction zone model is developed for non-ideal explosives that propagate well below the steady-planar Chapman-Jouguet velocity. A programmed burn method utilizing Detonation Shock Dynamics (DSD) and a detonation velocity dependent pseudo-reaction rate has been developed for non-ideal explosives and applied to the explosive mixture of ammonium nitrate and fuel oil (ANFO). The pseudo-reaction rate is calibrated to the experimentally obtained normal detonation velocity—shock curvature relation. Cylinder test simulations predict the proper expansion to within 1% even though significant reaction occurs as the cylinder expands.

[Expression of aquaporin-4 during brain edema in rats with thioacetamide-induced acute encephalopathy].

PubMed

Wang, Li-Qing; Zhu, Sheng-Mei; Zhou, Heng-Jun; Pan, Cai-Fei

2011-09-27

To investigate the expression of aquaporin-4 (AQP4) during brain edema in rats with thioacetamide-induced acute liver failure and encephalopathy. The rat model of acute hepatic failure and encephalopathy was induced by intraperitoneal injection of thioacetamide (TAA) at a 24-hour interval for 2 consecutive days. Thirty-two SD rats were randomly divided into the model group (n = 24) and the control group (normal saline, n = 8). And then the model group was further divided into 3 subgroups by the timepoint of decapitation: 24 h (n = 8), 48 h (n = 8) and 60 h (n = 8). Then we observed their clinical symptoms and stages of HE, indices of liver function and ammonia, liver histology and brain water content. The expression of AQP4 protein in brain tissues was measured with Western blot and the expression of AQP4mRNA with RT-PCR (reverse transcription-polymerase chain reaction). Typical clinical manifestations of hepatic encephalopathy occurred in all TAA-administrated rats. The model rats showed the higher indices of ALT (alanine aminotransferase), AST (aspartate aminotransferase), TBIL (total bilirubin) and ammonia than the control rats (P < 0.05). The brain water content was significantly elevated in TAA-administrated rats compared with the control (P < 0.05). The expressions of AQP4 protein and mRNA in brain tissues significantly increased in TAA-administrated rats (P < 0.05). In addition, the expressions of AQP4 protein and mRNA were positively correlated with brain water content (r = 0.536, P < 0.01; r = 0.566, P = 0.01). The high expression of AQP4 in rats with TAA-induced acute liver failure and encephalopathy plays a significant role during brain edema. AQP4 is one of the molecular mechanisms for the occurrence of brain edema in hepatic encephalopathy.

Development of a second order closure model for computation of turbulent diffusion flames

NASA Technical Reports Server (NTRS)

Varma, A. K.; Donaldson, C. D.

1974-01-01

A typical eddy box model for the second-order closure of turbulent, multispecies, reacting flows developed. The model structure was quite general and was valid for an arbitrary number of species. For the case of a reaction involving three species, the nine model parameters were determined from equations for nine independent first- and second-order correlations. The model enabled calculation of any higher-order correlation involving mass fractions, temperatures, and reaction rates in terms of first- and second-order correlations. Model predictions for the reaction rate were in very good agreement with exact solutions of the reaction rate equations for a number of assumed flow distributions.

Modeling and simulation of pressure waves generated by nano-thermite reactions

NASA Astrophysics Data System (ADS)

Martirosyan, Karen S.; Zyskin, Maxim; Jenkins, Charles M.; (Yuki) Horie, Yasuyuki

2012-11-01

This paper reports the modeling of pressure waves from the explosive reaction of nano-thermites consisting of mixtures of nanosized aluminum and oxidizer granules. Such nanostructured thermites have higher energy density (up to 26 kJ/cm3) and can generate a transient pressure pulse four times larger than that from trinitrotoluene (TNT) based on volume equivalence. A plausible explanation for the high pressure generation is that the reaction times are much shorter than the time for a shock wave to propagate away from the reagents region so that all the reaction energy is dumped into the gaseous products almost instantaneously and thereby a strong shock wave is generated. The goal of the modeling is to characterize the gas dynamic behavior for thermite reactions in a cylindrical reaction chamber and to model the experimentally measured pressure histories. To simplify the details of the initial stage of the explosive reaction, it is assumed that the reaction generates a one dimensional shock wave into an air-filled cylinder and propagates down the tube in a self-similar mode. Experimental data for Al/Bi2O3 mixtures were used to validate the model with attention focused on the ratio of specific heats and the drag coefficient. Model predictions are in good agreement with the measured pressure histories.

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

PubMed

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

2007-06-16

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

Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model

NASA Astrophysics Data System (ADS)

Borges Sebastião, Israel; Alexeenko, Alina

2016-10-01

The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.

A mesoscopic reaction rate model for shock initiation of multi-component PBX explosives.

PubMed

Liu, Y R; Duan, Z P; Zhang, Z Y; Ou, Z C; Huang, F L

2016-11-05

The primary goal of this research is to develop a three-term mesoscopic reaction rate model that consists of a hot-spot ignition, a low-pressure slow burning and a high-pressure fast reaction terms for shock initiation of multi-component Plastic Bonded Explosives (PBX). Thereinto, based on the DZK hot-spot model for a single-component PBX explosive, the hot-spot ignition term as well as its reaction rate is obtained through a "mixing rule" of the explosive components; new expressions for both the low-pressure slow burning term and the high-pressure fast reaction term are also obtained by establishing the relationships between the reaction rate of the multi-component PBX explosive and that of its explosive components, based on the low-pressure slow burning term and the high-pressure fast reaction term of a mesoscopic reaction rate model. Furthermore, for verification, the new reaction rate model is incorporated into the DYNA2D code to simulate numerically the shock initiation process of the PBXC03 and the PBXC10 multi-component PBX explosives, and the numerical results of the pressure histories at different Lagrange locations in explosive are found to be in good agreements with previous experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

Model validation of simple-graph representations of metabolism

PubMed Central

Holme, Petter

2009-01-01

The large-scale properties of chemical reaction systems, such as metabolism, can be studied with graph-based methods. To do this, one needs to reduce the information, lists of chemical reactions, available in databases. Even for the simplest type of graph representation, this reduction can be done in several ways. We investigate different simple network representations by testing how well they encode information about one biologically important network structure—network modularity (the propensity for edges to be clustered into dense groups that are sparsely connected between each other). To achieve this goal, we design a model of reaction systems where network modularity can be controlled and measure how well the reduction to simple graphs captures the modular structure of the model reaction system. We find that the network types that best capture the modular structure of the reaction system are substrate–product networks (where substrates are linked to products of a reaction) and substance networks (with edges between all substances participating in a reaction). Furthermore, we argue that the proposed model for reaction systems with tunable clustering is a general framework for studies of how reaction systems are affected by modularity. To this end, we investigate statistical properties of the model and find, among other things, that it recreates correlations between degree and mass of the molecules. PMID:19158012

Spallation reactions: A successful interplay between modeling and applications

NASA Astrophysics Data System (ADS)

David, J.-C.

2015-06-01

The spallation reactions are a type of nuclear reaction which occur in space by interaction of the cosmic rays with interstellar bodies. The first spallation reactions induced with an accelerator took place in 1947 at the Berkeley cyclotron (University of California) with 200MeV deuterons and 400MeV alpha beams. They highlighted the multiple emission of neutrons and charged particles and the production of a large number of residual nuclei far different from the target nuclei. In the same year, R. Serber described the reaction in two steps: a first and fast one with high-energy particle emission leading to an excited remnant nucleus, and a second one, much slower, the de-excitation of the remnant. In 2010 IAEA organized a workshop to present the results of the most widely used spallation codes within a benchmark of spallation models. If one of the goals was to understand the deficiencies, if any, in each code, one remarkable outcome points out the overall high-quality level of some models and so the great improvements achieved since Serber. Particle transport codes can then rely on such spallation models to treat the reactions between a light particle and an atomic nucleus with energies spanning from few tens of MeV up to some GeV. An overview of the spallation reactions modeling is presented in order to point out the incomparable contribution of models based on basic physics to numerous applications where such reactions occur. Validations or benchmarks, which are necessary steps in the improvement process, are also addressed, as well as the potential future domains of development. Spallation reactions modeling is a representative case of continuous studies aiming at understanding a reaction mechanism and which end up in a powerful tool.

A reaction limited in vivo dissolution model for the study of drug absorption: Towards a new paradigm for the biopharmaceutic classification of drugs.

PubMed

Macheras, Panos; Iliadis, Athanassios; Melagraki, Georgia

2018-05-30

The aim of this work is to develop a gastrointestinal (GI) drug absorption model based on a reaction limited model of dissolution and consider its impact on the biopharmaceutic classification of drugs. Estimates for the fraction of dose absorbed as a function of dose, solubility, reaction/dissolution rate constant and the stoichiometry of drug-GI fluids reaction/dissolution were derived by numerical solution of the model equations. The undissolved drug dose and the reaction/dissolution rate constant drive the dissolution rate and determine the extent of absorption when high-constant drug permeability throughout the gastrointestinal tract is assumed. Dose is an important element of drug-GI fluids reaction/dissolution while solubility exclusively acts as an upper limit for drug concentrations in the lumen. The 3D plots of fraction of dose absorbed as a function of dose and reaction/dissolution rate constant for highly soluble and low soluble drugs for different "stoichiometries" (0.7, 1.0, 2.0) of the drug-reaction/dissolution with the GI fluids revealed that high extent of absorption was found assuming high drug- reaction/dissolution rate constant and high drug solubility. The model equations were used to simulate in vivo supersaturation and precipitation phenomena. The model developed provides the theoretical basis for the interpretation of the extent of drug's absorption on the basis of the parameters associated with the drug-GI fluids reaction/dissolution. A new paradigm emerges for the biopharmaceutic classification of drugs, namely, a model independent biopharmaceutic classification scheme of four drug categories based on either the fulfillment or not of the current dissolution criteria and the high or low % drug metabolism. Copyright © 2018. Published by Elsevier B.V.

Formal Derivation of Lotka-Volterra-Haken Amplitude Equations of Task-Related Brain Activity in Multiple, Consecutively Performed Tasks

NASA Astrophysics Data System (ADS)

Frank, T. D.

The Lotka-Volterra-Haken equations have been frequently used in ecology and pattern formation. Recently, the equations have been proposed by several research groups as amplitude equations for task-related patterns of brain activity. In this theoretical study, the focus is on the circular causality aspect of pattern formation systems as formulated within the framework of synergetics. Accordingly, the stable modes of a pattern formation system inhibit the unstable modes, whereas the unstable modes excite the stable modes. Using this circular causality principle it is shown that under certain conditions the Lotka-Volterra-Haken amplitude equations can be derived from a general model of brain activity akin to the Wilson-Cowan model. The model captures the amplitude dynamics for brain activity patterns in experiments involving several consecutively performed multiple-choice tasks. This is explicitly demonstrated for two-choice tasks involving grasping and walking. A comment on the relevance of the theoretical framework for clinical psychology and schizophrenia is given as well.

Effective Stochastic Model for Reactive Transport

NASA Astrophysics Data System (ADS)

Tartakovsky, A. M.; Zheng, B.; Barajas-Solano, D. A.

2017-12-01

We propose an effective stochastic advection-diffusion-reaction (SADR) model. Unlike traditional advection-dispersion-reaction models, the SADR model describes mechanical and diffusive mixing as two separate processes. In the SADR model, the mechanical mixing is driven by random advective velocity with the variance given by the coefficient of mechanical dispersion. The diffusive mixing is modeled as a fickian diffusion with the effective diffusion coefficient. Both coefficients are given in terms of Peclet number (Pe) and the coefficient of molecular diffusion. We use the experimental results of to demonstrate that for transport and bimolecular reactions in porous media the SADR model is significantly more accurate than the traditional dispersion model, which overestimates the mass of the reaction product by as much as 25%.

TRIM timber projections: an evaluation based on forest inventory measurements.

Treesearch

John R. Mills

1989-01-01

Two consecutive timberland inventories collected from permanent plots in the natural pine type in North Carolina were used to evaluate the timber resource inventory model (TRIM). This study compares model predictions with field measurements and examines the effect of inventory data aggregation on the accuracy of projections. Projections were repeated for two geographic...

Priority queues with bursty arrivals of incoming tasks

NASA Astrophysics Data System (ADS)

Masuda, N.; Kim, J. S.; Kahng, B.

2009-03-01

Recently increased accessibility of large-scale digital records enables one to monitor human activities such as the interevent time distributions between two consecutive visits to a web portal by a single user, two consecutive emails sent out by a user, two consecutive library loans made by a single individual, etc. Interestingly, those distributions exhibit a universal behavior, D(τ)˜τ-δ , where τ is the interevent time, and δ≃1 or 3/2 . The universal behaviors have been modeled via the waiting-time distribution of a task in the queue operating based on priority; the waiting time follows a power-law distribution Pw(τ)˜τ-α with either α=1 or 3/2 depending on the detail of queuing dynamics. In these models, the number of incoming tasks in a unit time interval has been assumed to follow a Poisson-type distribution. For an email system, however, the number of emails delivered to a mail box in a unit time we measured follows a power-law distribution with general exponent γ . For this case, we obtain analytically the exponent α , which is not necessarily 1 or 3/2 and takes nonuniversal values depending on γ . We develop the generating function formalism to obtain the exponent α , which is distinct from the continuous time approximation used in the previous studies.

Predicting residential air exchange rates from questionnaires and meteorology: model evaluation in central North Carolina.

PubMed

Breen, Michael S; Breen, Miyuki; Williams, Ronald W; Schultz, Bradley D

2010-12-15

A critical aspect of air pollution exposure models is the estimation of the air exchange rate (AER) of individual homes, where people spend most of their time. The AER, which is the airflow into and out of a building, is a primary mechanism for entry of outdoor air pollutants and removal of indoor source emissions. The mechanistic Lawrence Berkeley Laboratory (LBL) AER model was linked to a leakage area model to predict AER from questionnaires and meteorology. The LBL model was also extended to include natural ventilation (LBLX). Using literature-reported parameter values, AER predictions from LBL and LBLX models were compared to data from 642 daily AER measurements across 31 detached homes in central North Carolina, with corresponding questionnaires and meteorological observations. Data was collected on seven consecutive days during each of four consecutive seasons. For the individual model-predicted and measured AER, the median absolute difference was 43% (0.17 h(-1)) and 40% (0.17 h(-1)) for the LBL and LBLX models, respectively. Additionally, a literature-reported empirical scale factor (SF) AER model was evaluated, which showed a median absolute difference of 50% (0.25 h(-1)). The capability of the LBL, LBLX, and SF models could help reduce the AER uncertainty in air pollution exposure models used to develop exposure metrics for health studies.

Efficient reactive Brownian dynamics

DOE PAGES

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

2018-01-21

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently processmore » reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.« less

Efficient reactive Brownian dynamics

NASA Astrophysics Data System (ADS)

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

2018-01-01

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently process reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.

Efficient reactive Brownian dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently processmore » reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.« less

In vitro biosynthesis of galactans by membrane-bound galactosyltransferase from radish ( Raphanus sativus L.) seedlings.

PubMed

Kato, Hideaki; Takeuchi, Yoshimi; Tsumuraya, Yoichi; Hashimoto, Yohichi; Nakano, Hirofumi; Kovác, Pavol

2003-06-01

We investigated a galactosyltransferase (GalT) involved in the synthesis of the carbohydrate portion of arabinogalactan-proteins (AGPs), which consist of a beta-(1-->3)-galactan backbone from which consecutive (1-->6)-linked beta-Gal p residues branch off. A membrane preparation from 6-day-old primary roots of radish ( Raphanus sativus L.) transferred [(14)C]Gal from UDP-[(14)C]Gal onto a beta-(1-->3)-galactan exogenous acceptor. The reaction occurred maximally at pH 5.9-6.3 and 30 degrees C in the presence of 15 mM Mn(2+) and 0.75% Triton X-100. The apparent K(m) and V(max) values for UDP-Gal were 0.41 mM and 1,000 pmol min(-1) (mg protein)(-1), respectively. The reaction with beta-(1-->3)-galactan showed a bi-phasic kinetic character with K(m) values of 0.43 and 2.8 mg ml(-1). beta-(1-->3)-Galactooligomers were good acceptors and enzyme activity increased with increasing polymerization of Gal residues. In contrast, the enzyme was less efficient on beta-(1-->6)-oligomers. The transfer reaction for an AGP from radish mature roots was negligible but could be increased by prior enzymatic or chemical removal of alpha- l-arabinofuranose (alpha- l-Ara f) residues or both alpha- l-Ara f residues and (1-->6)-linked beta-Gal side chains. Digestion of radiolabeled products formed from beta-(1-->3)-galactan and the modified AGP with exo-beta-(1-->3)-galactanase released mainly radioactive beta-(1-->6)-galactobiose, indicating that the transfer of [(14)C]Gal occurred preferentially onto consecutive (1-->3)-linked beta-Gal chains through beta-(1-->6)-linkages, resulting in the formation of single branching points. The enzyme produced mainly a branched tetrasaccharide, Galbeta(1-->3)[Galbeta(1-->6)] Galbeta(1-->3)Gal, from beta-(1-->3)-galactotriose by incubation with UDP-Gal, confirming the preferential formation of the branching linkage. Localization of the GalT in the Golgi apparatus was revealed on a sucrose density gradient. The membrane preparation also incorporated [(14)C]Gal into beta-(1-->4)-galactan, indicating that the membranes contained different types of GalT isoform catalyzing the synthesis of different types of galactosidic linkage.

Hybrid deterministic/stochastic simulation of complex biochemical systems.

PubMed

Lecca, Paola; Bagagiolo, Fabio; Scarpa, Marina

2017-11-21

In a biological cell, cellular functions and the genetic regulatory apparatus are implemented and controlled by complex networks of chemical reactions involving genes, proteins, and enzymes. Accurate computational models are indispensable means for understanding the mechanisms behind the evolution of a complex system, not always explored with wet lab experiments. To serve their purpose, computational models, however, should be able to describe and simulate the complexity of a biological system in many of its aspects. Moreover, it should be implemented by efficient algorithms requiring the shortest possible execution time, to avoid enlarging excessively the time elapsing between data analysis and any subsequent experiment. Besides the features of their topological structure, the complexity of biological networks also refers to their dynamics, that is often non-linear and stiff. The stiffness is due to the presence of molecular species whose abundance fluctuates by many orders of magnitude. A fully stochastic simulation of a stiff system is computationally time-expensive. On the other hand, continuous models are less costly, but they fail to capture the stochastic behaviour of small populations of molecular species. We introduce a new efficient hybrid stochastic-deterministic computational model and the software tool MoBioS (MOlecular Biology Simulator) implementing it. The mathematical model of MoBioS uses continuous differential equations to describe the deterministic reactions and a Gillespie-like algorithm to describe the stochastic ones. Unlike the majority of current hybrid methods, the MoBioS algorithm divides the reactions' set into fast reactions, moderate reactions, and slow reactions and implements a hysteresis switching between the stochastic model and the deterministic model. Fast reactions are approximated as continuous-deterministic processes and modelled by deterministic rate equations. Moderate reactions are those whose reaction waiting time is greater than the fast reaction waiting time but smaller than the slow reaction waiting time. A moderate reaction is approximated as a stochastic (deterministic) process if it was classified as a stochastic (deterministic) process at the time at which it crosses the threshold of low (high) waiting time. A Gillespie First Reaction Method is implemented to select and execute the slow reactions. The performances of MoBios were tested on a typical example of hybrid dynamics: that is the DNA transcription regulation. The simulated dynamic profile of the reagents' abundance and the estimate of the error introduced by the fully deterministic approach were used to evaluate the consistency of the computational model and that of the software tool.

The Jarisch-Herxheimer reaction in syphilis: could molecular typing help to understand it better?

PubMed

Arando, M; Fernandez, C; Mota-Foix, M; Alvarez, A; Armegol, P; Barberá, M J; Esperalba, J; Vall-Mayans, M

2018-05-18

The Jarisch-Herxheimer reaction (JHR) is a febrile inflammatory reaction that may occur in patients after treatment of syphilis. The overall rate is estimated to be 10-25% with broad variations over time. It appears to be related to factors like stage of the disease or reagin titres. In this study we aimed to describe the incidence of and risk factors including strain typing for JHR among patients with syphilis. From January through October 2015, 224 consecutive patients (82 of them with HIV) who were diagnosed with early syphilis were enrolled in this prospective observational study in a referral STI clinic in Barcelona. An appointment was offered to them after 10-14 days of treatment to inquire about the reaction with the use of a standardized form. T. pallidum molecular typing was made to detect a possible strain related to reaction. Overall, 28% of patients developed JHR. This varied from 56% in secondary, 37% in primary to 7% in early latent syphilis. The most frequent types of reaction were fever (57.5%) and worsening of the lesions (31%). The median time to development of JHR was 6 hours [IQR 4-10 hours] and lasted a median of 9 hours [IQR 4-24 hours]. The JHR was less probable in early latent compared to primary/secondary syphilis (P=0.04) and in patients treated with doxycycline compared to those treated with penicillin (P=0.01). No differences were seen regarding reagin titres or HIV status and no association with a specific strain was found. In this study, JHR occurred in a similar frequency as in other contemporary studies. Symptomatic syphilis and treatment with penicillin were associated with an increased risk of JHR, whereas the previous episode of syphilis was associated with a low risk of it. We could not find associations with specific strains of T. pallidum. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

NASA Astrophysics Data System (ADS)

Chang, C.; Li, M.; Yeh, G.

2010-12-01

The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

Developing multi-tracer approaches to constrain the parameterisation of leaf and soil CO2 and H2O exchange in land surface models

NASA Astrophysics Data System (ADS)

Ogée, Jerome; Wehr, Richard; Commane, Roisin; Launois, Thomas; Meredith, Laura; Munger, Bill; Nelson, David; Saleska, Scott; Zahniser, Mark; Wofsy, Steve; Wingate, Lisa

2016-04-01

The net flux of carbon dioxide between the land surface and the atmosphere is dominated by photosynthesis and soil respiration, two of the largest gross CO2 fluxes in the carbon cycle. More robust estimates of these gross fluxes could be obtained from the atmospheric budgets of other valuable tracers, such as carbonyl sulfide (COS) or the carbon and oxygen isotope compositions (δ13C and δ18O) of atmospheric CO2. Over the past decades, the global atmospheric flask network has measured the inter-annual and intra-annual variations in the concentrations of these tracers. However, knowledge gaps and a lack of high-resolution multi-tracer ecosystem-scale measurements have hindered the development of process-based models that can simulate the behaviour of each tracer in response to environmental drivers. We present novel datasets of net ecosystem COS, 13CO2 and CO18O exchange and vertical profile data collected over 3 consecutive growing seasons (2011-2013) at the Harvard forest flux site. We then used the process-based model MuSICA (multi-layer Simulator of the Interactions between vegetation Canopy and the Atmosphere) to include the transport, reaction, diffusion and production of each tracer within the forest and exchanged with the atmosphere. Model simulations over the three years captured well the impact of diurnally and seasonally varying environmental conditions on the net ecosystem exchange of each tracer. The model also captured well the dynamic vertical features of tracer behaviour within the canopy. This unique dataset and model sensitivity analysis highlights the benefit in the collection of multi-tracer high-resolution field datasets and the developement of multi-tracer land surface models to provide valuable constraints on photosynthesis and respiration across scales in the near future.

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

Valorization of peanut shells: Manufacture of bioactive oligosaccharides.

PubMed

Rico, Xiana; Gullón, Beatriz; Alonso, José Luis; Parajó, Juan Carlos; Yáñez, Remedios

2018-03-01

Peanut shells were subjected to non-isothermal aqueous treatments to cause the partial breakdown of hemicelluloses into soluble oligosaccharides and lignin-derived compounds with high antioxidant activity. The effects of temperature on the chemical composition of the substrate and soluble reaction products were assessed. Under selected conditions (210°C, severity=4.09), the overall amount of poly- and oligo- saccharides present in the liquid phase reached 9.8g/L. This solution was refined by consecutive stages of discontinuous diafiltration, yielding a refined product containing about 72.4wt% of oligomers at a global yield of 8.5kg/100kg oven-dry PS. The purified products were characterized by HPLC, MALDI-TOF-MS and FTIR, confirming the major reaction products were saccharides made up of xylose with degrees of polymerization up to 17, substituted with acetyl and methylglucuronosyl groups, for which a number of pharmaceutical and food applications have been proposed. Solubilization of hemicelluloses in the treatments resulted in the production of solids enriched in cellulose and lignin suitable for further applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Oligonucleotide derivatives in the nucleic acid hybridization analysis. II. Isothermal signal amplification in process of DNA analysis by minisequencing].

PubMed

Dmitrienko, E V; Khomiakova, E A; Pyshnaia; Bragin, A G; Vedernikov, V E; Pyshnyĭ, D V

2010-01-01

The isothermal amplification of reporter signal via limited probe extension (minisequencing) upon hybridization of nucleic acids has been studied. The intensity of reporter signal has been shown to increase due to enzymatic labeling of multiple probes upon consecutive hybridization with one DNA template both in homophase and heterophase assays using various kinds of detection signal: radioisotope label, fluorescent label, and enzyme-linked assay. The kinetic scheme of the process has been proposed and kinetic parameters for each step have been determined. The signal intensity has been shown to correlate with physicochemical characteristics of both complexes: probe/DNA and product/DNA. The maximum intensity has been observed at minimal difference between the thermodynamic stability of these complexes, provided the reaction temperature has been adjusted near their melting temperature values; rising or lowering the reaction temperature reduces the amount of reporting product. The signal intensity has been shown to decrease significantly upon hybridization with the DNA template containing single-nucleotide mismatches. Limited probe extension assay is useful not only for detection of DNA template but also for its quantitative characterization.

A new photoelectrochemical biosensors based on DNA conformational changes and isothermal circular strand-displacement polymerization reaction.

PubMed

Zhang, Xiaoru; Xu, Yunpeng; Zhao, Yanqing; Song, Weiling

2013-01-15

We report a strategy for the transduction of DNA hybridization into a readily detectable photoelectrochemical signal by means of a conformational change analogous to electrochemical DNA (E-DNA) approach. To demonstrate the effect of distance change for photosensitizer to the surface of electrode on the change of photocurrent, photosensitizer Ru(bpy)(2)(dcbpy)(2+) tagged DNA stem-loop structures were self-assembled onto a nanogold modified ITO electrode. Hybridization induced a large conformational change in DNA structure, which in turn significantly altered the electron-transfer tunneling distance between the electrode and photosensitizer. The resulting change in photocurrent was proportional to the concentration of DNA in the range of 1.0×10(-10)-8.0×10(-9)M. In order to improve the sensitivity of the photoelectrochemical biosensor, an amplified detection method based on isothermal strand displacement polymerization reaction was employed. With multiple rounds of isothermal strand replication, which led to strand displacement and constituted consecutive signal amplification, a detection limit of 9.4×10(-14)M target DNA was achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

Human metapneumovirus-associated hospital admissions over five consecutive epidemic seasons: evidence for alternating circulation of different genotypes.

PubMed

Apostoli, Paola; Zicari, Sonia; Lo Presti, Alessandra; Ciccozzi, Massimo; Ciotti, Marco; Caruso, Arnaldo; Fiorentini, Simona

2012-03-01

Human metapneumovirus (hMPV) is a pathogen of the respiratory tract with a worldwide distribution. The purpose of this study was to identify hMPV as the cause of acute respiratory diseases in children admitted at Spedali Civili, a public hospital in Brescia, Italy. Eight hundred forty-six nasopharyngeal aspirate samples negative for the presence of other common respiratory viruses were tested for the presence of hMPV RNA by reverse transcription-polymerase chain reaction. Of the 846 samples, 79 (9.3%) were positive for hMPV. Polymerase chain reaction products, obtained by amplification of the partial nucleotide sequence of gene F, were sequenced and compared with sequences deposited in GenBank. All four hMPV subtypes were identified, including the proposed subtype A2 sublineages "A" and "B". In successive epidemic seasons, large outbreaks of hMPV alternated with small outbreaks in a biannual pattern. This local study provides further evidence that hMPV infection should be considered as a reason for hospital admission for acute respiratory disease in children. Copyright © 2012 Wiley Periodicals, Inc.

Production of bioadditives from glycerol esterification over zirconia supported heteropolyacids.

PubMed

Zhu, Shanhui; Zhu, Yulei; Gao, Xiaoqing; Mo, Tao; Zhu, Yifeng; Li, Yongwang

2013-02-01

The synthesis of bioadditives for biofuels from glycerol esterification with acetic acid was performed over zirconia supported heteropolyacids catalysts using H(4)SiW(12)O(40) (HSiW), H(3)PW(12)O(40) (HPW) and H(3)PMo(12)O(40) (HPMo) as active compounds. The as-prepared catalysts were characterized by N(2)-physisorption, XRD, Raman spectroscopy, NH(3)-TPD, FTIR of pyridine adsorption and H(2)O-TPD. Among the catalysts tested, HSiW/ZrO(2) achieved the best catalytic performance owing to the better combination of surface Brønsted acid sites and hydrothermal stability. A 93.6% combined selectivity of glyceryl diacetate and glyceryl triacetate with complete glycerol conversion was obtained at 120°C and 4h of reaction time in the presence of HSiW/ZrO(2). This catalyst also presented consistent activity for four consecutive reaction cycles, while HPW/ZrO(2) and HPMo/ZrO(2) exhibited distinct deactivation after reusability tests. In addition, HSiW/ZrO(2) can be resistant to the impurities present in bulk glycerol. Copyright © 2012 Elsevier Ltd. All rights reserved.

Expressed emotion is not associated with disorder severity in first-episode mental disorder.

PubMed

Heikkilä, Jyrki; Karlsson, Hasse; Taiminen, Tero; Lauerma, Hannu; Ilonen, Tuula; Leinonen, Kirsi-Marja; Wallenius, Elina; Virtanen, Hilkka; Heinimaa, Markus; Koponen, Salla; Jalo, Päivi; Kaljonen, Anne; Salakangas, Raimo K R

2002-08-30

A family atmosphere characterized by expressed emotion (EE) is a robust predictor of clinical outcome of patients with schizophrenia and mood disorders. However, there is ongoing discussion as to whether EE is more a cause of clinical outcome or a parental reaction to disorder severity. This cross-sectional study examines a sample of 42 consecutive first-episode patients from a defined geographical area with severe mental disorders (schizophrenia-related disorders, psychotic mood disorders, and non-psychotic mood disorders). Their 42 relatives were interviewed, and the relationships between EE variables derived with the five-minute speech sample method (FMSS) and the patients' demographic, premorbid and clinical measures were analyzed. A high EE score was found in 40% of the relatives. High EE was associated with the interviewed relative's not being a spouse and the patient's being young and unmarried. It was not associated with premorbid characteristics, symptom dimensions or the diagnostic group of the patient. These results do not support the hypothesis that EE is a reaction to the clinical features of the patient. Instead, demographic factors may partly mediate the effect of EE on prognosis.

Investigation of the aroma of commercial peach (Prunus persica L. Batsch) types by Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and sensory analysis.

PubMed

Bianchi, Tiago; Weesepoel, Yannick; Koot, Alex; Iglesias, Ignasi; Eduardo, Iban; Gratacós-Cubarsí, Marta; Guerrero, Luis; Hortós, Maria; van Ruth, Saskia

2017-09-01

The aim of this study was to investigate the aroma and sensory profiles of various types of peaches (Prunus persica L. Batsch.). Forty-three commercial cultivars comprising peaches, flat peaches, nectarines, and canning peaches (pavías) were grown over two consecutive harvest years. Fruits were assessed for chemical aroma and sensory profiles. Chemical aroma profile was obtained by proton transfer reaction-mass spectrometry (PTR-MS) and spectral masses were tentatively identified with PTR-Time of Flight-MS (PTR-Tof-MS). Sensory analysis was performed at commercial maturity considering seven aroma/flavor attributes. The four types of peaches showed both distinct chemical aroma and sensory profiles. Flat peaches and canning peaches showed most distinct patterns according to discriminant analysis. The sensory data were related to the volatile compounds by partial least square regression. γ-Hexalactone, γ-octalactone, hotrienol, acetic acid and ethyl acetate correlated positively, and benzeneacetaldehyde, trimethylbenzene and acetaldehyde negatively to the intensities of aroma and ripe fruit sensory scores. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multifunctional Co₀.₈₅Se/graphene hybrid nanosheets: controlled synthesis and enhanced performances for the oxygen reduction reaction and decomposition of hydrazine hydrate.

PubMed

Zhang, Lin-fei; Zhang, Chun-yang

2014-01-01

Ultrathin nanosheets possess novel electronic structures and physical properties as compared with their corresponding bulk samples. However, the controlled synthesis of ultrathin monolayer nanosheets still remains a great challenge due to the lack of an intrinsic driving force for anisotropic growth of two-dimensional (2D) structures. Here we demonstrate, for the first time to our knowledge, the in situ synthesis of large-scale ultrathin single-crystalline Co₀.₈₅Se nanosheets on graphene oxide (GO) sheets, with a thickness of 3 nm. Owing to the synergetic chemical coupling effects between GO and Co₀.₈₅Se, the Co₀.₈₅Se/graphene hybrid nanosheets exhibit the highest catalytic performance among the available cobalt chalcogenide-based catalysts for the oxygen reduction reaction (ORR). Moreover, Co₀.₈₅Se/graphene hybrid nanosheets can catalyze the decomposition of hydrazine hydrate rapidly, with 97% of hydrazine hydrate being degraded in 12 min and the degradation rate remaining constant over 10 consecutive cycles, thus having great potential as long-term catalysts in wastewater treatment.

Reaction behaviors of decomposition of monocrotophos in aqueous solution by UV and UV/O processes.

PubMed

Ku, Y; Wang, W; Shen, Y S

2000-02-01

The decomposition of monocrotophos (cis-3-dimethoxyphosphinyloxy-N-methyl-crotonamide) in aqueous solution by UV and UV/O(3) processes was studied. The experiments were carried out under various solution pH values to investigate the decomposition efficiencies of the reactant and organic intermediates in order to determine the completeness of decomposition. The photolytic decomposition rate of monocrotophos was increased with increasing solution pH because the solution pH affects the distribution and light absorbance of monocrotophos species. The combination of O(3) with UV light apparently promoted the decomposition and mineralization of monocrotophos in aqueous solution. For the UV/O(3) process, the breakage of the >C=C< bond of monocrotophos by ozone molecules was found to occur first, followed by mineralization by hydroxyl radicals to generate CO(3)(2-), PO4(3-), and NO(3)(-) anions in sequence. The quasi-global kinetics based on a simplified consecutive-parallel reaction scheme was developed to describe the temporal behavior of monocrotophos decomposition in aqueous solution by the UV/O(3) process.

PARTICLE FLOW, MIXING, AND CHEMICAL REACTION IN CIRCULATING FLUIDIZED BED ABSORBERS

EPA Science Inventory

A mixing model has been developed to simulate the particle residence time distribution (RTD) in a circulating fluidized bed absorber (CFBA). Also, a gas/solid reaction model for sulfur dioxide (SO2) removal by lime has been developed. For the reaction model that considers RTD dis...

The Variance Reaction Time Model

ERIC Educational Resources Information Center

Sikstrom, Sverker

2004-01-01

The variance reaction time model (VRTM) is proposed to account for various recognition data on reaction time, the mirror effect, receiver-operating-characteristic (ROC) curves, etc. The model is based on simple and plausible assumptions within a neural network: VRTM is a two layer neural network where one layer represents items and one layer…

Multicenter Patch Testing With Methylchloroisothizoline/Methylisothiazolinone in 100 and 200 ppm Within the International Contact Dermatitis Research Group.

PubMed

Engfeldt, Malin; Ale, Iris; Andersen, Klaus E; Elsner, Peter; Goh, Chee-Leok; Goossens, An; Jerajani, Hemangi; Matsunaga, Kayoko; Bruze, Magnus

The preservative methylchloroisothiazolinone/methylisothiazolinone (MCI/MI) is a well-known contact sensitizer. Historically, there have been different opinions on the optimal patch test concentration of MCI/MI, and both 0.01% and 0.02% aqueous (aq.) have been proposed. In 2011, based on literature reviews, it was recommended that the concentration of 0.02% aq. should be used in the international baseline series. The aim of this study was to verify the recommendation from 2011 by comparing the patch test results from consecutive patch testing with MCI/MI 0.01% and 0.02% in clinics representing countries around the world. Two thousand seven hundred three consecutive patients with dermatitis in 8 dermatology clinics representing 8 countries were patch tested with MCI/MI 0.01% aq. and, in parallel with MCI/MI 0.02% aq., provisionally included in the baseline series. Contact allergy to MCI/MI at 0.01% and 0.02% was found in 3.7% and 5.6% of the patients, respectively (P < 0.001). Methylchloroisothiazolinone/MI 0.02% aq. (dose, 6 μg/cm) diagnoses significantly more contact allergy than 0.01% (dose, 3 μg/cm), without resulting in more adverse reactions. Methylchloroisothiazolinone/MI at 0.02% aq. should therefore be continuously used in the international baseline series.

Breath acetone to monitor life style interventions in field conditions: an exploratory study.

PubMed

Samudrala, Devasena; Lammers, Gerwen; Mandon, Julien; Blanchet, Lionel; Schreuder, Tim H A; Hopman, Maria T; Harren, Frans J M; Tappy, Luc; Cristescu, Simona M

2014-04-01

To assess whether breath acetone concentration can be used to monitor the effects of a prolonged physical activity on whole body lipolysis and hepatic ketogenesis in field conditions. Twenty-three non-diabetic, 11 type 1 diabetic, and 17 type 2 diabetic subjects provided breath and blood samples for this study. Samples were collected during the International Four Days Marches, in the Netherlands. For each participant, breath acetone concentration was measured using proton transfer reaction ion trap mass spectrometry, before and after a 30-50 km walk on four consecutive days. Blood non-esterified free fatty acid (NEFA), beta-hydroxybutyrate (BOHB), and glucose concentrations were measured after walking. Breath acetone concentration was significantly higher after than before walking, and was positively correlated with blood NEFA and BOHB concentrations. The effect of walking on breath acetone concentration was repeatedly observed on all four consecutive days. Breath acetone concentrations were higher in type 1 diabetic subjects and lower in type 2 diabetic subjects than in control subjects. Breath acetone can be used to monitor hepatic ketogenesis during walking under field conditions. It may, therefore, provide real-time information on fat burning, which may be of use for monitoring the lifestyle interventions. Copyright © 2014 The Obesity Society.

Efficacy and safety of a transdermal contraceptive system.

PubMed

Smallwood, G H; Meador, M L; Lenihan, J P; Shangold, G A; Fisher, A C; Creasy, G W

2001-11-01

To evaluate the efficacy, cycle control, compliance, and safety of a transdermal contraceptive system that delivers norelgestromin 150 microg and ethinyl estradiol 20 microg daily. In this open-label, 73-center study, 1672 healthy, ovulatory, sexually active women received ORTHO EVRA/EVRA for six (n = 1171) or 13 cycles (n = 501). The treatment regimen for each cycle was three consecutive 7-day patches (21 days) followed by 1 patch-free week. The overall and method-failure probabilities of pregnancy through 13 cycles were 0.7% and 0.4%, respectively. The incidence of breakthrough bleeding was low throughout the study. Perfect compliance (21 consecutive days of dosing, followed by a 7-day drug-free interval; no patch could be worn for more than 7 days) was achieved in 90% of subject cycles; only 1.9% of patches detached completely. Adverse events were typical of hormonal contraception, and most were mild-to-moderate in severity and not treatment limiting. The most common adverse events resulting in discontinuation were application site reactions (1.9%), nausea (1.8%), emotional lability (1.5%), headache (1.1%), and breast discomfort (1.0%). The transdermal contraceptive patch provides effective contraception and cycle control, and is well tolerated. The weekly change schedule for the contraceptive patch is associated with excellent compliance and wearability characteristics.

[YEL-AND meningoencephalitis in a 4-year-old boy consecutive to a yellow-fever vaccine].

PubMed

Gerin, M; Wroblewski, I; Bost-Bru, C; N'guyen, M-A; Debillon, T

2014-04-01

Yellow fever is a vector-borne disease transmitted by an endemic mosquito in sub-Saharan Africa and tropical South America. It causes fever and possibly liver and renal failure with hemorrhagic signs, which may be fatal. The yellow-fever vaccine is an attenuated vaccine that is recommended for all travelers over the age of 9 months in high-risk areas. Adverse effects have been reported: minor symptoms (such as viral syndrome), hypersensitivity reactions, and major symptoms such as viscerotropic disease (YEL-AVD) and neurotropic disease (YEL-AND). The yellow-fever vaccine-associated autoimmune disease with central nervous system involvement (such as acute disseminated encephalomyelitis) associates fever and headaches, neurologic dysfunction, seizures, cerebrospinal fluid (CSF) pleocytosis, and elevated protein, with neuroimaging consistent with multifocal areas of demyelization. The presence of antibodies or virus in CSF, within 1-30 days following vaccination, and the exclusion of other causes is necessary for diagnosis. We describe herein the case of a 4-year-old child who presented with severe encephalitis consecutive to a yellow-fever vaccine, with favorable progression. Diagnosis is based on the chronology of clinical and paraclinical signs and the presence of yellow-fever-specific antibodies in CSF. The treatment consists of symptomatic treatment and immunoglobulin injection. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Biodiesel forming reactions using heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Liu, Yijun

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with other comparisons between the catalytic behaviors of liquid and solid acids suggests a common mode of operation of their Bronsted acid sites in carrying out esterification of a carboxylic acid with alcohol. The hypothesized Eley-Rideal type heterogeneous reaction mechanism involving a nucleophilic attack between adsorbed carboxylic acid and unadsorbed alcohol as the rate-limiting step was found to fit well the experimental observations and successfully predict the esterification rate obtained with SAC-13 as reaction progresses. The SAC-13 catalysis assay was also extended to carboxylic acids of higher molecular weights. A set of carboxylic acids with various alkyl chain lengths was used to investigate the structural effect of reacting carboxylic acids on heterogeneous catalyzed esterification. It was found that the reactivity of carboxylic acids was controlled by steric factors as the alkyl chain linearly lengthened. Despite their increased hydrophobicity, large carboxylic acids hardly impacted the deactivating effect of water on Bronsted acid sites. However, catalyst reusability and regeneration showed significant dependency on the size of the carboxylic acid used. With the use of larger reacting carboxylic acids, SAC-13 underwent more significant activity loss in consecutive reaction cycles due to stronger adsorption of the larger organics in the polymeric domains of the Nafion resin. In parallel to the research activity on acid catalyzed esterification, the use of strong solid bases with organic functionality (quarternary ammonium, QN+) was investigated from a fundamental perspective. Using triacetin as a model compound for TG molecules, the effectiveness of this Bronsted base functionality in transesterification was demonstrated even at mild reaction conditions. But its catalytic behavior including catalyst selectivity and deactivation was significantly affected by the nature of the adopted support. A purposive design of the immobilizing matrix is expected to optimize the activity, selectivity, and stability of the QN+ groups, thus enhancing their applicability in practical biodiesel synthesis from lipid feedstocks. As the solid organic base-matrix composite catalyst remains to be better designed to fit the need of TG methanolysis, inorganic solid bases composed of metal oxides appear to be a more feasible choice given that their thermal robustness generally allows the achievement of sufficient activity by increasing reaction temperature and potentially permits a convenient regeneration by recalcination. A study dealing with the methanolysis of real lipid feedstock (poultry fat) was carried out using Mg-Al hydrotalcite derived catalysts. From a practical standpoint, the impact of a variety of operational variables on reaction, such as catalyst pretreatments, temperature, reactants molar ratio, and usage of co-solvent were addressed. As a result, biodiesel synthesis from poultry fat was successfully conducted by appropriately adjusting these variables. However, many underlying aspects associated with catalyst performance remain unexamined and unexplained.

Model free simulations of a high speed reacting mixing layer

NASA Technical Reports Server (NTRS)

Steinberger, Craig J.

1992-01-01

The effects of compressibility, chemical reaction exothermicity and non-equilibrium chemical modeling in a combusting plane mixing layer were investigated by means of two-dimensional model free numerical simulations. It was shown that increased compressibility generally had a stabilizing effect, resulting in reduced mixing and chemical reaction conversion rate. The appearance of 'eddy shocklets' in the flow was observed at high convective Mach numbers. Reaction exothermicity was found to enhance mixing at the initial stages of the layer's growth, but had a stabilizing effect at later times. Calculations were performed for a constant rate chemical rate kinetics model and an Arrhenius type kinetics prototype. The Arrhenius model was found to cause a greater temperature increase due to reaction than the constant kinetics model. This had the same stabilizing effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

Simulation of large-scale rule-based models

PubMed Central

Colvin, Joshua; Monine, Michael I.; Faeder, James R.; Hlavacek, William S.; Von Hoff, Daniel D.; Posner, Richard G.

2009-01-01

Motivation: Interactions of molecules, such as signaling proteins, with multiple binding sites and/or multiple sites of post-translational covalent modification can be modeled using reaction rules. Rules comprehensively, but implicitly, define the individual chemical species and reactions that molecular interactions can potentially generate. Although rules can be automatically processed to define a biochemical reaction network, the network implied by a set of rules is often too large to generate completely or to simulate using conventional procedures. To address this problem, we present DYNSTOC, a general-purpose tool for simulating rule-based models. Results: DYNSTOC implements a null-event algorithm for simulating chemical reactions in a homogenous reaction compartment. The simulation method does not require that a reaction network be specified explicitly in advance, but rather takes advantage of the availability of the reaction rules in a rule-based specification of a network to determine if a randomly selected set of molecular components participates in a reaction during a time step. DYNSTOC reads reaction rules written in the BioNetGen language which is useful for modeling protein–protein interactions involved in signal transduction. The method of DYNSTOC is closely related to that of StochSim. DYNSTOC differs from StochSim by allowing for model specification in terms of BNGL, which extends the range of protein complexes that can be considered in a model. DYNSTOC enables the simulation of rule-based models that cannot be simulated by conventional methods. We demonstrate the ability of DYNSTOC to simulate models accounting for multisite phosphorylation and multivalent binding processes that are characterized by large numbers of reactions. Availability: DYNSTOC is free for non-commercial use. The C source code, supporting documentation and example input files are available at http://public.tgen.org/dynstoc/. Contact: dynstoc@tgen.org Supplementary information: Supplementary data are available at Bioinformatics online. PMID:19213740

A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

NASA Astrophysics Data System (ADS)

Kruskopf, Ari; Visuri, Ville-Valtteri

2017-12-01

In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

Detection of feline coronavirus in cheetah (Acinonyx jubatus) feces by reverse transcription-nested polymerase chain reaction in cheetahs with variable frequency of viral shedding.

PubMed

Gaffney, Patricia M; Kennedy, Melissa; Terio, Karen; Gardner, Ian; Lothamer, Chad; Coleman, Kathleen; Munson, Linda

2012-12-01

Cheetahs (Acinonyx jubatus) are a highly threatened species because of habitat loss, human conflict, and high prevalence of disease in captivity. An epidemic of feline infectious peritonitis and concern for spread of infectious disease resulted in decreased movement of cheetahs between U.S. zoological facilities for managed captive breeding. Identifying the true feline coronavirus (FCoV) infection status of cheetahs is challenging because of inconsistent correlation between seropositivity and fecal viral shedding. Because the pattern of fecal shedding of FCoV is unknown in cheetahs, this study aimed to assess the frequency of detectable fecal viral shedding in a 30-day period and to determine the most efficient fecal sampling strategy to identify cheetahs shedding FCoV. Fecal samples were collected from 16 cheetahs housed at seven zoological facilities for 30 to 46 consecutive days; the samples were evaluated for the presence of FCoV by reverse transcription-nested polymerase chain reaction (RT-nPCR). Forty-four percent (7/16) of cheetahs had detectable FCoV in feces, and the proportion of positive samples for individual animals ranged from 13 to 93%. Cheetahs shed virus persistently, intermittently, or rarely over 30-46 days. Fecal RT-nPCR results were used to calculate the probability of correctly identifying a cheetah known to shed virus given multiple hypothetical fecal collection schedules. The most efficient hypothetical fecal sample collection schedule was evaluation of five individual consecutive fecal samples, resulting in a 90% probability of identifying a known shedder. Demographic and management risk factors were not significantly associated (P < or = 0.05) with fecal viral shedding. Because some cheetahs shed virus intermittently to rarely, fecal sampling schedules meant to identify all known shedders would be impractical with current tests and eradication of virus from the population unreasonable. Managing the captive population as endemically infected with FCoV may be a more feasible approach.

Regulation of the catalytic behavior of pullulanases chelated onto nickel (II)-modified magnetic nanoparticles.

PubMed

Wang, Jianfeng; Liu, Zhongmei; Zhou, Zhemin

2017-06-01

Chelating of pullulanases onto nickel (II)-modified magnetic nanoparticles results in one-step purification and immobilization of pullulanase, and facilitates the commercial application of pullulanase in industrial scale. To improve the catalytic behavior, especially the operational stability, of the nanocatalyst in consecutive batch reactions, we prepared various iminodiacetic acid-modified magnetic nanoparticles differed in surface polarity and spacer length, on which the His6-tagged pullulanases were chelated via nickel ions, and then studied the correlation between the MNPs surface property and the corresponding catalyst behavior. When pullulanases were chelated onto the surface-modified MNPs, the thermostability of all pullulanase derivatives were lower than that of free counterpart, being not relevant to the protein orientation guided by the locality of the His6-tag, but related to the MNPs basal surface polarity and the grafted spacer length. After chelating of pullulanases onto MNPs, there were changes observed in the pH-activity profile and the apparent Michaelis constant toward pullulan. The changing tendencies were mainly dependent on the His6-tagged pullulanase orientation, and the changing extents were tuned by the spacer length. The reusability of pullulanase immobilized by N-terminal His6-tag was higher than that of pullulanase immobilized by C-terminal His6-tag. Moreover, the reusability of the immobilized pullulanase tested increased till grafting polyether amine-400 as spacer-arm, therefore the N-terminal His6-tagged pullulanase chelating MNPs grafted polyether amine-400 gave the best reusability, which retained 60% of initial activity after 18 consecutive cycles with a total reaction time of 9h. Additionally, the correlation analysis of the catalyst behaviors indicated that the reusability was independent from other catalytic properties such as thermostability and substrate affinity. All the results revealed that the catalyst behavior can be mainly controlled by the His6-tagged pullulanase orientation than by the MNPs surface property which can tune the catalyst function. Copyright © 2017. Published by Elsevier Inc.

Desensitizing the posterior interosseous nerve alters wrist proprioceptive reflexes.

PubMed

Hagert, Elisabet; Persson, Jonas K E

2010-07-01

The presence of wrist proprioceptive reflexes after stimulation of the dorsal scapholunate interosseous ligament has previously been described. Because this ligament is primarily innervated by the posterior interosseous nerve (PIN) we hypothesized altered ligamento-muscular reflex patterns following desensitization of the PIN. Eight volunteers (3 women, 5 men; mean age, 26 y; range 21-28 y) participated in the study. In the first study on wrist proprioceptive reflexes (study 1), the scapholunate interosseous ligament was stimulated through a fine-wire electrode with 4 1-ms bipolar pulses at 200 Hz, 30 times consecutively, while EMG activity was recorded from the extensor carpi radialis brevis, extensor carpi ulnaris, flexor carpi radialis, and flexor carpi ulnaris, with the wrist in extension, flexion, radial deviation, and ulnar deviation. After completion of study 1, the PIN was anesthetized in the radial aspect of the fourth extensor compartment using 2-mL lidocaine (10 mg/mL) infiltration anesthesia. Ten minutes after desensitization, the experiment was repeated as in study 1. The average EMG results from the 30 consecutive stimulations were rectified and analyzed using Student's t-test. Statistically significant changes in EMG amplitude were plotted along time lines so that the results of study 1 and 2 could be compared. Dramatic alterations in reflex patterns were observed in wrist flexion, radial deviation, and ulnar deviation following desensitization of the PIN, with an average of 72% reduction in excitatory reactions. In ulnar deviation, the inhibitory reactions of the extensor carpi ulnaris were entirely eliminated. In wrist extension, no differences in the reflex patterns were observed. Wrist proprioception through the scapholunate ligament in flexion, radial deviation, and ulnar deviation depends on an intact PIN function. The unchanged reflex patterns in wrist extension suggest an alternate proprioceptive pathway for this position. Routine excision of the PIN during wrist surgical procedures should be avoided, as it alters the proprioceptive function of the wrist. Therapeutic IV. Copyright 2010 American Society for Surgery of the Hand. Published by Elsevier Inc. All rights reserved.

Multiscale Simulations of Reactive Transport

NASA Astrophysics Data System (ADS)

Tartakovsky, D. M.; Bakarji, J.

2014-12-01

Discrete, particle-based simulations offer distinct advantages when modeling solute transport and chemical reactions. For example, Brownian motion is often used to model diffusion in complex pore networks, and Gillespie-type algorithms allow one to handle multicomponent chemical reactions with uncertain reaction pathways. Yet such models can be computationally more intensive than their continuum-scale counterparts, e.g., advection-dispersion-reaction equations. Combining the discrete and continuum models has a potential to resolve the quantity of interest with a required degree of physicochemical granularity at acceptable computational cost. We present computational examples of such "hybrid models" and discuss the challenges associated with coupling these two levels of description.

A fully coupled 3D transport model in SPH for multi-species reaction-diffusion systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adami, Stefan; Hu, X. Y.; Adams, N. A.

2011-08-23

Abstract—In this paper we present a fully generalized transport model for multiple species in complex two and threedimensional geometries. Based on previous work [1] we have extended our interfacial reaction-diffusion model to handle arbitrary numbers of species allowing for coupled reaction models. Each species is tracked independently and we consider different physics of a species with respect to the bulk phases in contact. We use our SPH model to simulate the reaction-diffusion problem on a pore-scale level of a solid oxide fuel cell (SOFC) with special emphasize on the effect of surface diffusion.

Reply to 'Comment on kinetic modeling of microbially-driven redox chemistry of subsurface environments: coupling transport, microbial metabolism and geochemistry' by J. Griffioen

NASA Astrophysics Data System (ADS)

Hunter, K. S.; Van Cappellen, P.

2000-01-01

Our paper, 'Kinetic modeling of microbially-driven redox chemistry of subsurface environments: coupling transport, microbial metabolism and geochemistry' (Hunter et al., 1998), presents a theoretical exploration of biogeochemical reaction networks and their importance to the biogeochemistry of groundwater systems. As with any other model, the kinetic reaction-transport model developed in our paper includes only a subset of all physically, biologically and chemically relevant processes in subsurface environments. It considers aquifer systems where the primary energy source driving microbial activity is the degradation of organic matter. In addition to the primary biodegradation pathways of organic matter (i.e. respiration and fermentation), the redox chemistry of groundwaters is also affected by reactions not directly involving organic matter oxidation. We refer to the latter as secondary reactions. By including secondary redox reactions which consume reduced reaction products (e.g., Mn2+, FeS, H2S), and in the process compete with microbial heterotrophic populations for available oxidants (i.e. O2, NO3-, Mn(IV), Fe(III), SO42-), we predict spatio-temporal distributions of microbial activity which differ significantly from those of models which consider only the biodegradation reactions. That is, the secondary reactions have a significant impact on the distributions of the rates of heterotrophic and chemolithotrophic metabolic pathways. We further show that secondary redox reactions, as well as non-redox reactions, significantly influence the acid-base chemistry of groundwaters. The distributions of dissolved inorganic redox species along flowpaths, however, are similar in simulations with and without secondary reactions (see Figs. 3(b) and 7(b) in Hunter et al., 1998), indicating that very different biogeochemical reaction dynamics may lead to essentially the same chemical redox zonation of a groundwater system.

The repetition of large-earthquake ruptures.

PubMed Central

Sieh, K

1996-01-01

This survey of well-documented repeated fault rupture confirms that some faults have exhibited a "characteristic" behavior during repeated large earthquakes--that is, the magnitude, distribution, and style of slip on the fault has repeated during two or more consecutive events. In two cases faults exhibit slip functions that vary little from earthquake to earthquake. In one other well-documented case, however, fault lengths contrast markedly for two consecutive ruptures, but the amount of offset at individual sites was similar. Adjacent individual patches, 10 km or more in length, failed singly during one event and in tandem during the other. More complex cases of repetition may also represent the failure of several distinct patches. The faults of the 1992 Landers earthquake provide an instructive example of such complexity. Together, these examples suggest that large earthquakes commonly result from the failure of one or more patches, each characterized by a slip function that is roughly invariant through consecutive earthquake cycles. The persistence of these slip-patches through two or more large earthquakes indicates that some quasi-invariant physical property controls the pattern and magnitude of slip. These data seem incompatible with theoretical models that produce slip distributions that are highly variable in consecutive large events. Images Fig. 3 Fig. 7 Fig. 9 PMID:11607662

Fatigue-life distributions for reaction time data.

PubMed

Tejo, Mauricio; Niklitschek-Soto, Sebastián; Marmolejo-Ramos, Fernando

2018-06-01

The family of fatigue-life distributions is introduced as an alternative model of reaction time data. This family includes the shifted Wald distribution and a shifted version of the Birnbaum-Saunders distribution. Although the former has been proposed as a way to model reaction time data, the latter has not. Hence, we provide theoretical, mathematical and practical arguments in support of the shifted Birnbaum-Saunders as a suitable model of simple reaction times and associated cognitive mechanisms.

Simulation studies of chemical erosion on carbon based materials at elevated temperatures

NASA Astrophysics Data System (ADS)

Kenmotsu, T.; Kawamura, T.; Li, Zhijie; Ono, T.; Yamamura, Y.

1999-06-01

We simulated the fluence dependence of methane reaction yield in carbon with hydrogen bombardment using the ACAT-DIFFUSE code. The ACAT-DIFFUSE code is a simulation code based on a Monte Carlo method with a binary collision approximation and on solving diffusion equations. The chemical reaction model in carbon was studied by Roth or other researchers. Roth's model is suitable for the steady state methane reaction. But this model cannot estimate the fluence dependence of the methane reaction. Then, we derived an empirical formula based on Roth's model for methane reaction. In this empirical formula, we assumed the reaction region where chemical sputtering due to methane formation takes place. The reaction region corresponds to the peak range of incident hydrogen distribution in the target material. We adopted this empirical formula to the ACAT-DIFFUSE code. The simulation results indicate the similar fluence dependence compared with the experiment result. But, the fluence to achieve the steady state are different between experiment and simulation results.

Genome scale metabolic reconstruction of Chlorella variabilis for exploring its metabolic potential for biofuels.

PubMed

Juneja, Ankita; Chaplen, Frank W R; Murthy, Ganti S

2016-08-01

A compartmentalized genome scale metabolic network was reconstructed for Chlorella variabilis to offer insight into various metabolic potentials from this alga. The model, iAJ526, was reconstructed with 1455 reactions, 1236 metabolites and 526 genes. 21% of the reactions were transport reactions and about 81% of the total reactions were associated with enzymes. Along with gap filling reactions, 2 major sub-pathways were added to the model, chitosan synthesis and rhamnose metabolism. The reconstructed model had reaction participation of 4.3 metabolites per reaction and average lethality fraction of 0.21. The model was effective in capturing the growth of C. variabilis under three light conditions (white, red and red+blue light) with fair agreement. This reconstructed metabolic network will serve an important role in systems biology for further exploration of metabolism for specific target metabolites and enable improved characteristics in the strain through metabolic engineering. Copyright © 2016 Elsevier Ltd. All rights reserved.

A mathematical model for foreign body reactions in 2D.

PubMed

Su, Jianzhong; Gonzales, Humberto Perez; Todorov, Michail; Kojouharov, Hristo; Tang, Liping

2011-02-01

The foreign body reactions are commonly referred to the network of immune and inflammatory reactions of human or animals to foreign objects placed in tissues. They are basic biological processes, and are also highly relevant to bioengineering applications in implants, as fibrotic tissue formations surrounding medical implants have been found to substantially reduce the effectiveness of devices. Despite of intensive research on determining the mechanisms governing such complex responses, few mechanistic mathematical models have been developed to study such foreign body reactions. This study focuses on a kinetics-based predictive tool in order to analyze outcomes of multiple interactive complex reactions of various cells/proteins and biochemical processes and to understand transient behavior during the entire period (up to several months). A computational model in two spatial dimensions is constructed to investigate the time dynamics as well as spatial variation of foreign body reaction kinetics. The simulation results have been consistent with experimental data and the model can facilitate quantitative insights for study of foreign body reaction process in general.

On a new ironmaking process to produce hydrogen and reduce energy consumption

NASA Astrophysics Data System (ADS)

Corbari, Rodrigo

The primary purpose of the present work is to compute the volume and composition of the products of a theoretical charring unit for high volatile coals. In particular, the compositions of volatile gas and char and the hydrogen yield of the process. The volume of oxygen necessary to supply the energy for the process was also calculated. The model consists of materials and energy balance equations and local thermodynamic equilibrium. The model was combined with experimental results relating the effect of temperature on the extent of devolatilization and chemistry evolution of coal. Results of the model indicated that temperature plays a major role defining the quantities and composition of charring products. The H2 concentration of the volatile gas increased from about 16vol% at 700°C to 47vol% at 900°C, leveling off at approximately 52vol% at 1100°C. The hydrogen yield of the process increased from 7 to 60 percent at 700°C and 1100°C respectively. For a typical high volatile coal considered, the volume of gas generated varied from about 210 to 780 liters/kg-coal(STP) according to temperature and fraction of solids combusted. The char becomes enriched in carbon and depleted in hydrogen as temperature is increased. As much as 97 percent of the hydrogen in coal is removed at 1100°C. In the second part of this study, the kinetics of reduction of iron oxide fines with simulated smelter gas was experimentally studied by thermogravimetry. An equimolar CO/CO2 mixture was selected to simulate the off-gas of a smelter operating with char at 50 percent post combustion. Reduction temperatures ranged from 590°C to 1000°C. Under these conditions, reduction was limited to wustite. Results indicated that the reduction kinetics and dominating reaction mechanism varied with temperature, extent of reduction and type of iron oxide employed. Reduction from hematite to wustite proceeded in two consecutive reaction steps with magnetite as an intermediate oxide. The first reduction step, hematite to magnetite, was fast and controlled by external gas mass transfer independently of type of iron oxide and temperature employed in this work. The second reduction step, magnetite to wustite, was the overall reaction controlling step. The reduction mechanism varied with temperature and type of iron oxide. For moderately porous oxide fines (VALE and Taconite ores), the magnetite to wustite reduction followed a uniform internal reaction regime, where the chemical reaction at the gas-solid surface is the slowest step. For highly porous oxide (PAH), the magnetite to wustite reduction step was controlled by external gas mass transfer above 700°C. Below that, a mixed regime involving external gas mass transfer and limited mixed control, which comprises pore diffusion and chemical reaction, took place. The rate equations for this mixed control reaction mechanism were developed and the limited mixed control rate constant (klm) was computed. For denser oxides under uniform internal reaction, the product of the rate constant and pore surface area (k·S) was calculated. The final part of this research focused on the study of the mechanisms contributing for the distribution of sulfur in the smelter process. A methodology was developed for this purpose, which computes the sulfur concentration and distribution between the metal, slag and gas phases of the smelter for selected case scenarios. The model assumed the smelter as an ideal continuous stirred reactor under steady state conditions. Sulfur in the gas phase resulted from slag desulfurization by reaction with gas and the direct transfer of sulfur from coal or char. In general, it was found that a large fraction of sulfur leaves the smelter with the gas when coal or char is the only sulfur input to the process. However, the predominant mechanism for transfer of sulfur into the gas depended on process operating conditions. The effect of recycling sulfur back into the smelter was also evaluated. This is important when sulfur leaving with the smelter gas is captured by pre-reduced iron oxide or by dust particles and re-introduced in the process. In general, the more sulfur is recycled into the smelter, the higher the metal and slag sulfur concentration. However, the increasing sulfur content of metal and slag when sulfur is recycled may be partially counter-balanced by the use of char in place of coal. (Abstract shortened by UMI.)

Solute transport with multiple equilibrium-controlled or kinetically controlled chemical reactions

USGS Publications Warehouse

Friedly, John C.; Rubin, Jacob

1992-01-01

A new approach is applied to the problem of modeling solute transport accompanied by many chemical reactions. The approach, based on concepts of the concentration space and its stoichiometric subspaces, uses elements of the subspaces as primary dependent variables. It is shown that the resulting model equations are compact in form, isolate the chemical reaction expressions from flow expressions, and can be used for either equilibrium or kinetically controlled reactions. The implications of the results on numerical algorithms for solving the equations are discussed. The application of the theory is illustrated throughout with examples involving a simple but broadly representative set of reactions previously considered in the literature. Numerical results are presented for four interconnected reactions: a homogeneous complexation reaction, two sorption reactions, and a dissolution/precipitation reaction. Three cases are considered: (1) four kinetically controlled reactions, (2) four equilibrium-controlled reactions, and (3) a system with two kinetically controlled reactions and two equilibrium-controlled reactions.

Kinetics of Electrocatalytic Reactions from First-Principles: A Critical Comparison with the Ab Initio Thermodynamics Approach.

PubMed

Exner, Kai S; Over, Herbert

2017-05-16

Multielectron processes in electrochemistry require the stabilization of reaction intermediates (RI) at the electrode surface after every elementary reaction step. Accordingly, the bond strengths of these intermediates are important for assessing the catalytic performance of an electrode material. Current understanding of microscopic processes in modern electrocatalysis research is largely driven by theory, mostly based on ab initio thermodynamics considerations, where stable reaction intermediates at the electrode surface are identified, while the actual free energy barriers (or activation barriers) are ignored. This simple approach is popular in electrochemistry in that the researcher has a simple tool at hand in successfully searching for promising electrode materials. The ab initio TD approach allows for a rough but fast screening of the parameter space with low computational cost. However, ab initio thermodynamics is also frequently employed (often, even based on a single binding energy only) to comprehend on the activity and on the mechanism of an electrochemical reaction. The basic idea is that the activation barrier of an endergonic reaction step consists of a thermodynamic part and an additional kinetically determined barrier. Assuming that the activation barrier scales with thermodynamics (so-called Brønsted-Polanyi-Evans (BEP) relation) and the kinetic part of the barrier is small, ab initio thermodynamics may provide molecular insights into the electrochemical reaction kinetics. However, for many electrocatalytic reactions, these tacit assumptions are violated so that ab initio thermodynamics will lead to contradictions with both experimental data and ab initio kinetics. In this Account, we will discuss several electrochemical key reactions, including chlorine evolution (CER), oxygen evolution reaction (OER), and oxygen reduction (ORR), where ab initio kinetics data are available in order to critically compare the results with those derived from a simple ab initio thermodynamics treatment. We show that ab initio thermodynamics leads to erroneous conclusions about kinetic and mechanistic aspects for the CER over RuO 2 (110), while the kinetics of the OER over RuO 2 (110) and ORR over Pt(111) are reasonably well described. Microkinetics of an electrocatalyzed reaction is largely simplified by the quasi-equilibria of the RI preceding the rate-determining step (rds) with the reactants. Therefore, in ab initio kinetics the rate of an electrocatalyzed reaction is governed by the transition state (TS) with the highest free energy G rds # , defining also the rate-determining step (rds). Ab initio thermodynamics may be even more powerful, when using the highest free energy of an reaction intermediate G max (RI) rather than the highest free energy difference between consecutive reaction intermediates, ΔG loss , as a descriptor for the kinetics.

Testing an explanatory model of nurses' intention to report adverse drug reactions in hospital settings.

PubMed

Angelis, Alessia De; Pancani, Luca; Steca, Patrizia; Colaceci, Sofia; Giusti, Angela; Tibaldi, Laura; Alvaro, Rosaria; Ausili, Davide; Vellone, Ercole

2017-05-01

To test an explanatory model of nurses' intention to report adverse drug reactions in hospital settings, based on the theory of planned behaviour. Under-reporting of adverse drug reactions is an important problem among nurses. A cross-sectional design was used. Data were collected with the adverse drug reporting nurses' questionnaire. Confirmatory factor analysis was performed to test the factor validity of the adverse drug reporting nurses' questionnaire, and structural equation modelling was used to test the explanatory model. The convenience sample comprised 500 Italian hospital nurses (mean age = 43.52). Confirmatory factor analysis supported the factor validity of the adverse drug reporting nurses' questionnaire. The structural equation modelling showed a good fit with the data. Nurses' intention to report adverse drug reactions was significantly predicted by attitudes, subjective norms and perceived behavioural control (R² = 0.16). The theory of planned behaviour effectively explained the mechanisms behind nurses' intention to report adverse drug reactions, showing how several factors come into play. In a scenario of organisational empowerment towards adverse drug reaction reporting, the major predictors of the intention to report are support for the decision to report adverse drug reactions from other health care practitioners, perceptions about the value of adverse drug reaction reporting and nurses' favourable self-assessment of their adverse drug reaction reporting skills. © 2017 John Wiley & Sons Ltd.

A Joint Modeling Approach for Reaction Time and Accuracy in Psycholinguistic Experiments

ERIC Educational Resources Information Center

Loeys, T.; Rosseel, Y.; Baten, K.

2011-01-01

In the psycholinguistic literature, reaction times and accuracy can be analyzed separately using mixed (logistic) effects models with crossed random effects for item and subject. Given the potential correlation between these two outcomes, a joint model for the reaction time and accuracy may provide further insight. In this paper, a Bayesian…

A genetically optimized kinetic model for ethanol electro-oxidation on Pt-based binary catalysts used in direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Sánchez-Monreal, Juan; García-Salaberri, Pablo A.; Vera, Marcos

2017-09-01

A one-dimensional model is proposed for the anode of a liquid-feed direct ethanol fuel cell. The complex kinetics of the ethanol electro-oxidation reaction is described using a multi-step reaction mechanism that considers free and adsorbed intermediate species on Pt-based binary catalysts. The adsorbed species are modeled using coverage factors to account for the blockage of the active reaction sites on the catalyst surface. The reaction rates are described by Butler-Volmer equations that are coupled to a one-dimensional mass transport model, which incorporates the effect of ethanol and acetaldehyde crossover. The proposed kinetic model circumvents the acetaldehyde bottleneck effect observed in previous studies by incorporating CH3CHOHads among the adsorbed intermediates. A multi-objetive genetic algorithm is used to determine the reaction constants using anode polarization and product selectivity data obtained from the literature. By adjusting the reaction constants using the methodology developed here, different catalyst layers could be modeled and their selectivities could be successfully reproduced.

Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

Treesearch

Daniel J. Yelle; John Ralph; Charles R. Frihart

2011-01-01

To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

Modeling of Water-Breathing Propulsion Systems Utilizing the Aluminum-Seawater Reaction and Solid-Oxide Fuel Cells

DTIC Science & Technology

2011-01-01

ABSTRACT Title of Document: MODELING OF WATER-BREATHING PROPULSION SYSTEMS UTILIZING THE ALUMINUM-SEAWATER REACTION AND SOLID...Hybrid Aluminum Combustor (HAC): a novel underwater power system based on the exothermic reaction of aluminum with seawater. The system is modeled ...using a NASA-developed framework called Numerical Propulsion System Simulation (NPSS) by assembling thermodynamic models developed for each component

Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, Scott R.; Parkhurst, David L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel®, Visual Basic®, Python, or MATLAB". PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, S.R.; Parkhurst, D.L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server-for example, Excel??, Visual Basic??, Python, or MATLAB??. PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations. ?? 2011.

Poly (vinyl alcohol)/gum karaya electrospun plasma treated membrane for the removal of nanoparticles (Au, Ag, Pt, CuO and Fe3O4) from aqueous solutions.

PubMed

Padil, Vinod Vellora Thekkae; Černík, Miroslav

2015-04-28

In the present work, nanofibre membranes composed of polyvinyl alcohol (PVA) and a natural gum karaya (GK) hydrocolloid were prepared using electrospinning. The electrospun membranes of PVA/GK were cross-linked with heat treatment and later methane plasma was used to obtain a hydrophobic membrane. The morphology, characterization and adsorption ability of P-NFM was assessed using scanning electron microscopy, UV-vis spectroscopy, ATR-FTIR techniques, water contact angle and ICP-MS analytical methods. The membrane was employed for the extraction of nanoparticles (Ag, Au, Pt, CuO and Fe3O4) from water. The nanoparticle extraction kinetic and adsorption isotherm perform the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption capacities of the membrane for the removal of NPs from water diverge in the order Pt>Au>Ag>CuO>Fe3O4. The high adsorption efficiency for the removal of NPs from water was compared with an untreated membrane. Physisorption, functional group interactions, complexation reactions between metal/metal oxide nanoparticles with various functional groups present in NFM and modified surface properties such as the balance of hydrophilicity/hydrophobicity, surface free energy, and the high surface area of the plasma treated membrane were possible mechanisms of NPs adsorption onto NFM. The regeneration and reusability were tested in five consecutive adsorption/desorption cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

Invariant characteristics of self-organization modes in Belousov reaction modeling

NASA Astrophysics Data System (ADS)

Glyzin, S. D.; Goryunov, V. E.; Kolesov, A. Yu

2018-01-01

We consider the problem of mathematical modeling of oxidation-reduction oscillatory chemical reactions based on the mechanism of Belousov reaction. The process of the main components interaction in such reaction can be interpreted by a phenomenologically similar to it “predator-prey” model. Thereby, we consider a parabolic boundary value problem consisting of three Volterra-type equations, which is a mathematical model of this reaction. We carry out a local study of the neighborhood of the system’s non-trivial equilibrium state and construct the normal form of the considering system. Finally, we do a numerical analysis of the coexisting chaotic oscillatory modes of the boundary value problem in a flat area, which have different nature and occur as the diffusion coefficient decreases.

Optical frequency comb Faraday rotation spectroscopy

NASA Astrophysics Data System (ADS)

Johansson, Alexandra C.; Westberg, Jonas; Wysocki, Gerard; Foltynowicz, Aleksandra

2018-05-01

We demonstrate optical frequency comb Faraday rotation spectroscopy (OFC-FRS) for broadband interference-free detection of paramagnetic species. The system is based on a femtosecond doubly resonant optical parametric oscillator and a fast-scanning Fourier transform spectrometer (FTS). The sample is placed in a DC magnetic field parallel to the light propagation. Efficient background suppression is implemented via switching the direction of the field on consecutive FTS scans and subtracting the consecutive spectra, which enables long-term averaging. In this first demonstration, we measure the entire Q- and R-branches of the fundamental band of nitric oxide in the 5.2-5.4 µm range and achieve good agreement with a theoretical model.

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

Experimental Studies of Nuclear Physics Input for γ -Process Nucleosynthesis

NASA Astrophysics Data System (ADS)

Scholz, Philipp; Heim, Felix; Mayer, Jan; Netterdon, Lars; Zilges, Andreas

The predictions of reaction rates for the γ process in the scope of the Hauser-Feshbach statistical model crucially depend on nuclear physics input-parameters as optical-model potentials (OMP) or γ -ray strength functions. Precise cross-section measurements at astrophysically relevant energies help to constrain adopted models and, therefore, to reduce the uncertainties in the theoretically predicted reaction rates. During the last years, several cross-sections of charged-particle induced reactions on heavy nuclei have been measured at the University of Cologne. Either by means of the in-beam method at the HORUS γ -ray spectrometer or the activation technique using the Cologne Clover Counting Setup, total and partial cross-sections could be used to further constrain different models for nuclear physics input-parameters. It could be shown that modifications on the α -OMP in the case of the 112Sn(α , γ ) reaction also improve the description of the recently measured cross sections of the 108Cd(α , γ ) and 108Cd(α , n) reaction and other reactions as well. Partial cross-sections of the 92Mo(p, γ ) reaction were used to improve the γ -strength function model in 93Tc in the same way as it was done for the 89Y(p, γ ) reaction.

Phototherapy and orange-tinted goggles for night-shift adaptation of police officers on patrol.

PubMed

Boivin, Diane B; Boudreau, Philippe; Tremblay, Geneviève M

2012-06-01

The aim of the present combined field and laboratory study was to assess circadian entrainment in two groups of police officers working seven consecutive 8/8.5-h night shifts as part of a rotating schedule. Eight full-time police officers on patrol (mean age ± SD: 29.8 ± 6.5 yrs) were provided an intervention consisting of intermittent exposure to wide-spectrum bright light at night, orange-tinted goggles at sunrise, and maintenance of a regular sleep/darkness episode in the day. Orange-tinted goggles have been shown to block the melatonin-suppressing effect of light significantly more than neutral gray density goggles. Nine control group police officers (mean age ± SD: 30.3 ± 4.1 yrs) working the same schedule were enrolled. Police officers were studied before, after (in the laboratory), and during (ambulatory) a series of seven consecutive nights. Urine samples were collected at wake time and bedtime throughout the week of night work and during laboratory visits (1 × /3 h) preceding and following the work week to measure urinary 6-sulfatoxymelatonin (UaMT6s) excretion rate. Subjective alertness was assessed at the start, middle, and end of night shifts. A 10-min psychomotor vigilance task was performed at the start and end of each shift. Both laboratory visits consisted of two 8-h sleep episodes based on the prior schedule. Saliva samples were collected 2 × /h during waking episodes to assay their melatonin content. Subjective alertness (3 × /h) and performance (1 × /2 h) were assessed during wake periods in the laboratory. A mixed linear model was used to analyze the progression of UaMt6s excreted during daytime sleep episodes at home, as well as psychomotor performance and subjective alertness during night shifts. Two-way analysis of variance (ANOVA) (factors: laboratory visit and group) were used to compare peak salivary melatonin and UaMT6s excretion rate in the laboratory. In both groups of police officers, the excretion rate of UaMT6s at home was higher during daytime sleep episodes at the end compared to the start of the work week (p < .001). This rate increased significantly more in the intervention than control group (p = .032). A significant phase delay of salivary melatonin was observed in both groups at the end of study (p = .009), although no significant between-group difference was reached. Reaction speed dropped, and subjective alertness decreased throughout the night shift in both groups (p < .001). Reaction speed decreased throughout the work week in the control group (p ≤ .021), whereas no difference was observed in the intervention group. Median reaction time was increased as of the 5th and 6th nights compared to the 2nd night in controls (p ≤ .003), whereas it remained stable in the intervention group. These observations indicate better physiological adaptation in the intervention group compared to the controls.

Site-specific recombination in the cyanobacterium Anabaena sp. strain PCC 7120 catalyzed by the integrase of coliphage HK022.

PubMed

Melnikov, Olga; Zaritsky, Arieh; Zarka, Aliza; Boussiba, Sammy; Malchin, Natalia; Yagil, Ezra; Kolot, Mikhail

2009-07-01

The integrase (Int) of the lambda-like coliphage HK022 catalyzes the site-specific integration and excision of the phage DNA into and from the chromosome of its host, Escherichia coli. Int recognizes two different pairs of recombining sites attP x attB and attL x attR for integration and excision, respectively. This system was adapted to the cyanobacterium Anabaena sp. strain PCC 7120 as a potential tool for site-specific gene manipulations in the cyanobacterium. Two plasmids were consecutively cointroduced by conjugation into Anabaena cells, one plasmid that expresses HK022 Int recombinase and the other plasmid that carries the excision substrate P(glnA)-attL-T1/T2-attR-lacZ, where T1/T2 are the strong transcription terminators of rrnB, to prevent expression of the lacZ reporter under the constitutive promoter P(glnA). The Int-catalyzed site-specific recombination reaction was monitored by the expression of lacZ emanating as a result of T1/T2 excision. Int catalyzed the site-specific excision reaction in Anabaena cells when its substrate was located either on the plasmid or on the chromosome with no need to supply an accessory protein, such as integration host factor and excisionase (Xis), which are indispensable for this reaction in its host, E. coli.

Cu3(BTC)2 catalyzed dehydrogenative coupling of dimethylphenylsilane with phenol and homocoupling of dimethylphenylsilane to disiloxane.

PubMed

Anbu, Nagaraj; Dhakshinamoorthy, Amarajothi

2017-03-15

Cu 3 (BTC) 2 (BTC: 1,3,5-benzenetricarboxylic acid) showed to be an efficient and reusable heterogeneous solid catalyst for the formation of SiO bond through dehydrogenative coupling of dimethylphenylsilane (1) with phenol under mild reaction conditions. It is observed that Fe(BTC), MIL-101(Cr) and UiO-66(Zr) are not able to promote this cross coupling between 1 and phenol. Cu 3 (BTC) 2 exhibits higher stability and activity compared to other MOFs studied here. Furthermore, Cu 3 (BTC) 2 is reused for three consecutive cycles with a slight decay in its activity. Comparison of the powder XRD patterns of the fresh with three times used Cu 3 (BTC) 2 showed no significant difference in the crystalline structure, thus, indicating the catalyst stability under the optimized reaction conditions. Furthermore, EPR, FT-IR and SEM images of the fresh and reused Cu 3 (BTC) 2 did not show any change in the oxidation state of copper or structural morphology. Also, no leaching of copper is detected under optimized reaction conditions. In addition, Cu 3 (BTC) 2 showed higher activity compared to Pt, Pd, Au and Cu supported on active carbon as heterogeneous catalysts in the synthesis of disiloxane from 1 through SiH activation. Copyright © 2016 Elsevier Inc. All rights reserved.

Rational Design of High-Number dsDNA Fragments Based on Thermodynamics for the Construction of Full-Length Genes in a Single Reaction.

PubMed

Birla, Bhagyashree S; Chou, Hui-Hsien

2015-01-01

Gene synthesis is frequently used in modern molecular biology research either to create novel genes or to obtain natural genes when the synthesis approach is more flexible and reliable than cloning. DNA chemical synthesis has limits on both its length and yield, thus full-length genes have to be hierarchically constructed from synthesized DNA fragments. Gibson Assembly and its derivatives are the simplest methods to assemble multiple double-stranded DNA fragments. Currently, up to 12 dsDNA fragments can be assembled at once with Gibson Assembly according to its vendor. In practice, the number of dsDNA fragments that can be assembled in a single reaction are much lower. We have developed a rational design method for gene construction that allows high-number dsDNA fragments to be assembled into full-length genes in a single reaction. Using this new design method and a modified version of the Gibson Assembly protocol, we have assembled 3 different genes from up to 45 dsDNA fragments at once. Our design method uses the thermodynamic analysis software Picky that identifies all unique junctions in a gene where consecutive DNA fragments are specifically made to connect to each other. Our novel method is generally applicable to most gene sequences, and can improve both the efficiency and cost of gene assembly.

Fever Therapy With Intravenously Applied Mistletoe Extracts for Cancer Patients: A Retrospective Study.

PubMed

Schläppi, Marc; Ewald, Christoph; Kuehn, Jürgen Johannes; Weinert, Tomas; Huber, Roman

2017-12-01

So-called spontaneous remissions in cancer often seem to occur after febrile events. Mistletoe preparations (MPs) are used off-label intravenously to induce fever within concepts of integrative oncology. We wanted to investigate the frequency of febrile reactions and safety related to intravenously applied MPs (IAMPs). This was a retrospective analysis of data from consecutive cancer patients who were treated in 2 anthroposophic hospitals with IAMPs. The main outcome parameter was the rate of core temperature increase to ≥38.5°C within 24 hours after IAMPs. Secondary outcome parameters were Common Toxicity Criteria for Adverse Events (CTCAE; version 4.0). 59 patients, with in total 567 IAMPs, were analyzed; 45 patients (76%, 95% CI = 65%-87%) had an increase of core temperature to ≥38.5°C after at least 1 treatment. Mean increase in temperature was 1.5°C ± 0.8°C. Adverse events were mostly fever-related symptoms (headache, joint pain, shivering). Grade 1 allergic reactions were documented in 0.6% of treatments. CTCAEs grade 3 to 5 did not occur; 38/59 patients had advanced and/or metastatic disease. IAMPs resulted in febrile reactions to >38.5°C in the majority of patients and can be considered as safe. Adverse events were mostly related to fever and were not severe.

Numerical modeling of particle generation from ozone reactions with human-worn clothing in indoor environments

NASA Astrophysics Data System (ADS)

Rai, Aakash C.; Lin, Chao-Hsin; Chen, Qingyan

2015-02-01

Ozone-terpene reactions are important sources of indoor ultrafine particles (UFPs), a potential health hazard for human beings. Humans themselves act as possible sites for ozone-initiated particle generation through reactions with squalene (a terpene) that is present in their skin, hair, and clothing. This investigation developed a numerical model to probe particle generation from ozone reactions with clothing worn by humans. The model was based on particle generation measured in an environmental chamber as well as physical formulations of particle nucleation, condensational growth, and deposition. In five out of the six test cases, the model was able to predict particle size distributions reasonably well. The failure in the remaining case demonstrated the fundamental limitations of nucleation models. The model that was developed was used to predict particle generation under various building and airliner cabin conditions. These predictions indicate that ozone reactions with human-worn clothing could be an important source of UFPs in densely occupied classrooms and airliner cabins. Those reactions could account for about 40% of the total UFPs measured on a Boeing 737-700 flight. The model predictions at this stage are indicative and should be improved further.

Thermodynamically Feasible Kinetic Models of Reaction Networks

PubMed Central

Ederer, Michael; Gilles, Ernst Dieter

2007-01-01

The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilibrium all fluxes vanish. We introduce a thermodynamic-kinetic modeling (TKM) formalism that adapts the concepts of potentials and forces from irreversible thermodynamics to kinetic modeling. In the proposed formalism, the thermokinetic potential of a compound is proportional to its concentration. The proportionality factor is a compound-specific parameter called capacity. The thermokinetic force of a reaction is a function of the potentials. Every reaction has a resistance that is the ratio of thermokinetic force and reaction rate. For mass-action type kinetics, the resistances are constant. Since it relies on the thermodynamic concept of potentials and forces, the TKM formalism structurally observes detailed balance for all values of capacities and resistances. Thus, it provides an easy way to formulate physically feasible, kinetic models of biological reaction networks. The TKM formalism is useful for modeling large biological networks that are subject to many detailed balance relations. PMID:17208985

Computational Study of a Model System of Enzyme-Mediated [4+2] Cycloaddition Reaction

PubMed Central

2015-01-01

A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reac-tion was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation. PMID:25853669

Chemical reactions simulated by ground-water-quality models

USGS Publications Warehouse

Grove, David B.; Stollenwerk, Kenneth G.

1987-01-01

Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru

Manifestations of the “cage” effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the “cage complex,” just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of themore » “cage” effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.« less

SurfKin: an ab initio kinetic code for modeling surface reactions.

PubMed

Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

2014-10-05

In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

An Examination of Amotivated Students within the Sport Education Model

ERIC Educational Resources Information Center

Perlman, Dana

2012-01-01

The purpose of this study was to examine the perceptions and experiences of 33 amotivated students (i.e. students with low levels of motivation) during four consecutive seasons of the Sport Education Model. A qualitative case-study approach was utilized within this study and data was collected using interviews, field notes and reflective journals.…

Academic Motivation, Self-Concept, Engagement, and Performance in High School: Key Processes from a Longitudinal Perspective

ERIC Educational Resources Information Center

Green, Jasmine; Liem, Gregory Arief D.; Martin, Andrew J.; Colmar, Susan; Marsh, Herbert W.; McInerney, Dennis

2012-01-01

The study tested three theoretically/conceptually hypothesized longitudinal models of academic processes leading to academic performance. Based on a longitudinal sample of 1866 high-school students across two consecutive years of high school (Time 1 and Time 2), the model with the most superior heuristic value demonstrated: (a) academic motivation…

Vulnerability and Resilience in Women with Arthritis: Test of a Two-Factor Model

ERIC Educational Resources Information Center

Smith, Bruce W.; Zautra, Alex J.

2008-01-01

The purpose of this study was to test a 2-factor model of affective health in women with rheumatoid arthritis (RA; n = 82) or osteoarthritis (OA; n = 88). Positive and negative social interactions and affect were assessed for 11 consecutive weeks. For each participant, Vulnerability and Resilience factors were created from factor analyses of…

29 CFR 2520.101-3 - Notice of blackout periods under individual account plans.

Code of Federal Regulations, 2010 CFR

2010-07-01

... paragraph 4. of the model notice in paragraph (e)(2) of this section will satisfy this requirement); (v) In.... of the model notice in paragraph (e)(2) of this section will satisfy this requirement), and (B) An... three consecutive business days. (ii) Exclusions. The term “blackout period” does not include a...

A computational study of pyrolysis reactions of lignin model compounds

Treesearch

Thomas Elder

2010-01-01

Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

The Acceptance of Exceptionality: A Three Dimensional Model.

ERIC Educational Resources Information Center

Martin, Larry L.; Nivens, Maryruth K.

A model extrapolates from E. Kubler-Ross' conception of the stages of grief to apply to parent and family reactions when an exceptionality is identified. A chart lists possible parent feelings and reactions, possible school reactions to the parent in grief, and the child's reactions during each of five stages: denial, rage and anger, bargaining,…

A comprehensive model to determine the effects of temperature and species fluctuations on reactions in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Antaki, P. J.

1981-01-01

The joint probability distribution function (pdf), which is a modification of the bivariate Gaussian pdf, is discussed and results are presented for a global reaction model using the joint pdf. An alternative joint pdf is discussed. A criterion which permits the selection of temperature pdf's in different regions of turbulent, reacting flow fields is developed. Two principal approaches to the determination of reaction rates in computer programs containing detailed chemical kinetics are outlined. These models represent a practical solution to the modeling of species reaction rates in turbulent, reacting flows.

Calibration of Complex Subsurface Reaction Models Using a Surrogate-Model Approach

EPA Science Inventory

Application of model assessment techniques to complex subsurface reaction models involves numerous difficulties, including non-trivial model selection, parameter non-uniqueness, and excessive computational burden. To overcome these difficulties, this study introduces SAMM (Simult...

Production of pyrite nanoparticles using high energy planetary ball milling for sonocatalytic degradation of sulfasalazine.

PubMed

Khataee, Alireza; Fathinia, Siavash; Fathinia, Mehrangiz

2017-01-01

Sonocatalytic performance of pyrite nanoparticles was evaluated by the degradation of sulfasalazine (SSZ). Pyrite nanoparticles were produced via a high energy mechanical ball milling (MBM) in different processing time from 2h to 6h, in the constant milling speed of 320rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer-Emmett-Teller (BET) confirmed the production of pyrite nanoparticles during 6h of ball milling with the average size distribution of 20-80nm. The effects of various operational parameters including pH value, catalyst amount (mg/L), SSZ concentration (mg/L), ultrasonic frequency (kHz) and reaction time on the SSZ removal efficiency were examined. The obtained results showed that the maximum removal efficiency of 97.00% was obtained at pH value of 4, catalyst dosage of 0.5g/L, SSZ concentration of 10mg/L and reaction time of 30min. Experimental results demonstrated that the kinetic of the degradation process can be demonstrated using Langmuir-Hinshelwood (L-H) kinetic model. The effect of different inorganic ions such as Cl - , CO 3 2- and SO 4 2- was investigated on the L-H reaction rate (k r ) and adsorption (K s ) constants. Results showed that the presence of the mentioned ions significantly influenced the L-H constants. The impact of ethanol as a OH radical scavenger and some enhancers including H 2 O 2 and K 2 S 2 O 8 was investigated on the SSZ removal efficiency. Accordingly, the presence of ethanol suppressed SSZ degradation due to the quenching of OH radicals and the addition of K 2 S 2 O 8 and H 2 O 2 increased the SSZ removal efficiency, due to the formation of SO 4 - and additional OH radicals, respectively. Under the identical conditions of operating parameters, pyrite nanoparticles maintained their catalytic activity during four consecutive runs. Copyright © 2016 Elsevier B.V. All rights reserved.

Six-year longitudinal study of pathways leading to explosive anger involving the traumas of recurrent conflict and the cumulative sense of injustice in Timor-Leste.

PubMed

Silove, Derrick; Mohsin, Mohammed; Tay, Alvin Kuowei; Steel, Zachary; Tam, Natalino; Savio, Elisa; Da Costa, Zelia Maria; Rees, Susan

2017-10-01

Cumulative evidence suggests that explosive anger may be a common reaction among survivors of mass conflict. However, little is known about the course of explosive anger in the years following mass conflict, or the psychosocial factors that influence the trajectory of that reaction pattern. We examined these issues in a 6-year longitudinal study (2004-2010) conducted among adult residents of a rural and an urban village in Timor-Leste (n = 1022). We derived a brief, context-specific index of explosive anger using qualitative methods. Widely used measures of post-traumatic stress disorder (PTSD) and severe psychological distress were calibrated to the Timor context. We developed an index of the cumulative sense of injustice related to consecutive historical periods associated with conflict in Timor-Leste. We applied partial structural equation modeling (SEM) to examine pathways from baseline explosive anger, socio-demographic factors, recurrent trauma, mental health indices (PTSD, severe psychological distress) and the sense of injustice, to explosive anger. Half of the sample with explosive anger at baseline continued to report that reaction pattern after 6 years; and a third of those who did not report explosive anger at baseline developed the response by follow-up. A symmetrical pattern of younger age, female gender and the trauma count for the preceding historical period predicted explosive anger at each assessment point. The sense of injustice was related to explosive anger at follow-up. Explosive anger was associated with impairment in functioning and conflict with the intimate partner and wider family. Sampling constraints caution against generalizing our findings to other populations. Nevertheless, our data suggest that explosive anger may persist for a prolonged period of time following mass conflict and that the response pattern is initiated and maintained by recurrent trauma exposure associated with a sense of injustice. Averting recurrence of mass violence and addressing persisting feelings of injustice may assist in reducing anger in conflict-affected societies. Whether explosive anger at the individual level increases risk of collective violence under conditions of social and political instability requires further inquiry.

Monodisperse cobalt ferrite nanoparticles assembled on mesoporous graphitic carbon nitride (CoFe2O4/mpg-C3N4): A magnetically recoverable nanocomposite for the photocatalytic degradation of organic dyes

NASA Astrophysics Data System (ADS)

Hassani, Aydin; Eghbali, Paria; Ekicibil, Ahmet; Metin, Önder

2018-06-01

Monodisperse cobalt ferrite (CoFe2O4) nanoparticles (NPs) were synthesized by thermal decomposition of metal precursors in the presence of surfactants and then assembled on mesoporous graphitic carbon nitride (mpg-C3N4) via sonication of two components in ethanol solution. The yielded nanocomposite, namely CoFe2O4/mpg-C3N4, were characterized by using many advanced analytical techniques (TEM, HR-SEM, EDX, XRD, BET, PPMS-VSM, UV-vis DRS and ICP-MS). The magnetic properties of the CoFe2O4/mpg-C3N4 nanocomposite were studied by using M-H and M-T loops and the magnetic saturation and blocking temperature of the nanocomposite were found to be 6.1 emu/g and 269 K, respectively. The nanocomposite were then tested in the photocatalytic degradation of Malachite Green (MG) and showed considerably high photocatalytic activity under UV-light irradiation. The effects of various key operating parameters comprising catalyst amount, initial dye concentration, pH and reaction time span for the degradation of MG dye were studied to optimize the reaction conditions. The maximum degradation efficiency (DE %) of 93.41% was obtained by using 0.08 g L-1 catalyst and 10 mg L-1 MG dye at pH 5 within 120 min reaction time. Besides MG, the photocatalytic degradation of several other organic dyes (methylene blue, acid orange 7 and rhodamine B) was also studied to exhibit the performance of CoFe2O4/mpg-C3N4 nanocomposite under the optimized conditions. The results revealed that the kinetic of dye removal process could be designated through the application of pseudo-first-order kinetic model. In addition to high photocatalytic activity, CoFe2O4/mpg-C3N4 nanocomposite could be magnetically recovered after the dye degradation and reused for consecutive five runs without a significant loss (nearly 17%) in their initial performance.

Reduced Order Models for Reactions of Energetic Materials

NASA Astrophysics Data System (ADS)

Kober, Edward

The formulation of reduced order models for the reaction chemistry of energetic materials under high pressures is needed for the development of mesoscale models in the areas of initiation, deflagration and detonation. Phenomenologically, 4-8 step models have been formulated from the analysis of cook-off data by analyzing the temperature rise of heated samples. Reactive molecular dynamics simulations have been used to simulate many of these processes, but reducing the results of those simulations to simple models has not been achieved. Typically, these efforts have focused on identifying molecular species and detailing specific chemical reactions. An alternative approach is presented here that is based on identifying the coordination geometries of each atom in the simulation and tracking classes of reactions by correlated changes in these geometries. Here, every atom and type of reaction is documented for every time step; no information is lost from unsuccessful molecular identification. Principal Component Analysis methods can then be used to map out the effective chemical reaction steps. For HMX and TATB decompositions simulated with ReaxFF, 90% of the data can be explained by 4-6 steps, generating models similar to those from the cook-off analysis. By performing these simulations at a variety of temperatures and pressures, both the activation and reaction energies and volumes can then be extracted.

Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

NASA Astrophysics Data System (ADS)

D'Ulivo, Alessandro

2016-05-01

A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

Influence of reaction-induced fracturing on serpentinisation rate

NASA Astrophysics Data System (ADS)

Malvoisin, B.; Brantut, N.; Kaczmarek, M. A.

2017-12-01

The alteration of mantle rocks at mid-ocean ridges (i.e. serpentinisation) can lead to a solid volume increase responsible for stress build-up and cracking during reaction (reaction-induced fracturing). This mechanism has been proposed to play a key role for maintaining fluid pathways during reaction. However, its impact on the reaction rate is not yet quantified. We propose here a micromechanical model to quantify the influence of the crystallisation pressure generated during serpentine precipitation on crack propagation in olivine. This model is then coupled to a simple geometrical model to calculate the generation of reactive surface area during grain splitting, and thus bulk reaction rate. The model is able to reproduce experimental kinetic data as well as the mesh texture observed in natural samples. The model results are compared to olivine grain size distribution in serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papuan New Guinea). The observations and the model both indicate a decrease of the mean grain size by one order of magnitude as the reaction progresses from 5 to 40 %. Based on this good agreement, we use our model to predict that cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values comprised between 10 and 1,000 yr. The peak serpentinisation is also shifted 4 km above the previous predictions due to effective pressure increase with depth.

Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

NASA Astrophysics Data System (ADS)

Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

2015-12-01

With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

NASA Astrophysics Data System (ADS)

Zhang, Hong; Zuo, Ran; Zhang, Guoyi

2017-11-01

In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

Frequency of Extrapyramidal Adverse Reactions in Schizophrenic Outpatients Treated with Risperidone, Olanzapine, Quetiapine or Haloperidol : Results of the EIRE Study.

PubMed

Bobes, Julio; Rejas, J; Garcia-Garcia, M; Rico-Villademoros, F; García-Portilla, M P; Madrigal, M; Hernández, G

2002-09-01

The EIRE (Estudio de Investigaciön de Resultados en Esquizofrenia - Outcomes Research Study in Schizophrenia) study was initiated in order to assess the frequency of adverse reactions [extrapyramidal symptoms (EPS), hyperprolactinaemia, sexual dysfunction and weight gain] caused by atypical antipsychotics and haloperidol in patients with schizophrenia during routine treatment in clinical practice. This paper presents the results of the assessment of extrapyramidal adverse reactions. Outpatients diagnosed with schizophrenia according to the Diagnostic and Statistical Manual of mental disorders, 4th edition (DSM-IV), criteria and receiving a single antipsychotic (risperidone, olanzapine, quetiapine or haloperidol) for at least 4 weeks were consecutively recruited. In this cross-sectional and non-interventional study data were collected in a single visit; this included demographic and clinical characteristics, current antipsychotic and concomitant treatment, and data on several adverse effects listed in a modified version of the UKU (Udvalg for Kliniske Undersogelser - Committee on Clinical Investigations) scale. For paired comparisons of the frequency of adverse reactions between treatments the Chi-squared (χ 2 ) test was used. For estimation of the risk of a given adverse reaction with a given treatment a logistic regression method was used. 636 evaluable patients (of 669 recruited) were assessed. The frequency of EPS with haloperidol (78.3% of the cases) was higher than with risperidone (55.1%), quetiapine (39.5%) and olanzapine (35.8%) [χ 2 : p < 0.05], and the difference between risperidone and olanzapine was also statistically significant (χ 2 : p < 0.05). Very similar results were obtained in the individualised analysis of the items as regards the occurrence of akathisia, which was also more frequent in the haloperidol (36.8%) and risperidone (19.7%) groups than in the olanzapine (11.4%) and quetiapine (2.6%) groups (χ 2 : p < 0.05). Olanzapine, quetiapine and risperidone also showed a lower risk of EPS than haloperidol when adjusting by dose. Our results suggest that the atypical antipsychotics studied are less likely to induce extrapyramidal adverse reactions compared with haloperidol in stabilised patients, although these reactions are still common.

The Measurement of Electrical Conductivity in Detonating Condensed Explosives

DTIC Science & Technology

1993-03-01

in the light of our existing understanding. DETONATION CONDUCTION MODELS Various models of conduction have been considered during the course of these...reduction, shock induced conduction in the reaction products, and conduction in coagulated carbon behind the reaction zone. The first model , due to...results below show. The second model was proposed by Griem. 3 For relative simplicity, he assumed that the reaction zone could be represented by a

DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cyburt, R. H.; Keek, L.; Schatz, H.

2016-10-20

X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to matchmore » calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.« less

Multi-criteria comparative evaluation of spallation reaction models

NASA Astrophysics Data System (ADS)

Andrianov, Andrey; Andrianova, Olga; Konobeev, Alexandr; Korovin, Yury; Kuptsov, Ilya

2017-09-01

This paper presents an approach to a comparative evaluation of the predictive ability of spallation reaction models based on widely used, well-proven multiple-criteria decision analysis methods (MAVT/MAUT, AHP, TOPSIS, PROMETHEE) and the results of such a comparison for 17 spallation reaction models in the presence of the interaction of high-energy protons with natPb.

SSER: Species specific essential reactions database.

PubMed

Labena, Abraham A; Ye, Yuan-Nong; Dong, Chuan; Zhang, Fa-Z; Guo, Feng-Biao

2017-04-19

Essential reactions are vital components of cellular networks. They are the foundations of synthetic biology and are potential candidate targets for antimetabolic drug design. Especially if a single reaction is catalyzed by multiple enzymes, then inhibiting the reaction would be a better option than targeting the enzymes or the corresponding enzyme-encoding gene. The existing databases such as BRENDA, BiGG, KEGG, Bio-models, Biosilico, and many others offer useful and comprehensive information on biochemical reactions. But none of these databases especially focus on essential reactions. Therefore, building a centralized repository for this class of reactions would be of great value. Here, we present a species-specific essential reactions database (SSER). The current version comprises essential biochemical and transport reactions of twenty-six organisms which are identified via flux balance analysis (FBA) combined with manual curation on experimentally validated metabolic network models. Quantitative data on the number of essential reactions, number of the essential reactions associated with their respective enzyme-encoding genes and shared essential reactions across organisms are the main contents of the database. SSER would be a prime source to obtain essential reactions data and related gene and metabolite information and it can significantly facilitate the metabolic network models reconstruction and analysis, and drug target discovery studies. Users can browse, search, compare and download the essential reactions of organisms of their interest through the website http://cefg.uestc.edu.cn/sser .

Critical evaluation of Jet-A spray combustion using propane chemical kinetics in gas turbine combustion simulated by KIVA-2

NASA Technical Reports Server (NTRS)

Nguyen, H. L.; Ying, S.-J.

1990-01-01

Jet-A spray combustion has been evaluated in gas turbine combustion with the use of propane chemical kinetics as the first approximation for the chemical reactions. Here, the numerical solutions are obtained by using the KIVA-2 computer code. The KIVA-2 code is the most developed of the available multidimensional combustion computer programs for application of the in-cylinder combustion dynamics of internal combustion engines. The released version of KIVA-2 assumes that 12 chemical species are present; the code uses an Arrhenius kinetic-controlled combustion model governed by a four-step global chemical reaction and six equilibrium reactions. Researchers efforts involve the addition of Jet-A thermophysical properties and the implementation of detailed reaction mechanisms for propane oxidation. Three different detailed reaction mechanism models are considered. The first model consists of 131 reactions and 45 species. This is considered as the full mechanism which is developed through the study of chemical kinetics of propane combustion in an enclosed chamber. The full mechanism is evaluated by comparing calculated ignition delay times with available shock tube data. However, these detailed reactions occupy too much computer memory and CPU time for the computation. Therefore, it only serves as a benchmark case by which to evaluate other simplified models. Two possible simplified models were tested in the existing computer code KIVA-2 for the same conditions as used with the full mechanism. One model is obtained through a sensitivity analysis using LSENS, the general kinetics and sensitivity analysis program code of D. A. Bittker and K. Radhakrishnan. This model consists of 45 chemical reactions and 27 species. The other model is based on the work published by C. K. Westbrook and F. L. Dryer.

MESOSCOPIC MODELING OF STOCHASTIC REACTION-DIFFUSION KINETICS IN THE SUBDIFFUSIVE REGIME

PubMed Central

BLANC, EMILIE; ENGBLOM, STEFAN; HELLANDER, ANDREAS; LÖTSTEDT, PER

2017-01-01

Subdiffusion has been proposed as an explanation of various kinetic phenomena inside living cells. In order to fascilitate large-scale computational studies of subdiffusive chemical processes, we extend a recently suggested mesoscopic model of subdiffusion into an accurate and consistent reaction-subdiffusion computational framework. Two different possible models of chemical reaction are revealed and some basic dynamic properties are derived. In certain cases those mesoscopic models have a direct interpretation at the macroscopic level as fractional partial differential equations in a bounded time interval. Through analysis and numerical experiments we estimate the macroscopic effects of reactions under subdiffusive mixing. The models display properties observed also in experiments: for a short time interval the behavior of the diffusion and the reaction is ordinary, in an intermediate interval the behavior is anomalous, and at long times the behavior is ordinary again. PMID:29046618

Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

NASA Astrophysics Data System (ADS)

Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

2016-04-01

Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

Kinetics of First-Row Transition Metal Cations (V+, Fe+, Co+) with OCS at Thermal Energies.

PubMed

Sweeny, Brendan C; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A

2018-05-03

The temperature-dependent kinetics for reactions of V + , Fe + , and Co + with OCS are measured using a selected ion flow tube apparatus heated to 300-600 K. All three reactions proceed solely by C-S activation at thermal energies, resulting in metal sulfide cation formation. Previously calculated reaction pathways were employed to inform statistical modeling of these reactions for comparison to the data. As surmised previously, all three reactions at thermal energies require spin crossing, with the Fe + reaction crossing once circumventing a prohibitive transition state, before crossing again to form ground state products. The Fe + and Co + reaction efficiencies increase with energy. For the Co + reaction, and to a lesser extent the Fe + reaction, the apparent activation energies are less than the reaction endothermicities, possibly indicating increasing diabatic behavior of the spin crossings with energy. The V + reaction was well modeled assuming an entirely adiabatic spin crossing, such that the resultant avoided crossing behaves similarly to a tight transition state. The subsequent reaction of VS + with OCS producing VS 2 + is also investigated; the rate-limiting transition state energy derived from statistical modeling is poorly reproduced by quantum calculations using a variety of methods, highlighting the large (1-2 eV) uncertainty in calculated energetics of transition-metal containing species.

Finite element modeling of contaminant transport in soils including the effect of chemical reactions.

PubMed

Javadi, A A; Al-Najjar, M M

2007-05-17

The movement of chemicals through soils to the groundwater is a major cause of degradation of water resources. In many cases, serious human and stock health implications are associated with this form of pollution. Recent studies have shown that the current models and methods are not able to adequately describe the leaching of nutrients through soils, often underestimating the risk of groundwater contamination by surface-applied chemicals, and overestimating the concentration of resident solutes. Furthermore, the effect of chemical reactions on the fate and transport of contaminants is not included in many of the existing numerical models for contaminant transport. In this paper a numerical model is presented for simulation of the flow of water and air and contaminant transport through unsaturated soils with the main focus being on the effects of chemical reactions. The governing equations of miscible contaminant transport including advection, dispersion-diffusion and adsorption effects together with the effect of chemical reactions are presented. The mathematical framework and the numerical implementation of the model are described in detail. The model is validated by application to a number of test cases from the literature and is then applied to the simulation of a physical model test involving transport of contaminants in a block of soil with particular reference to the effects of chemical reactions. Comparison of the results of the numerical model with the experimental results shows that the model is capable of predicting the effects of chemical reactions with very high accuracy. The importance of consideration of the effects of chemical reactions is highlighted.

A simple reaction-rate model for turbulent diffusion flames

NASA Technical Reports Server (NTRS)

Bangert, L. H.

1975-01-01

A simple reaction rate model is proposed for turbulent diffusion flames in which the reaction rate is proportional to the turbulence mixing rate. The reaction rate is also dependent on the mean mass fraction and the mean square fluctuation of mass fraction of each reactant. Calculations are compared with experimental data and are generally successful in predicting the measured quantities.

Abstract ID: 240 A probabilistic-based nuclear reaction model for Monte Carlo ion transport in particle therapy.

PubMed

Maria Jose, Gonzalez Torres; Jürgen, Henniger

2018-01-01

In order to expand the Monte Carlo transport program AMOS to particle therapy applications, the ion module is being developed in the radiation physics group (ASP) at the TU Dresden. This module simulates the three main interactions of ions in matter for the therapy energy range: elastic scattering, inelastic collisions and nuclear reactions. The simulation of the elastic scattering is based on the Binary Collision Approximation and the inelastic collisions on the Bethe-Bloch theory. The nuclear reactions, which are the focus of the module, are implemented according to a probabilistic-based model developed in the group. The developed model uses probability density functions to sample the occurrence of a nuclear reaction given the initial energy of the projectile particle as well as the energy at which this reaction will take place. The particle is transported until the reaction energy is reached and then the nuclear reaction is simulated. This approach allows a fast evaluation of the nuclear reactions. The theory and application of the proposed model will be addressed in this presentation. The results of the simulation of a proton beam colliding with tissue will also be presented. Copyright © 2017.

PYROTRON WITH TRANSLATIONAL CLOSURE FIELDS

DOEpatents

Hartwig, E.C.; Cummings, D.B.; Post, R.F.

1962-01-01

Circuit means is described for effecting inward transla- ' tory motion of the intensified terminal reflector field regions of a magnetic mirror plasma containment field with a simultaneous intensification of the over-all field configuration. The circuit includes a segmented magnetic field generating solenoid and sequentially actuated switch means to consecutively short-circuit the solenoid segments and place charged capacitor banks in shunt with the segments in an appropriate correlated sequence such that electrical energy is transferred inwardly between adjacent segments from the opposite ends of the solenoid. The resulting magnetic field is effective in both radially and axially adiabatically compressing a plasma in a reaction chamber disposed concentrically within the solenoid. In addition, one half of the circuit may be employed to unidirectionally accelerate plasma. (AEC)

Central vestibular syndrome in a red fox (Vulpes vulpes) with presumptive right caudal cerebral artery ischemic infarct and prevalent midbrain involvement.

PubMed

Ricciardi, Mario; Gernone, Floriana; Simone, Antonio De; Giannuzzi, Pasquale

2017-01-01

A wild young male red fox ( Vulpes vulpes ) was found in the mountainous hinterland of Rome (Italy) with a heavily depressed mental status and unresponsive to the surrounding environment. Neurological examination revealed depression, left circling, right head tilt, ventromedial positional strabismus and decreased postural reactions on the left side. Neurological abnormalities were suggestive of central vestibular syndrome. Two consecutive MRIs performed with 30 days interval were compatible with lacunar ischemic infarct in the territory of right caudal cerebral artery and its collateral branches. The lesion epicentre was in the right periaqueductal portion of the rostral mesencephalic tegmentum. Neuroanatomical and neurophysiological correlation between lesion localization and clinical presentation are discussed.

Computational investigation of rearrangements in huisgen cycloadducts of azolium N-dicyanomethanide 1,3-dipoles with alkynes: a mechanistic panoply.

PubMed

Burke, Luke A; Butler, Richard N

2009-08-07

The reaction surfaces leading to rearrangements and ring expansions of azapentalene cycloadducts of imidazolo- and triazolodicyanomethanide 1,3-dipoles with alkynes are studied with the B3LYP DFT method using the 6-31G(d) and 6-311+G(2d,p) basis sets. The surprisingly complex surface involves (1) consecutive but not combined pericyclic steps, a coarctate TS, and pseudopericyclic mechanisms, (2) anchimerically assisted H-atom transfer competing effectively with concerted symmetry-allowed sigmatropic steps, and (3) azolium methanide zwitterions and ketenimines as key intermediates. The azolium methanide is identified as the intermediate detected previously in a variable-temperature NMR experiment that converted the unstable cycloadduct to product imine.

Central vestibular syndrome in a red fox (Vulpes vulpes) with presumptive right caudal cerebral artery ischemic infarct and prevalent midbrain involvement

PubMed Central

Ricciardi, Mario; Gernone, Floriana; Simone, Antonio De; Giannuzzi, Pasquale

2017-01-01

A wild young male red fox (Vulpes vulpes) was found in the mountainous hinterland of Rome (Italy) with a heavily depressed mental status and unresponsive to the surrounding environment. Neurological examination revealed depression, left circling, right head tilt, ventromedial positional strabismus and decreased postural reactions on the left side. Neurological abnormalities were suggestive of central vestibular syndrome. Two consecutive MRIs performed with 30 days interval were compatible with lacunar ischemic infarct in the territory of right caudal cerebral artery and its collateral branches. The lesion epicentre was in the right periaqueductal portion of the rostral mesencephalic tegmentum. Neuroanatomical and neurophysiological correlation between lesion localization and clinical presentation are discussed. PMID:28717604

[Stapler and manual bronchial anastomosis--results of a consecutive trial series].

PubMed

Junginger, T; Walgenbach, S; Pichlmaier, H

1989-01-01

After lobectomy and pneumonectomy in experimental evaluations stapled bronchial closures showed the lowest incidence of inflammatory reaction and the highest strength determined by leakage pressure compared with other suture material. A total of 233 lung resections-performed at Surgical University Clinic Köln-Lindenthal and the Clinic for General and Abdominal Surgery of the Johannes-Gutenberg-Universität Mainz--were reviewed. Mechanical stapling reduced the rate of bronchopleural fistulas to 2.0% compared with 7.1% after manual suturing. In parallel, mortality related to bronchial stump leakage decreased to 0.7%. Main advantages of bronchial closure with staplers are the simplicity of their use, the speed and the uniformity of the closure. Thereby stapling devices are valuable completions in pulmonary surgery.

Two types of rate-determining step in chemical and biochemical processes.

PubMed Central

Yagisawa, S

1989-01-01

Close examination of the concept of the rate-determining step (RDS) shows that there are two types of RDS depending on the definition of 'rate'. One is represented by the highest peak of the free-energy diagram of consecutive reactions and holds true where the rate is defined in terms of the concentration of the first reactant. The other is represented by the peak showing the maximum free-energy difference, where the free-energy difference is the height of a peak measured from the bottom of any preceding troughs, where the definition of the rate is in terms of the total reactant concentration including intermediates. There are no criteria a priori for selecting one of them. PMID:2597141

The G209A mutation in the alpha-synuclein gene is not detected in familial cases of Parkinson disease in non-Greek and/or Italian populations.

PubMed

Wang, W W; Khajavi, M; Patel, B J; Beach, J; Jankovic, J; Ashizawa, T

1998-12-01

To determine whether the G-to-A substitution at nucleotide 209 (G209A) mutation in the alpha-synuclein gene is responsible for familial Parkinson disease (PD) in the US population. Polymerase chain reaction-based DNA analysis of consecutive patients with PD and family history of PD. A university-affiliated movement disorder clinic and a Veterans Affairs clinical research laboratory. Forty-four patients with PD and family history of PD and 29 patients with sporadic PD, all with no known Greek and/or Italian background. None of the DNA samples showed the G209A mutation. The G209A mutation is rare in US patients with familial PD.

Rapid hybridization of nucleic acids using isotachophoresis

PubMed Central

Bercovici, Moran; Han, Crystal M.; Liao, Joseph C.; Santiago, Juan G.

2012-01-01

We use isotachophoresis (ITP) to control and increase the rate of nucleic acid hybridization reactions in free solution. We present a new physical model, validation experiments, and demonstrations of this assay. We studied the coupled physicochemical processes of preconcentration, mixing, and chemical reaction kinetics under ITP. Our experimentally validated model enables a closed form solution for ITP-aided reaction kinetics, and reveals a new characteristic time scale which correctly predicts order 10,000-fold speed-up of chemical reaction rate for order 100 pM reactants, and greater enhancement at lower concentrations. At 500 pM concentration, we measured a reaction time which is 14,000-fold lower than that predicted for standard second-order hybridization. The model and method are generally applicable to acceleration of reactions involving nucleic acids, and may be applicable to a wide range of reactions involving ionic reactants. PMID:22733732

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

NASA Astrophysics Data System (ADS)

Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

2016-06-01

Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

40 CFR 60.3035 - May I conduct performance testing less often?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Model Rule-Continuous Compliance Requirements § 60.3035 May I conduct performance testing less often? (a) You can test less often for a given pollutant if you have test data for at least three consecutive...

Modeling thermal spike driven reactions at low temperature and application to zirconium carbide radiation damage

NASA Astrophysics Data System (ADS)

Ulmer, Christopher J.; Motta, Arthur T.

2017-11-01

The development of TEM-visible damage in materials under irradiation at cryogenic temperatures cannot be explained using classical rate theory modeling with thermally activated reactions since at low temperatures thermal reaction rates are too low. Although point defect mobility approaches zero at low temperature, the thermal spikes induced by displacement cascades enable some atom mobility as it cools. In this work a model is developed to calculate "athermal" reaction rates from the atomic mobility within the irradiation-induced thermal spikes, including both displacement cascades and electronic stopping. The athermal reaction rates are added to a simple rate theory cluster dynamics model to allow for the simulation of microstructure evolution during irradiation at cryogenic temperatures. The rate theory model is applied to in-situ irradiation of ZrC and compares well at cryogenic temperatures. The results show that the addition of the thermal spike model makes it possible to rationalize microstructure evolution in the low temperature regime.

A comparison of total reaction cross section models used in particle and heavy ion transport codes

NASA Astrophysics Data System (ADS)

Sihver, Lembit; Lantz, M.; Takechi, M.; Kohama, A.; Ferrari, A.; Cerutti, F.; Sato, T.

To be able to calculate the nucleon-nucleus and nucleus-nucleus total reaction cross sections with precision is very important for studies of basic nuclear properties, e.g. nuclear structure. This is also of importance for particle and heavy ion transport calculations because, in all particle and heavy ion transport codes, the probability function that a projectile particle will collide within a certain distance x in the matter depends on the total reaction cross sections. Furthermore, the total reaction cross sections will also scale the calculated partial fragmentation cross sections. It is therefore crucial that accurate total reaction cross section models are used in the transport calculations. In this paper, different models for calculating nucleon-nucleus and nucleus-nucleus total reaction cross sections are compared and discussed.

Transport—Reaction process in the reaction of flue gas desulfurization

NASA Astrophysics Data System (ADS)

Yan, Yan; Peng, Xiaofeng; Lee, Duu Jong

2000-12-01

A theoretical investigation was conducted to study the transport-reaction process in the spray-drying flue gas desulfurization. A transport-reaction model of single particle was proposed, which considered the water evaporation from the surface of droplet and the reaction at the same time. Based on this model, the reaction rate and the absorbent utilization can be calculated. The most appropriate particle radius and the initial absorbent concentration can be deduced through comparing the wet lifetime with the residence time, the result shows in the case that the partial pressure of vapor in the bulk flue gas is 2000Pa, the optimum initial radius and absorbent concentration are 210 310 µ m and 23% respectively. The model can supply the optimum parameters for semi-dry FGD system designed.

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

PubMed Central

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-01-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter’s L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R2) for their absorbance, Hunter’s L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter’s b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter’s b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine. PMID:28401086

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

PubMed

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-03-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

Catalytic diversity and homotropic allostery of two Cytochrome P450 monooxygenase like proteins from Trichoderma brevicompactum.

PubMed

Hussain, Razak; Kumari, Indu; Sharma, Shikha; Ahmed, Mushtaq; Khan, Tabreiz Ahmad; Akhter, Yusuf

2017-12-01

Trichothecenes are the secondary metabolites produced by Trichoderma spp. Some of these molecules have been reported for their ability to stimulate plant growth by suppressing plant diseases and hence enabling Trichoderma spp. to be efficiently used as biocontrol agents in modern agriculture. Many of the proteins involved in the trichothecenes biosynthetic pathway in Trichoderma spp. are encoded by the genes present in the tri cluster. Tri4 protein catalyzes three consecutive oxygenation reaction steps during biosynthesis of isotrichodiol in the trichothecenes biosynthetic pathway, while tri11 protein catalyzes the C4 hydroxylation of 12, 13-epoxytrichothec-9-ene to produce trichodermol. In the present study, we have homology modelled the three-dimensional structures of tri4 and tri11 proteins. Furthermore, molecular dynamics simulations were carried out to elucidate the mechanism of their action. Both tri4 and tri11 encode for cytochrome P450 monooxygenase like proteins. These data also revealed effector-induced allosteric changes on substrate binding at an alternative binding site and showed potential homotropic negative cooperativity. These analyses also showed that their catalytic mechanism relies on protein-ligand and protein-heme interactions controlled by hydrophobic and hydrogen-bonding interactions which orient the complex in optimal conformation within the active sites.

Plug-and-play, infrared, laser-mediated PCR in a microfluidic chip.

PubMed

Pak, Nikita; Saunders, D Curtis; Phaneuf, Christopher R; Forest, Craig R

2012-04-01

Microfluidic polymerase chain reaction (PCR) systems have set milestones for small volume (100 nL-5 μL), amplification speed (100-400 s), and on-chip integration of upstream and downstream sample handling including purification and electrophoretic separation functionality. In practice, the microfluidic chips in these systems require either insertion of thermocouples or calibration prior to every amplification. These factors can offset the speed advantages of microfluidic PCR and have likely hindered commercialization. We present an infrared, laser-mediated, PCR system that features a single calibration, accurate and repeatable precision alignment, and systematic thermal modeling and management for reproducible, open-loop control of PCR in 1 μL chambers of a polymer microfluidic chip. Total cycle time is less than 12 min: 1 min to fill and seal, 10 min to amplify, and 1 min to recover the sample. We describe the design, basis for its operation, and the precision engineering in the system and microfluidic chip. From a single calibration, we demonstrate PCR amplification of a 500 bp amplicon from λ-phage DNA in multiple consecutive trials on the same instrument as well as multiple identical instruments. This simple, relatively low-cost plug-and-play design is thus accessible to persons who may not be skilled in assembly and engineering.

Cutting the wires: modularization of cellular networks for experimental design.

PubMed

Lang, Moritz; Summers, Sean; Stelling, Jörg

2014-01-07

Understanding naturally evolved cellular networks requires the consecutive identification and revision of the interactions between relevant molecular species. In this process, initially often simplified and incomplete networks are extended by integrating new reactions or whole subnetworks to increase consistency between model predictions and new measurement data. However, increased consistency with experimental data alone is not sufficient to show the existence of biomolecular interactions, because the interplay of different potential extensions might lead to overall similar dynamics. Here, we present a graph-based modularization approach to facilitate the design of experiments targeted at independently validating the existence of several potential network extensions. Our method is based on selecting the outputs to measure during an experiment, such that each potential network extension becomes virtually insulated from all others during data analysis. Each output defines a module that only depends on one hypothetical network extension, and all other outputs act as virtual inputs to achieve insulation. Given appropriate experimental time-series measurements of the outputs, our modules can be analyzed, simulated, and compared to the experimental data separately. Our approach exemplifies the close relationship between structural systems identification and modularization, an interplay that promises development of related approaches in the future. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Cationized Carbohydrate Gas-Phase Fragmentation Chemistry

NASA Astrophysics Data System (ADS)

Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.

2017-04-01

We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms . Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

Cross-orientation interactions in human vision.

PubMed

Roeber, Urte; Wong, Elaine M Y; Freeman, Alan W

2008-03-18

Humans can discriminate one visual contour from another on the basis of small differences in orientation. This capability depends on cortical detectors that are selective for a small range of orientations. We have measured this orientation bandwidth and the suppression that helps to shape it, with a reverse correlation technique. Human subjects were presented with a stream of randomly oriented gratings at a rate of 30 per second. Their task was to press a key whenever they saw an orientation nominated as the target. We analyzed the data by finding the probability density of two orientations: One preceded the key-press by the reaction time, and the second preceded the first by up to 100 ms. The results were as follows: (1) One grating facilitated the following one in producing a key-press when the gratings differed little in orientation. The estimate of orientation bandwidth resulting from this facilitation was 38 degrees . (2) A large angle between the two orientations reduced the probability of a key-press. This finding was best modelled as a suppression that did not vary with orientation, consistent with the idea that cross-orientation suppression is non-oriented. (3) Analysis of non-consecutive grating pairs showed that cross-orientation interactions lasted no longer than 67 ms.

Understanding pretest and posttest reactions to cognitive ability and personality tests.

PubMed

Chan, D; Schmitt, N; Sacco, J M; DeShon, R P

1998-06-01

To understand the nature of test reactions and their relationship to test performance, the relationships among belief in tests, pretest reactions, test performance, and posttest reactions were modeled for cognitive ability and personality tests. Results from structural equation models that were fitted to responses from 197 undergraduate examinees supported the hypothesized relationships. On the cognitive ability test, pretest reactions affected test performance and mediated the relationship between belief in tests and test performance. Test performance affected posttest reactions even after taking into account the effect of pretest reactions. On the personality test, belief in tests affected pretest and posttest reactions, but the three variables were unrelated to test performance (Conscientiousness scores). Conceptual, methodological, and practical implications of the findings are discussed in the context of research on test reactions and test performance.

Learned Helplessness: A Model to Understand and Overcome a Child's Extreme Reaction to Failure.

ERIC Educational Resources Information Center

Balk, David

1983-01-01

The author reviews literature on childrens' reactions to perceived failure and offers "learned helplessness" as a model to explain why a child who makes a mistake gives up. Suggestions for preventing these reactions are given. (Author/JMK)

Modeling of molecular nitrogen collisions and dissociation processes for direct simulation Monte Carlo.

PubMed

Parsons, Neal; Levin, Deborah A; van Duin, Adri C T; Zhu, Tong

2014-12-21

The Direct Simulation Monte Carlo (DSMC) method typically used for simulating hypersonic Earth re-entry flows requires accurate total collision cross sections and reaction probabilities. However, total cross sections are often determined from extrapolations of relatively low-temperature viscosity data, so their reliability is unknown for the high temperatures observed in hypersonic flows. Existing DSMC reaction models accurately reproduce experimental equilibrium reaction rates, but the applicability of these rates to the strong thermal nonequilibrium observed in hypersonic shocks is unknown. For hypersonic flows, these modeling issues are particularly relevant for nitrogen, the dominant species of air. To rectify this deficiency, the Molecular Dynamics/Quasi-Classical Trajectories (MD/QCT) method is used to accurately compute collision and reaction cross sections for the N2(Σg+1)-N2(Σg+1) collision pair for conditions expected in hypersonic shocks using a new potential energy surface developed using a ReaxFF fit to recent advanced ab initio calculations. The MD/QCT-computed reaction probabilities were found to exhibit better physical behavior and predict less dissociation than the baseline total collision energy reaction model for strong nonequilibrium conditions expected in a shock. The MD/QCT reaction model compared well with computed equilibrium reaction rates and shock-tube data. In addition, the MD/QCT-computed total cross sections were found to agree well with established variable hard sphere total cross sections.

Surface complexation modeling

USDA-ARS?s Scientific Manuscript database

Adsorption-desorption reactions are important processes that affect the transport of contaminants in the environment. Surface complexation models are chemical models that can account for the effects of variable chemical conditions, such as pH, on adsorption reactions. These models define specific ...

EMPIRE: A Reaction Model Code for Nuclear Astrophysics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palumbo, A., E-mail: apalumbo@bnl.gov; Herman, M.; Capote, R.

The correct modeling of abundances requires knowledge of nuclear cross sections for a variety of neutron, charged particle and γ induced reactions. These involve targets far from stability and are therefore difficult (or currently impossible) to measure. Nuclear reaction theory provides the only way to estimate values of such cross sections. In this paper we present application of the EMPIRE reaction code to nuclear astrophysics. Recent measurements are compared to the calculated cross sections showing consistent agreement for n-, p- and α-induced reactions of strophysical relevance.

Evaluation of Data Used for Modelling the Stratosphere of Saturn

NASA Astrophysics Data System (ADS)

Armstrong, Eleanor Sophie; Irwin, Patrick G. J.; Moses, Julianne I.

2015-11-01

Planetary atmospheres are modeled through the use of a photochemical and kinetic reaction scheme constructed from experimentally and theoretically determined rate coefficients, photoabsorption cross sections and branching ratios for the molecules described within them. The KINETICS architecture has previously been developed to model planetary atmospheres and is applied here to Saturn’s stratosphere. We consider the pathways that comprise the reaction scheme of a current model, and update the reaction scheme according the to findings in a literature investigation. We evaluate contemporary photochemical literature, studying recent data sets of cross-sections and branching ratios for a number of hydrocarbons used in the photochemical scheme of Model C of KINETICS. In particular evaluation of new photodissociation branching ratios for CH4, C2H2, C2H4, C3H3, C3H5 and C4H2, and new cross-sectional data for C2H2, C2H4, C2H6, C3H3, C4H2, C6H2 and C8H2 are considered. By evaluating the techniques used and data sets obtained, a new reaction scheme selection was drawn up. These data are then used within the preferred reaction scheme of the thesis and applied to the KINETICS atmospheric model to produce a model of the stratosphere of Saturn in a steady state. A total output of the preferred reaction scheme is presented, and the data is compared both with the previous reaction scheme and with data from the Cassini spacecraft in orbit around Saturn.One of the key findings of this work is that there is significant change in the model’s output as a result of temperature dependent data determination. Although only shown within the changes to the photochemical portion of the preferred reaction scheme, it is suggested that an equally important temperature dependence will be exhibited in the kinetic section of the reaction scheme. The photochemical model output is shown to be highly dependent on the preferred reaction scheme used within it by this thesis. The importance of correct and temperature-appropriate photochemical and kinetic data for the atmosphere under examination is emphasised as a consequence.

Modeled Neutron Induced Nuclear Reaction Cross Sections for Radiochemsitry in the region of Thulium, Lutetium, and Tantalum I. Results of Built in Spherical Symmetry in a Deformed Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffman, R. D.

2013-09-06

We have developed a set of modeled nuclear reaction cross sections for use in radiochemical diagnostics. Systematics for the input parameters required by the Hauser-Feshbach statistical model were developed and used to calculate neutron induced nuclear reaction cross sections for targets ranging from Terbium (Z = 65) to Rhenium (Z = 75). Of particular interest are the cross sections on Tm, Lu, and Ta including reactions on isomeric targets.

Quantum mechanical study of solvent effects in a prototype S{sub N}2 reaction in solution: Cl{sup −} attack on CH{sub 3}Cl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; York, Darrin M., E-mail: york@biomaps.rutgers.edu

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype S{sub N}2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resultingmore » free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.« less

Quantitative analysis of microbial biomass yield in aerobic bioreactor.

PubMed

Watanabe, Osamu; Isoda, Satoru

2013-12-01

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value-added products such as compost on optimum condition. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl

NASA Astrophysics Data System (ADS)

Kuechler, Erich R.; York, Darrin M.

2014-02-01

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl.

PubMed

Kuechler, Erich R; York, Darrin M

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

Zea mays iRS1563: A Comprehensive Genome-Scale Metabolic Reconstruction of Maize Metabolism

PubMed Central

Saha, Rajib; Suthers, Patrick F.; Maranas, Costas D.

2011-01-01

The scope and breadth of genome-scale metabolic reconstructions have continued to expand over the last decade. Herein, we introduce a genome-scale model for a plant with direct applications to food and bioenergy production (i.e., maize). Maize annotation is still underway, which introduces significant challenges in the association of metabolic functions to genes. The developed model is designed to meet rigorous standards on gene-protein-reaction (GPR) associations, elementally and charged balanced reactions and a biomass reaction abstracting the relative contribution of all biomass constituents. The metabolic network contains 1,563 genes and 1,825 metabolites involved in 1,985 reactions from primary and secondary maize metabolism. For approximately 42% of the reactions direct literature evidence for the participation of the reaction in maize was found. As many as 445 reactions and 369 metabolites are unique to the maize model compared to the AraGEM model for A. thaliana. 674 metabolites and 893 reactions are present in Zea mays iRS1563 that are not accounted for in maize C4GEM. All reactions are elementally and charged balanced and localized into six different compartments (i.e., cytoplasm, mitochondrion, plastid, peroxisome, vacuole and extracellular). GPR associations are also established based on the functional annotation information and homology prediction accounting for monofunctional, multifunctional and multimeric proteins, isozymes and protein complexes. We describe results from performing flux balance analysis under different physiological conditions, (i.e., photosynthesis, photorespiration and respiration) of a C4 plant and also explore model predictions against experimental observations for two naturally occurring mutants (i.e., bm1 and bm3). The developed model corresponds to the largest and more complete to-date effort at cataloguing metabolism for a plant species. PMID:21755001

13C metabolic flux analysis at a genome-scale.

PubMed

Gopalakrishnan, Saratram; Maranas, Costas D

2015-11-01

Metabolic models used in 13C metabolic flux analysis generally include a limited number of reactions primarily from central metabolism. They typically omit degradation pathways, complete cofactor balances, and atom transition contributions for reactions outside central metabolism. This study addresses the impact on prediction fidelity of scaling-up mapping models to a genome-scale. The core mapping model employed in this study accounts for (75 reactions and 65 metabolites) primarily from central metabolism. The genome-scale metabolic mapping model (GSMM) (697 reaction and 595 metabolites) is constructed using as a basis the iAF1260 model upon eliminating reactions guaranteed not to carry flux based on growth and fermentation data for a minimal glucose growth medium. Labeling data for 17 amino acid fragments obtained from cells fed with glucose labeled at the second carbon was used to obtain fluxes and ranges. Metabolic fluxes and confidence intervals are estimated, for both core and genome-scale mapping models, by minimizing the sum of square of differences between predicted and experimentally measured labeling patterns using the EMU decomposition algorithm. Overall, we find that both topology and estimated values of the metabolic fluxes remain largely consistent between core and GSM model. Stepping up to a genome-scale mapping model leads to wider flux inference ranges for 20 key reactions present in the core model. The glycolysis flux range doubles due to the possibility of active gluconeogenesis, the TCA flux range expanded by 80% due to the availability of a bypass through arginine consistent with labeling data, and the transhydrogenase reaction flux was essentially unresolved due to the presence of as many as five routes for the inter-conversion of NADPH to NADH afforded by the genome-scale model. By globally accounting for ATP demands in the GSMM model the unused ATP decreased drastically with the lower bound matching the maintenance ATP requirement. A non-zero flux for the arginine degradation pathway was identified to meet biomass precursor demands as detailed in the iAF1260 model. Inferred ranges for 81% of the reactions in the genome-scale metabolic (GSM) model varied less than one-tenth of the basis glucose uptake rate (95% confidence test). This is because as many as 411 reactions in the GSM are growth coupled meaning that the single measurement of biomass formation rate locks the reaction flux values. This implies that accurate biomass formation rate and composition are critical for resolving metabolic fluxes away from central metabolism and suggests the importance of biomass composition (re)assessment under different genetic and environmental backgrounds. In addition, the loss of information associated with mapping fluxes from MFA on a core model to a GSM model is quantified. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Interplay between inhibited transport and reaction in nanoporous materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ackerman, David Michael

2013-01-01

This work presents a detailed formulation of reaction and diffusion dynamics of molecules in confined pores such as mesoporous silica and zeolites. A general reaction-diffusion model and discrete Monte Carlo simulations are presented. Both transient and steady state behavior is covered. Failure of previous mean-field models for these systems is explained and discussed. A coarse-grained, generalized hydrodynamic model is developed that accurately captures the interplay between reaction and restricted transport in these systems. This method incorporates the non-uniform chemical diffusion behavior present in finite pores with multi-component diffusion. Two methods of calculating these diffusion values are developed: a random walkmore » based approach and a driven diffusion model based on an extension of Fick's law. The effects of reaction, diffusion, pore length, and catalytic site distribution are investigated. In addition to strictly single file motion, quasi-single file diffusion is incorporated into the model to match a range of experimental systems. The connection between these experimental systems and model parameters is made through Langevin dynamics modeling of particles in confined pores.« less

Effect of Jian-Pi-Zhi-Dong Decoction on striatal glutamate and γ-aminobutyric acid levels detected using microdialysis in a rat model of Tourette syndrome

PubMed Central

Zhang, Wen; Wei, Li; Yu, Wenjing; Cui, Xia; Liu, Xiaofang; Wang, Qian; Wang, Sumei

2016-01-01

Background Jian-Pi-Zhi-Dong Decoction (JPZDD) is a dedicated treatment of Tourette syndrome (TS). The balance of neurotransmitters in the cortico-striato-pallido-thalamo-cortical network is crucial to the occurrence of TS and related to its severity. This study evaluated the effect of JPZDD on glutamate (Glu) and γ-aminobutyric acid (GABA) and their receptors in a TS rat model. Materials and methods Rats were divided into four groups (n=12 each). TS was induced in three of the groups by injecting them with 3,3′-iminodipropionitrile for 7 consecutive days. Two model groups were treated with tiapride (Tia) or JPZDD, while the control and the remaining model group were gavaged with saline. Behavior was assessed by stereotypic score and autonomic activity. Striatal Glu and GABA contents were detected using microdialysis. Expressions of N-methyl-D-aspartate receptor 1 and GABAA receptor (GABAAR) were observed using Western blot and real-time polymerase chain reaction. Results Tia and JPZDD groups had decreased stereotypy compared with model rats; however, the JPZDD group showed a larger decrease in stereotypy than the Tia group at a 4-week time point. In a spontaneous activity test, the total distance of the JPZDD and Tia groups was significantly decreased compared with the model group. The Glu levels of the model group were higher than the control group and decreased with Tia or JPZDD treatment. The GABA level was higher in the model group than the control group. Expressions of GABAAR protein in the model group were higher than in the control group. Treatment with Tia or JPZDD reduced the expression of GABAAR protein. In the case of the mRNA expression, only Tia reduced the expression of N-methyl-D-aspartate receptor 1, compared with the model group. Conclusion JPZDD could alleviate impairments in behavior and dysfunctional signaling by downregulating GABAAR in the striatum. We suggest that this acts to maintain the balance of Glu and GABA. PMID:27279743

Desensitizing Children's Emotional Reactions to the Mass Media.

ERIC Educational Resources Information Center

Wilson, Barbara J.

1989-01-01

Assesses effectiveness of two desensitization strategies for reducing children's emotional reactions to mass media. Examines children having passive exposure, modeled exposure, or no exposure to lizards before watching a horror movie involving lizards. Finds that modeled exposure decreases emotional reactions and negative interpretations, whereas…

Unraveling reaction pathways and specifying reaction kinetics for complex systems.

PubMed

Vinu, R; Broadbelt, Linda J

2012-01-01

Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed.

Water Quality, Cyanobacteria, and Environmental Factors and Their Relations to Microcystin Concentrations for Use in Predictive Models at Ohio Lake Erie and Inland Lake Recreational Sites, 2013-14

USGS Publications Warehouse

Francy, Donna S.; Graham, Jennifer L.; Stelzer, Erin A.; Ecker, Christopher D.; Brady, Amie M. G.; Pam Struffolino,; Loftin, Keith A.

2015-11-06

The results of this study showed that water-quality and environmental variables are promising for use in site-specific daily or long-term predictive models. In order to develop more accurate models to predict toxin concentrations at freshwater lake sites, data need to be collected more frequently and for consecutive days in future studies.

Understanding baseball team standings and streaks

NASA Astrophysics Data System (ADS)

Sire, C.; Redner, S.

2009-02-01

Can one understand the statistics of wins and losses of baseball teams? Are their consecutive-game winning and losing streaks self-reinforcing or can they be described statistically? We apply the Bradley-Terry model, which incorporates the heterogeneity of team strengths in a minimalist way, to answer these questions. Excellent agreement is found between the predictions of the Bradley-Terry model and the rank dependence of the average number team wins and losses in major-league baseball over the past century when the distribution of team strengths is taken to be uniformly distributed over a finite range. Using this uniform strength distribution, we also find very good agreement between model predictions and the observed distribution of consecutive-game team winning and losing streaks over the last half-century; however, the agreement is less good for the previous half-century. The behavior of the last half-century supports the hypothesis that long streaks are primarily statistical in origin with little self-reinforcing component. The data further show that the past half-century of baseball has been more competitive than the preceding half-century.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mondy, Lisa Ann; Rao, Rekha Ranjana; Shelden, Bion

We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane foam, PMDI. The polyurethane of interest is chemically blown, where carbon dioxide is produced via the reaction of water, the blowing agent, and isocyanate. The isocyanate also reacts with polyol in a competing reaction, which produces the polymer. Here we detail the experiments needed to populate a processing model and provide parameters for the model based on these experiments. The model entails solving the conservation equations, including the equations of motion, an energy balance, and two rate equations for the polymerization and foaming reactions,more » following a simplified mathematical formalism that decouples these two reactions. Parameters for the polymerization kinetics model are reported based on infrared spectrophotometry. Parameters describing the gas generating reaction are reported based on measurements of volume, temperature and pressure evolution with time. A foam rheology model is proposed and parameters determined through steady-shear and oscillatory tests. Heat of reaction and heat capacity are determined through differential scanning calorimetry. Thermal conductivity of the foam as a function of density is measured using a transient method based on the theory of the transient plane source technique. Finally, density variations of the resulting solid foam in several simple geometries are directly measured by sectioning and sampling mass, as well as through x-ray computed tomography. These density measurements will be useful for model validation once the complete model is implemented in an engineering code.« less

Mathematical model to predict drivers' reaction speeds.

PubMed

Long, Benjamin L; Gillespie, A Isabella; Tanaka, Martin L

2012-02-01

Mental distractions and physical impairments can increase the risk of accidents by affecting a driver's ability to control the vehicle. In this article, we developed a linear mathematical model that can be used to quantitatively predict drivers' performance over a variety of possible driving conditions. Predictions were not limited only to conditions tested, but also included linear combinations of these tests conditions. Two groups of 12 participants were evaluated using a custom drivers' reaction speed testing device to evaluate the effect of cell phone talking, texting, and a fixed knee brace on the components of drivers' reaction speed. Cognitive reaction time was found to increase by 24% for cell phone talking and 74% for texting. The fixed knee brace increased musculoskeletal reaction time by 24%. These experimental data were used to develop a mathematical model to predict reaction speed for an untested condition, talking on a cell phone with a fixed knee brace. The model was verified by comparing the predicted reaction speed to measured experimental values from an independent test. The model predicted full braking time within 3% of the measured value. Although only a few influential conditions were evaluated, we present a general approach that can be expanded to include other types of distractions, impairments, and environmental conditions.

Chemical Memory Reactions Induced Bursting Dynamics in Gene Expression

PubMed Central

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems. PMID:23349679

Chemical memory reactions induced bursting dynamics in gene expression.

PubMed

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

Negative illness perceptions associated with low mental and physical health status in general hospital outpatients in China.

PubMed

Wu, Heng; Zhao, Xudong; Fritzsche, Kurt; Salm, Florian; Leonhart, Rainer; Jing, Wei; Yang, Jianzhong; Schaefert, Rainer

2014-01-01

In western countries, negative illness perceptions are associated with poor health status and affect health outcomes in primary care populations. The aim of this study is to examine the relationship between illness perception and mental and physical health status in general hospital outpatients in China. This multicentre, cross-sectional study analysed a total of 281 consecutive patients from four general hospital outpatient departments of internal medicine and traditional Chinese medicine in Beijing and Kunming. The patients answered questionnaires concerning illness perception (Brief-IPQ), somatic symptom severity (Patient Health Questionnaire-15), illness behaviour (Scale for the Assessment of Illness Behaviour), emotional distress (Hospital Anxiety and Depression Scale) and health-related quality of life (Twelve-Item Short Form Health Survey). Negative illness perception, especially negative emotional reactions, perceived illness consequences, encumbering illness concerns, and strong illness identity were significantly associated with high emotional distress, impairing illness consequences, and a low mental and physical quality of life. Using a multiple linear regression model, five strongest correlates of negative illness perception were high anxiety, seeking diagnosis verification, low mental and physical quality of life and high somatic symptom severity. The variance explained by this model was 35%. Chinese general hospital outpatients showed associations between negative illness perceptions and poor mental and physical health status that were similar to those of primary care patients in western countries. The main difference was that no association with perceived illness control was found in Chinese patients. Chinese physicians should be sensitised to their patients' negative illness perceptions and should focus on helping patients cope with uncertainty and anxiety by providing an understandable illness model and increasing control beliefs.