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Sample records for myoglobin protein-centered radicals

  1. A hydrogen-donating monohydroxamate scavenges ferryl myoglobin radicals

    DEFF Research Database (Denmark)

    Cooper, C E; Green, E S; Rice-Evans, C A

    1994-01-01

    The addition of 25 microM hydrogen peroxide to 20 microM metmyoglobin produces ferryl (FeIV = O) myoglobin. Optical spectroscopy shows that the ferryl species reaches a maximum concentration (60-70% of total haem) after 10 minutes and decays slowly (hours). Low temperature EPR spectroscopy of the...

  2. Efficient reduction of Cys110 thiyl radical by glutathione in human myoglobin

    OpenAIRE

    Nagao, Satoshi; Asami, Osamu; Yasui, Hiroyuki; Hirota, Shun

    2011-01-01

    Human myoglobin (hMb) possesses a cysteine (Cys) residue which is rare among mammalian Mbs. To investigate the effects of this unique Cys residue at the amino acid position 110 (Cys110) on hMb reactions, we studied the reactions of wild type (WT) methMb and its alanine mutant at Cys110 (C110A) with H2O2, particularly in the presence of reduced glutathione (GSH) which is well known as a reducing agent. The formation rates of the ferryloxo (Fe(IV) = O) species by H2O2 under air were about the s...

  3. Myoglobin urine test

    Science.gov (United States)

    Urine myoglobin; Heart attack - myoglobin urine test; Myositis - myoglobin urine test; Rhabdomyolysis - myoglobin urine test ... The test involves only normal urination, which should cause no discomfort.

  4. Interaction of radiation-generated radicals with myoglobin in aqueous solution

    International Nuclear Information System (INIS)

    Whitburn, K.D.; Hoffman, M.Z.

    1985-01-01

    The γ-radiolysis of aqueous solutions of ferrimyoglobin in the presence of N 2 O at pH 7.3 has been examined as a function of added catalase and oxygen. Changes in the nature of the heme group have been monitored by visible absorption spectrophotometry and analysed quantitatively by a multiple wavelength method based on Beer's Law. Simple chemical analyses have been used to confirm qualitative identification of the product derivatives. As observed previously, the ferriheme is reduced by indirect globin-mediated action initiated by radical OH/H radical. The yield of reduced product decreases as [O 2 ] derived from irradiated water and from protein-mediated processes in oxygenated solution, is eliminated by the presence of catalase. Formation of a hemichrome form of ferrimyoglobin is apparent at higher doses in the presence of O 2 . These results demonstrate that oxygen plays an important role in controlling the nature and extent of redox that manifests ultimately on the heme group of ferrimyoglobin as a result of the initial interaction of radical OH/H radical. (author)

  5. Interaction of radiation-generated radicals with myoglobin in aqueous solution

    International Nuclear Information System (INIS)

    Whitburn, K.D.; Hoffman, M.Z.

    1984-01-01

    The interaction of radiation-generated OH/H with oxymyoglobin (MbO 2 ) has been studied in the presence of catalase at pH 7.3 over the range of 5 to 510 μM O 2 . The conversion of MbO 2 to heme-modified products has been examined under conditions where depletion of O 2 in irradiated solutions both can and cannot be compensated by O 2 -transfer across the solution phase boundary. In the theoretical limit of [O 2 ] -> 0 in bulk solution, MbO 2 is converted stoichiometrically to ferri- and ferromyoglobin with G(-MbO 2 ) approx.= 6.0, G(ferroMb) approx.3.0, and G(ferriMb) approx.= 3.0. An increase in [O 2 ] in bulk solution beyond the zero-limit progressively suppresses the conversion of MbO 2 to the heme-modified derivatives. At [O 2 ] >300 μM, an O 2 -independent path of ferriMb formation with G approx.= 0.6 is evident. Two sources of ferriMb induced by OH/H are proposed: an O 2 -independent path involving direct oxidative attack of OH at the oxyferroheme, and O 2 -dependent paths of production of ferriMb and ferroMb involving the mediation of O 2 -scavengeable secondary hemeprotein radicals. It is suggested that the modifications of the heme group in the absence of O 2 are accompanied by redox modifications on the globin moiety. (author)

  6. Myoglobin blood test

    Science.gov (United States)

    Serum myoglobin; Heart attack - myoglobin blood test; Myositis - myoglobin blood test; Rhabdomyolysis - myoglobin blood test ... too high, it can damage the kidneys. This test is ordered when your health care provider suspects ...

  7. Myoglobin chemistry and meat color.

    Science.gov (United States)

    Suman, Surendranath P; Joseph, Poulson

    2013-01-01

    Consumers rely heavily on fresh meat color as an indicator of wholesomeness at the point of sale, whereas cooked color is exploited as an indicator of doneness at the point of consumption. Deviations from the bright cherry-red color of fresh meat lead to product rejection and revenue loss. Myoglobin is the sarcoplasmic heme protein primarily responsible for the meat color, and the chemistry of myoglobin is species specific. The mechanistic interactions between myoglobin and multiple extrinsic and intrinsic factors govern the color of raw as well as cooked meats. The objective of this review is to provide an overview of the current research in meat color and how the findings are applied in the meat industry. Characterizing the fundamental basis of myoglobin's interactions with biomolecules in postmortem skeletal muscles is necessary to interpret the chemistry of meat color phenomena and to engineer innovative processing strategies to minimize meat discoloration-induced revenue loss to the agricultural economy.

  8. Radioimmunoassay for human myoglobin

    International Nuclear Information System (INIS)

    Kondo, Akira

    1981-01-01

    1 A new radioimmunoassay (RIA) for human myoglobin (Mb) using two antibody technique was developed as a microassay of Mb. This RIA is characterized as follows; 1) Radioiodination of human Mb was successfully done for the first time by chloramine T method, which yielded Iabelled Mb with high specific activities ranging 40 - 60 μCi/μg. 2) Affinity chromatography was used to obtain purified anti-human Mb antibody, which improved the sensitivity of the RIA remarkably, and excluded the effects of serum and urine. 2 The sensitivity of the RIA was 1 ng/ml in sera and 2 ng/ml in urine. The average recovery was 92.7%. Both intra-assay and inter-assay coefficients of variation were below 10%. 3 With this method, Mb purified from skeletal and cardiac muscles was shown to have same immunological nature. 4 Serum concentrations of Mb in normal adults were 13.1 +- 6.1 ng/ml (mean +- S.D.) with a range of 1 - 28 ng/ml. No sex difference was observed. Urinary Mb Ievels in normal adults were less than 4 ng/ml and 24-hour urinary excretions were less than 6 μg. With this method, serum and urinary Mb concentrations were determined in patients with various disorders such as myopathies and myocardial disorders and with anesthesia. Serum Mb concentrations were revealed to be elevated to 50000 ng/ml in malignant hyperthermia, 4000 ng/ml in acute myocardial infarction, 1000 ng/ml in Duchenne muscular dystrophy and 4000 ng/ml in polymyositis. Urinary Mb level was elevated when serum Mb rose to 2000 - 3000 ng/ml. 5 In order to apply RIA of Mb in daily clinical practices, time needed for the assay was shortened by separation of free and antibody-bound Mb by the polyethylene glycol method immediately after incubation was performed at 37 0 C for 2 hours. (author)

  9. Radioimmunoassay for human myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, A. (Tokushima Univ. (Japan). School of Medicine)

    1981-04-01

    1 A new radioimmunoassay (RIA) for human myoglobin (Mb) using two antibody technique was developed as a microassay of Mb. This RIA is characterized as follows; 1) Radioiodination of human Mb was successfully done for the first time by chloramine T method, which yielded Iabelled Mb with high specific activities ranging 40 - 60 ..mu..Ci/..mu..g. 2) Affinity chromatography was used to obtain purified anti-human Mb antibody, which improved the sensitivity of the RIA remarkably, and excluded the effects of serum and urine. 2 The sensitivity of the RIA was 1 ng/ml in sera and 2 ng/ml in urine. The average recovery was 92.7%. Both intra-assay and inter-assay coefficients of variation were below 10%. 3 With this method, Mb purified from skeletal and cardiac muscles was shown to have same immunological nature. 4 Serum concentrations of Mb in normal adults were 13.1 +- 6.1 ng/ml (mean +- S.D.) with a range of 1 - 28 ng/ml. No sex difference was observed. Urinary Mb Ievels in normal adults were less than 4 ng/ml and 24-hour urinary excretions were less than 6 ..mu..g. With this method, serum and urinary Mb concentrations were determined in patients with various disorders such as myopathies and myocardial disorders and with anesthesia. Serum Mb concentrations were revealed to be elevated to 50000 ng/ml in malignant hyperthermia, 4000 ng/ml in acute myocardial infarction, 1000 ng/ml in Duchenne muscular dystrophy and 4000 ng/ml in polymyositis. Urinary Mb level was elevated when serum Mb rose to 2000 - 3000 ng/ml. 5 In order to apply RIA of Mb in daily clinical practices, time needed for the assay was shortened by separation of free and antibody-bound Mb by the polyethylene glycol method immediately after incubation was performed at 37/sup 0/C for 2 hours.

  10. Radioimmunoassay of serum myoglobin in neuromuscular diseases

    Energy Technology Data Exchange (ETDEWEB)

    Askmark, H; Osterman, P O; Roxin, L E; Venge, P [University Hospital, Uppsala (Sweden)

    1981-01-01

    Radioimmunoassay of serum myoglobin was performed in 85 patients with muscular symptoms. Elevated levels were found in 93% of patients with myogenic myopathy, in 54% with myasthenia gravis and in 50% with neurogenic myopathy. All 11 patients with polymyositis had elevated myoglobin concentrations. In six of seven patients with polymyositis, who were followed up with repeated determinations, a clear relationship between myoglobin levels and clinical course was found. In general serum myoglobin seemed to be a more sensitive indicator of muscle disease than creatine kinase.

  11. Radioimmunoassay of serum myoglobin in neuromuscular diseases

    International Nuclear Information System (INIS)

    Askmark, H.; Osterman, P.O.; Roxin, L.-E.; Venge, P.

    1981-01-01

    Radioimmunoassay of serum myoglobin was performed in 85 patients with muscular symptoms. Elevated levels were found in 93% of patients with myogenic myopathy, in 54% with myasthenia gravis and in 50% with neurogenic myopathy. All 11 patients with polymyositis had elevated myoglobin concentrations. In six of seven patients with polymyositis, who were followed up with repeated determinations, a clear relationship between myoglobin levels and clinical course was found. In general serum myoglobin seemed to be a more sensitive indicator of muscle disease than creatine kinase. (author)

  12. Expression and Purification of Sperm Whale Myoglobin

    Science.gov (United States)

    Miller, Stephen; Indivero, Virginia; Burkhard, Caroline

    2010-01-01

    We present a multiweek laboratory exercise that exposes students to the fundamental techniques of bacterial expression and protein purification through the preparation of sperm whale myoglobin. Myoglobin, a robust oxygen-binding protein, contains a single heme that gives the protein a reddish color, making it an ideal subject for the teaching…

  13. Riboflavin photosensitized oxidation of myoglobin.

    Science.gov (United States)

    Grippa, Juliana M; de Zawadzki, Andressa; Grossi, Alberto B; Skibsted, Leif H; Cardoso, Daniel R

    2014-02-05

    The reaction of the fresh meat pigment oxymyoglobin, MbFe(II)O₂, and its oxidized form metmyoglobin, MbFe(III), with triplet-state riboflavin involves the pigment protein, which is oxidatively cleaved or dimerized as shown by SDS-PAGE and Western blotting. The overall rate constant for oxidation of MbFe(II)O₂ by ³Rib is (3.0 ± 0.5) × 10⁹ L·mol⁻¹·s⁻¹ and (3.1 ± 0.4) × 10⁹ L·mol⁻¹·s⁻¹ for MbFe(III) in phosphate buffer of pH 7.4 at 25 °C as determined by laser flash photolysis. The high rates are rationalized by ground state hydrophobic interactions as detected as static quenching of fluorescence from singlet-excited state riboflavin by myoglobins using time-resolved fluorescence spectroscopy and a Stern-Volmer approach. Binding of riboflavin to MbFe(III) has K(a) = (1.2 ± 0.2) × 10⁴ mol·L⁻¹ with ΔH° = -112 ± 22 kJ·mol⁻¹ and ΔS° = -296 ± 75 J·mol⁻¹·K⁻¹. For meat, riboflavin is concluded to be a photosensitizer for protein oxidation but not for discoloration.

  14. Myoglobin production in emperor penguins.

    Science.gov (United States)

    Ponganis, P J; Welch, T J; Welch, L S; Stockard, T K

    2010-06-01

    Increased oxygen storage is essential to the diving capacities of marine mammals and seabirds. However, the molecular mechanisms underlying this adaptation are unknown. Myoglobin (Mb) and Mb mRNA concentrations were analyzed in emperor penguin (Aptenodytes forsteri) adults and chicks with spectrophotometric and RNase protection assays to evaluate production of their large Mb-bound O(2) stores. Mean pectoral Mb concentration and Mb mRNA content increased throughout the pre-fledging period and were 15-fold and 3-fold greater, respectively, in adults than in 3.5 month old chicks. Mean Mb concentration in 5.9 month old juveniles was 2.7+/-0.4 g 100 g(-1) muscle (44% that of wild adults), and in adults that had been captive all their lives it was 3.7+/-0.1 g 100 g(-1) muscle. The Mb and Mb mRNA data are consistent with regulation of Mb production at the level of transcription as in other animals. Significant Mb and Mb mRNA production occurred in chicks and young juveniles even without any diving activity. The further increase in adult Mb concentrations appears to require the exercise/hypoxia of diving because Mb concentration in captive, non-diving adults only reached 60% of that of wild adults. The much greater relative increase in Mb concentration than in Mb mRNA content between young chicks and adults suggests that there is not a simple 1:1 relationship between Mb mRNA content and Mb concentration. Nutritional limitation in young chicks and post-transcriptional regulation of Mb concentration may also be involved.

  15. Myoglobins: the link between discoloration and lipid oxidation in muscle and meat

    Directory of Open Access Journals (Sweden)

    Jens K. S. Møller

    2006-12-01

    Full Text Available Aerobic metabolism changes rapidly to glycolysis post-mortem resulting in a pH-decrease during the transformation of muscle in to meat affecting ligand binding and redox potential of the heme iron in myoglobin, the meat pigment. The "inorganic chemistry" of meat involves (i redox-cycling between iron(II, iron(III, and iron(IV/protein radicals; (ii ligand exchange processes; and (iii spin-equilibra with a change in coordination number for the heme iron. In addition to the function of myoglobin for oxygen storage, new physiological roles of myoglobin are currently being discovered, which notably find close parallels in the processes in fresh meat and nitrite-cured meat products. Myoglobin may be characterized as a bioreactor for small molecules like O2, NO, CO, CO2, H2O, and HNO with importance in bio-regulation and in protection against oxidative stress in vivo otherwise affecting lipids in membranes. Many of these processes may be recognised as colour changes in fresh meat and cured meat products under different atmospheric conditions, and could also be instructive for teaching purposes.

  16. Myocardial myoglobin release after acute myocardial infarction

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, P S; Saltissi, S; Coltart, D J; Croft, D N [Saint Thomas' Hospital, London (UK)

    1980-03-01

    The magnitude and time course of myoglobin release from the myocardium following infarction was assessed by radioimmunoassay. The assay showed acceptable precision over a working range from 50 to 750 ng cm/sup -3/, provided careful control of the assay temperature was maintained. The use of this radioimmunoassay as an early diagnostic test for infarction and as a potential measure of the extent of necrosis is considered and comparison made with the release of CK-MB, the myocardial specific isoenzyme of creatine kinase. Of the twenty patients studied with myocardial infarction, all had elevated levels of serum myoglobin including those admitted within 3 hours of the onset of pain. In contrast, CK-MB was not detected in the serum within 5 hours of the onset of pain. Peak serum levels of myoglobin (mean 852 +- 365 ng cm/sup -3/) and CK-MB (mean 71 +- 25 mIU cm/sup -3/) were detected at 8-16 hours and 20-24 hours respectively after the onset of pain. A comparison of peak serum levels of myoglobin and CK-MB showed a good correlation (r = 0.84).

  17. Conformational change of spin labelled myoglobin

    International Nuclear Information System (INIS)

    Wajnberg, E.; Ribeiro, P.C.; Nascimento, O.R.; Bemski, G.

    1978-01-01

    A conformational change of spin labelled myoglobin have been followed by measuring the spin label's (isothiocyanate) correlation time for temperatures between 18 0 C and 44 0 C. The correlation time was calculated from Electrom Paramagnetic Ressonance Spectra using the components of the espectroscopic and hiperfine tensors obtained by fitting the powder spectra using Lefebvre and Maruani's program- [pt

  18. Clinical usefulness of radioimmune measurement of serum myoglobin

    International Nuclear Information System (INIS)

    Ruibal, A.; Sabria, M.; Rey, C.; Fraile, M.; Foz, M.; Domenech-Torne, F.M.

    1983-01-01

    In order to ascertain the behaviour in different muscular diseases, as well as its potential clinical usefulness, we have determined by radioimmunoassay the seric levels of myoglobin in 212 patients with different muscular diseases. Our results led us to the following: 1) The myoglobin determination is an early marker and very useful during the first 24 hours in I.A.M.; 2) The myoglobin determination is useful in diagnostic of Duchenne's and Steinert's disease; 3) In healthy carriers of Duchenne's disease and limb-girdle myopathy, total CK was better than myoglobin as a biochemical marker; 4) Higher increases of seric myoglobin were shown in non-trained subjects after exercice. Then, the myoglobin determination may become a wide field of application for sport medicine

  19. The zinc-myoglobin relationships in porcine muscles

    International Nuclear Information System (INIS)

    Fogd Joergensen, P.; Wegger, I.

    1976-01-01

    Zinc and myoglobin content in muscles from pigs were studied under various conditions. Zinc concentration was considerably higher in red than in white muscles. In muscles, where the metabolic pattern changes from glycolytic to oxidative during the period from birth to weaning, a simultaneous increase in zinc content was seen. A significant positive correlation exists between myoglobin and zinc content under normal conditions. However, while myoglobin concentration decreases due to iron deficiency anaemia no changes occur in zinc content. It is concluded that no functional link seems to exist between zinc metabolism and myoglobin synthesis in porcine muscles. (author)

  20. The role of myoglobin degradation in nephrotoxicity after rhabdomyolysis.

    Science.gov (United States)

    Zorova, Ljubava D; Pevzner, Irina B; Chupyrkina, Anastasia A; Zorov, Savva D; Silachev, Denis N; Plotnikov, Egor Y; Zorov, Dmitry B

    2016-08-25

    The fate of myoglobin in renal cells was explored in an animal model of rhabdomyolysis known as the pathology highly related to oxidative stress resulting in impairment of renal functioning. The working hypothesis was that the proper degradation of myoglobin in rhabdomyolytic kidney can activate the reparative processes in the tissue. We found that incubation of myoglobin with kidney cells causes its accumulation in the cytoplasm. In rhabdomyolytic rats, the level of heme and free iron in cytoplasm and mitochondria of kidney cells is remarkably increased while inhibition of proteolysis results in further elevation of myoglobin content in the renal tissue. Heme oxygenase and ferritin levels were found to be increased in the kidney tissue at rhabdomyolysis and simulating conditions performed by i/v injection of myoglobin. In addition, the level of peroxidized lipids was high in rhabdomyolytic kidney and became even higher after inhibition of proteolysis by aprotinin. Elevated levels of carbonylated proteins were also observed after rhabdomyolysis, however, if prior to induction of rhabdomyolysis the injection of myoglobin was done, the level of carbonylated proteins dropped versus unprimed kidney tissue thus affording protection to the kidney against oxidative stress. Injection of myoglobin to the rat results in impairment of renal functioning and inhibition of myoglobin degradation in the rhabdomyolytic animal aggravates acute renal failure, demonstrating that degradation of myoglobin is somehow beneficial although it may result in undesired release of free iron which can participate in toxic redox cycling. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  1. Diagnostic strategies using myoglobin measurement in myocardial infarction.

    Science.gov (United States)

    Plebani, M; Zaninotto, M

    1998-04-06

    Myoglobin, a low molecular-weight heme protein (17800 D) present in both cardiac and skeletal muscle, is an old test with new perspectives. Advantages and disadvantages of myoglobin determination are well known. Myoglobin is the earliest known, commercially available, biochemical marker of acute myocardial infarction (AMI) and its rapid kinetics make it an early, good marker of reperfusion. However, since myoglobin is present in both skeletal and cardiac muscle, any damage to these muscle types results in its release into blood. Serum myoglobin levels are falsely elevated in conditions unrelated to AMI as skeletal muscle and neuromuscular disorders, renal failure, intramuscular injection, strenuous exercise, and after several toxins and drugs intake. New strategies for myoglobin measurement may resolve this limitation. These strategies include both the combined measurement of myoglobin and a skeletal specific marker (carbonic anhydrase III) or a cardiac specific marker (troponin I), as well as the myoglobin evaluation on serial samples. In particular, the diagnostic algorithm based on the combined measurement of myoglobin and troponin I, assuring a satisfactory analytical turnaround time, significantly improves the diagnostic efficiency of laboratory assessment of suspected AMI patients, allowing the successive monitoring of coronary reperfusion.

  2. Microcontact imprinted surface plasmon resonance sensor for myoglobin detection

    International Nuclear Information System (INIS)

    Osman, Bilgen; Uzun, Lokman; Beşirli, Necati; Denizli, Adil

    2013-01-01

    In this study, we prepared surface plasmon resonance (SPR) sensor using the molecular imprinting technique for myoglobin detection in human serum. For this purpose, we synthesized myoglobin imprinted poly(hydroxyethyl methacrylate-N-methacryloyl-L-tryptophan methyl ester) [poly(HEMA-MATrp)] nanofilm on the surface of SPR sensor. We also synthesized non-imprinted poly(HEMA-MATrp) nanofilm without myoglobin for the control experiments. The SPR sensor was characterized with contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, and ellipsometry. We investigated the effectiveness of the sensor using the SPR system. We evaluated the ability of SPR sensor to sense myoglobin with myoglobin solutions (pH 7.4, phosphate buffer) in different concentration range and in the serum taken from a patient with acute myocardial infarction. We found that the Langmuir adsorption model was the most suitable for the sensor system. The detection limit was 87.6 ng/mL. In order to show the selectivity of the SPR sensor, we investigated the competitive detection of myoglobin, lysozyme, cytochrome c and bovine serum albumin. The results showed that the SPR sensor has high selectivity and sensitivity for myoglobin. - Highlights: • Micro-contact imprinted surface plasmon resonance sensor. • Real-time myoglobin detection in the serum taken from a patient with acute myocardial infarction • Reproducible results for consecutive myoglobin solution supplement • LOD and LOQ values of the SPR sensor were determined to be 26.3 and 87.6 ng/mL. • The SPR sensor has potential for myoglobin sensing during acute MI cases

  3. Myoglobin solvent structure at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Daniels, B.V.; Korszun, Z.R. [Brookhaven National Laboratory, Upton, NY (United States); Schoenborn, B.P. [Los Alamos National Laboratory, NM (United States)

    1994-12-31

    The structure of the solvent surrounding myoglobin crystals has been analyzed using neutron diffraction data, and the results indicate that the water around the protein is not disordered, but rather lies in well-defined hydration shells. We have analyzed the structure of the solvent surrounding the protein by collecting neutron diffraction data at four different temperatures, namely, 80, 130, 180, and 240K. Relative Wilson Statistics applied to low resolution data showed evidence of a phase transition in the region of 180K. A plot of the liquidity factor, B{sub sn}, versus distance from the protein surface begins with a high plateau near the surface of the protein and drops to two minima at distances from the protein surface of about 2.35{Angstrom} and 3.85{Angstrom}. Two distinct hydration shells are observed. Both hydration shells are observed to expand as the temperature is increased.

  4. Myoglobin-Catalyzed Olefination of Aldehydes.

    Science.gov (United States)

    Tyagi, Vikas; Fasan, Rudi

    2016-02-12

    The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Myoglobin solvent structure at different temperatures

    International Nuclear Information System (INIS)

    Daniels, B.V.; Korszun, Z.R.; Schoenborn, B.P.

    1994-01-01

    The structure of the solvent surrounding myoglobin crystals has been analyzed using neutron diffraction data, and the results indicate that the water around the protein is not disordered, but rather lies in well-defined hydration shells. We have analyzed the structure of the solvent surrounding the protein by collecting neutron diffraction data at four different temperatures, namely, 80, 130, 180, and 240K. Relative Wilson Statistics applied to low resolution data showed evidence of a phase transition in the region of 180K. A plot of the liquidity factor, B sn , versus distance from the protein surface begins with a high plateau near the surface of the protein and drops to two minima at distances from the protein surface of about 2.35 Angstrom and 3.85 Angstrom. Two distinct hydration shells are observed. Both hydration shells are observed to expand as the temperature is increased

  6. Radioimmunoassay of plasma myoglobin concentrations in normal persons

    Energy Technology Data Exchange (ETDEWEB)

    Milanov, S.; Milkov, V. (Meditsinska Akademiya, Sofia (Bulgaria). Nauchen Inst. po Rentgenologiya i Radiobiologiya)

    1982-01-01

    Plasma myoglobin concentrations by radioimmunoassay in 53 normal persons (29 women and 24 men) with ages ranging from 19 to 76 years. The average values for myoglobin concentrations in the plasma of 29 women, aged 19 to 76 years, are 4a.09 +- 4.51 ng/ml, while in 24 healthy men, aged 20 to 74 years, they are 54.39 +-4.68 ng/ml. The obtained results for the plasma myoglobin level in men are higher than the ones recorded in women at statistical significance p<0.05. In the group under study the plasma myoglobin values disclose also age-related differences, although lacking statistical significance (p>0.10).

  7. Met-myoglobin formation, accumulation, degradation, and myoglobin oxygenation monitoring based on multiwavelength attenuance measurement in porcine meat

    Science.gov (United States)

    Nguyen, Thien; Phan, Kien Nguyen; Lee, Jee-Bum; Kim, Jae Gwan

    2016-05-01

    We propose a simple, rapid, and nondestructive method to investigate formation, accumulation, and degradation of met-myoglobin (met-Mb) and myoglobin oxygenation from the interior of porcine meat. For the experiment, color photos and attenuance spectra of porcine meat (well-bled muscle, fat, and mixed) were collected daily to perform colorimetric analysis and to obtain the differences of attenuance between 578 and 567 nm (A578-A567) and between 615 and 630 nm (A630-A615), respectively. Oxy-, deoxy-, and met-myoglobin concentration changes over storage time were also calculated using Beer-Lamberts' law with reflectance intensities at 557, 582, and 630 nm. The change of A578-A567 was well matched with the change of myoglobin oxygenation, and the change of A630-A615 corresponded well with the formation and degradation of met-Mb. In addition, attenuation differences, A578-A567 and A630-A615, were able to show the formation of met-Mb earlier than colorimetric analysis. Therefore, the attenuance differences between wavelengths can be indicators for estimating myoglobin oxygenation and met-Mb formation, accumulation, and degradation, which enable us to design a simple device to monitor myoglobin activities in porcine meat.

  8. Myoglobin Expression in Chelonia mydas Brain, Heart and Liver Tissues

    Directory of Open Access Journals (Sweden)

    RINI PUSPITANINGRUM

    2010-09-01

    Full Text Available An understanding of the underpinning physiology and biochemistry of animals is essential to properly understand the impact of anthropogenic changes and natural catastrophes upon the conservation of endangered species. An observation on the tissue location of the key respiratory protein, myoglobin, now opens up new opportunities for understanding how hypoxia tolerance impacts on diving lifestyle in turtles. The respiratory protein, myoglobin has functions other than oxygen binding which are involved in hypoxia tolerance, including metabolism of reactive oxygen species and of the vascular function by metabolism of nitric oxide. Our work aims to determine whether myoglobin expression in the green turtle exists in multiple non muscle tissues and to confirm the hypothesis that reptiles also have a distributed myoglobin expression which is linked to the hypoxiatolerant trait. This initial work in turtle hatch Chelonia mydas confirms the presence of myoglobin transcriptin brain, heart and liver tissues. Furthermore, it will serve as a tool for completing the sequence and generating an in situ hybridization probe for verifying of cell location in expressing tissues.

  9. Myoglobin Expression in Chelonia mydas Brain, Heart and Liver Tissues

    Directory of Open Access Journals (Sweden)

    RINI PUSPITANINGRUM

    2010-09-01

    Full Text Available An understanding of the underpinning physiology and biochemistry of animals is essential to properly understand the impact of anthropogenic changes and natural catastrophes upon the conservation of endangered species. An observation on the tissue location of the key respiratory protein, myoglobin, now opens up new opportunities for understanding how hypoxia tolerance impacts on diving lifestyle in turtles. The respiratory protein, myoglobin has functions other than oxygen binding which are involved in hypoxia tolerance, including metabolism of reactive oxygen species and of the vascular function by metabolism of nitric oxide. Our work aims to determine whether myoglobin expression in the green turtle exists in multiple non muscle tissues and to confirm the hypothesis that reptiles also have a distributed myoglobin expression which is linked to the hypoxia-tolerant trait. This initial work in turtle hatch Chelonia mydas confirms the presence of myoglobin transcriptin brain, heart and liver tissues. Furthermore, it will serve as a tool for completing the sequence and generating an in situ hybridization probe for verifying of cell location in expressing tissues.

  10. Understanding water: Molecular dynamics simulations of solubilized and crystallized myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Wei Gu; Garcia, A.E.; Schoenborn, B.P. [Los Alamos National Laboratory, NM (United States)

    1994-12-31

    Molecular dynamics simulations were performed on CO myoglobin to evaluate the stability of the bound water molecules as determined in a neutron diffraction analysis. The myoglobin structure derived from the neutron analysis provided the starting coordinate set used in the simulations. The simulations show that only a few water molecules are tightly bound to protein atoms, while most solvent molecules are labile, breaking and reforming hydrogen bonds. Comparison between myoglobin in solution and in a single crystal highlighted some of the packing effects on the solvent structure and shows that water solvent plays an indispensable role in protein dynamics and structural stability. The described observations explain some of the differences in the experimental results of protein hydration as observed in NMR, neutron and X-ray diffraction studies.

  11. Myoglobin structure and function: A multiweek biochemistry laboratory project.

    Science.gov (United States)

    Silverstein, Todd P; Kirk, Sarah R; Meyer, Scott C; Holman, Karen L McFarlane

    2015-01-01

    We have developed a multiweek laboratory project in which students isolate myoglobin and characterize its structure, function, and redox state. The important laboratory techniques covered in this project include size-exclusion chromatography, electrophoresis, spectrophotometric titration, and FTIR spectroscopy. Regarding protein structure, students work with computer modeling and visualization of myoglobin and its homologues, after which they spectroscopically characterize its thermal denaturation. Students also study protein function (ligand binding equilibrium) and are instructed on topics in data analysis (calibration curves, nonlinear vs. linear regression). This upper division biochemistry laboratory project is a challenging and rewarding one that not only exposes students to a wide variety of important biochemical laboratory techniques but also ties those techniques together to work with a single readily available and easily characterized protein, myoglobin. © 2015 International Union of Biochemistry and Molecular Biology.

  12. Understanding water: Molecular dynamics simulations of solubilized and crystallized myoglobin

    International Nuclear Information System (INIS)

    Wei Gu; Garcia, A.E.; Schoenborn, B.P.

    1994-01-01

    Molecular dynamics simulations were performed on CO myoglobin to evaluate the stability of the bound water molecules as determined in a neutron diffraction analysis. The myoglobin structure derived from the neutron analysis provided the starting coordinate set used in the simulations. The simulations show that only a few water molecules are tightly bound to protein atoms, while most solvent molecules are labile, breaking and reforming hydrogen bonds. Comparison between myoglobin in solution and in a single crystal highlighted some of the packing effects on the solvent structure and shows that water solvent plays an indispensable role in protein dynamics and structural stability. The described observations explain some of the differences in the experimental results of protein hydration as observed in NMR, neutron and X-ray diffraction studies

  13. Cardiac Troponin I, Creatine Phosphokinase and Myoglobine Levels in Preeclampsia

    Directory of Open Access Journals (Sweden)

    Ahmet Kale

    2005-01-01

    Full Text Available To evaluate minor myocardial injury in preeclamptic pregnancies by serum markers of cardiac troponin-I, creatine phosphokinase and myoglobine. Group I consisted of 45 preeclamptic pregnancies, Group 2 consisted of uncomplicated pregnancies. The groups were compared for maternal age, parity, mean troponin–I, creatine phosphokinase and myoglobine values. Student-t test were used in statistical analyses. Significance was accepted as p<0.05. Cardiac troponin-I levels were statistically significantly higher in preeclamptic pregnancies (0,97 ± 0,11ng/ml than control groups (0,12 ± 0.09 ng/ml (p<0.001. No statistically significant difference was found with mean levels of creatine phosphokinase and myoglobin levels between two groups. Higher values of troponin-I’in preeclamptic patients is thought to be a result of myocardial injury and associated with pregnancy-induced hypertension.

  14. ESR studies of heat denaturation in Cu myoglobin complexes

    International Nuclear Information System (INIS)

    Louro, S.R.W.; Ribeiro, S.C.; Bemski, G.

    1975-01-01

    An investigation is made on the behaviour of Cu2 + and Fe3 + in copper doped myoglobin, subjected to heat treatment. ESR is observed at X-band. The amplitude of the g = 5.9 line of the high spin F 3 + in met-myoglobin is studied as a function of the temperature of the heat treatment, the pH and the length of time of exposure to the heat treatment. These experiments are performed for both the pure protein and for the copper-myoglobin complex, at pH between 5 and 8.5. Results concerning the decrease of the amplitude of Fe 3+ high spin signal are discussed in comparison with Hollocher's results in hemoglobin. The Cu spectra obtained are interpreted, with the aid of a computer program, Kivelson and Neiman's results being used to analyse the authors data

  15. Myoglobin Structure and Function: A Multiweek Biochemistry Laboratory Project

    Science.gov (United States)

    Silverstein, Todd P.; Kirk, Sarah R.; Meyer, Scott C.; Holman, Karen L. McFarlane

    2015-01-01

    We have developed a multiweek laboratory project in which students isolate myoglobin and characterize its structure, function, and redox state. The important laboratory techniques covered in this project include size-exclusion chromatography, electrophoresis, spectrophotometric titration, and FTIR spectroscopy. Regarding protein structure,…

  16. Immobilization of myoglobin in sodium alginate composite membranes

    Directory of Open Access Journals (Sweden)

    Katia Cecília de Souza Figueiredo

    2015-06-01

    Full Text Available AbstractThe immobilization of myoglobin in sodium alginate films was investigated with the aim of evaluating the protein stability in an ionic polymeric matrix. Myoglobin was chosen due to the resemblance to each hemoglobin tetramer. Sodium alginate, being a natural polysaccharide, was selected as the polymeric matrix because of its chemical structure and film-forming ability. To improve the mechanical resistance of sodium alginate films, the polymer was deposited over the surface of a cellulose acetate support by means of ultrafiltration. The ionic crosslink of sodium alginate was investigated by calcium ions. Composite membrane characterization comprised water swelling tests, water flux, SEM images and UV-visible spectroscopy. The electrostatic interaction between the protein and the polysaccharide did not damage the UV-visible pattern of native myoglobin. A good affinity between sodium alginate and cellulose acetate was observed. The top layer of the dense composite membrane successfully immobilized Myoglobin, retaining the native UV-visible pattern for two months.

  17. Enhancing the electrochemical response of myoglobin with carbon nanotube electrodes.

    Science.gov (United States)

    Esplandiu, M J; Pacios, M; Cyganek, L; Bartroli, J; del Valle, M

    2009-09-02

    In this paper, the electrochemical behavior of different myoglobin-modified carbon electrodes is evaluated. In particular, the performance of voltammetric biosensors made of forest-like carbon nanotubes, carbon nanotube composites and graphite composites is compared by monitoring mainly the electrocatalytic reduction of H(2)O(2) by myoglobin and their corresponding electroanalytical characteristics. Graphite composites showed the worst electroanalytical performance, exhibiting a small linear range, a limit of detection (LOD) of 9 x 10(-5) M and low sensitivity. However, it was found that the electrochemical response was enhanced with the use of carbon nanotube-based electrodes with LOD up to 5 x 10(-8) M, higher sensitivities and wider linear range response. On the one hand, in the case of the CNT epoxy composite, the improvement in the response can be mainly attributed to its more porous surface which allows the immobilization of higher amounts of the electroactive protein. On the other hand, in the case of the forest-like CNT electrodes, the enhancement is due to an increase in the electron transfer kinetics. These findings encourage the use of myoglobin-modified carbon nanotube electrodes as potential (bio)sensors of H(2)O(2) or O(2) in biology, microbiology and environmental fields.

  18. Introduction of gold nanoparticles into myoglobin-Nafion film for direct electrochemistry application.

    Science.gov (United States)

    Xie, Wenting; Kong, Linlin; Kan, Meixiu; Han, Dongmei; Wang, Xueji; Zhang, Hui-Min

    2010-10-01

    An effective myoglobin-Nafion film is prepared by introducing gold nanoparticles in through a simple procedure by ion-exchange combined with electrochemical reduction. Gold nanoparticles are highly dispersed in myoglobin-Nafion film with an average size of 2.3 +/- 0.2 nm. The electrochemical behavior of myoglobin entrapped in the film has been carefully investigated with cyclic voltammetry. The results show that the introduction of gold nanoparticles into myoglobin-Nafion film makes the direct electron transfer of myoglobin efficient. A pair of well-defined redox peaks for myoglobin heme Fe(II)/Fe(III) is observed with a formal potential of -0.150 V in 0.1 M phosphate buffer (pH 7.0). The electrochemical parameters of myoglobin in the composite film are further calculated with the results of the electron-transfer rate constant (k(s)) as 0.93 s(-1) and the charge transfer coefficient (alpha) as 0.69. The experimental results also demonstrate that the immobilized myoglobin retains its electrocatalytic activity for the reduction of hydrogen peroxide and the catalytic reduction peak of myoglobin appear in a linear relationship with H2O2 concentration in the range of 10.0-235.0 microM with correlation coefficient of 0.9970. Thus fabricated Au/Mb/Nafion electrode should give a new approach for developing redox protein or enzyme-based biosensors.

  19. Neonatal hyper- and hypothyroidism alter the myoglobin gene expression program in adulthood.

    Science.gov (United States)

    Souza, K de Picoli; Nunes, M T

    2014-08-01

    Myoglobin acts as an oxygen store and a reactive oxygen species acceptor in muscles. We examined myoglobin mRNA in rat cardiac ventricle and skeletal muscles during the first 42 days of life and the impact of transient neonatal hypo- and hyperthyroidism on the myoglobin gene expression pattern. Cardiac ventricle and skeletal muscles of Wistar rats at 7-42 days of life were quickly removed, and myoglobin mRNA was determined by Northern blot analysis. Rats were treated with propylthiouracil (5-10 mg/100 g) and triiodothyronine (0.5-50 µg/100 g) for 5, 15, or 30 days after birth to induce hypo- and hyperthyroidism and euthanized either just after treatment or at 90 days. During postnatal (P) days 7-28, the ventricle myoglobin mRNA remained unchanged, but it gradually increased in skeletal muscle (12-fold). Triiodothyronine treatment, from days P0-P5, increased the skeletal muscle myoglobin mRNA 1.5- to 4.5-fold; a 2.5-fold increase was observed in ventricle muscle, but only when triiodothyronine treatment was extended to day P15. Conversely, hypothyroidism at P5 markedly decreased (60%) ventricular myoglobin mRNA. Moreover, transient hyperthyroidism in the neonatal period increased ventricle myoglobin mRNA (2-fold), and decreased heart rate (5%), fast muscle myoglobin mRNA (30%) and body weight (20%) in adulthood. Transient hypothyroidism in the neonatal period also permanently decreased fast muscle myoglobin mRNA (30%) and body weight (14%). These results indicated that changes in triiodothyronine supply in the neonatal period alter the myoglobin expression program in ventricle and skeletal muscle, leading to specific physiological repercussions and alterations in other parameters in adulthood.

  20. Neonatal hyper- and hypothyroidism alter the myoglobin gene expression program in adulthood

    International Nuclear Information System (INIS)

    Picoli Souza, K. de; Nunes, M.T.

    2014-01-01

    Myoglobin acts as an oxygen store and a reactive oxygen species acceptor in muscles. We examined myoglobin mRNA in rat cardiac ventricle and skeletal muscles during the first 42 days of life and the impact of transient neonatal hypo- and hyperthyroidism on the myoglobin gene expression pattern. Cardiac ventricle and skeletal muscles of Wistar rats at 7-42 days of life were quickly removed, and myoglobin mRNA was determined by Northern blot analysis. Rats were treated with propylthiouracil (5-10 mg/100 g) and triiodothyronine (0.5-50 µg/100 g) for 5, 15, or 30 days after birth to induce hypo- and hyperthyroidism and euthanized either just after treatment or at 90 days. During postnatal (P) days 7-28, the ventricle myoglobin mRNA remained unchanged, but it gradually increased in skeletal muscle (12-fold). Triiodothyronine treatment, from days P0-P5, increased the skeletal muscle myoglobin mRNA 1.5- to 4.5-fold; a 2.5-fold increase was observed in ventricle muscle, but only when triiodothyronine treatment was extended to day P15. Conversely, hypothyroidism at P5 markedly decreased (60%) ventricular myoglobin mRNA. Moreover, transient hyperthyroidism in the neonatal period increased ventricle myoglobin mRNA (2-fold), and decreased heart rate (5%), fast muscle myoglobin mRNA (30%) and body weight (20%) in adulthood. Transient hypothyroidism in the neonatal period also permanently decreased fast muscle myoglobin mRNA (30%) and body weight (14%). These results indicated that changes in triiodothyronine supply in the neonatal period alter the myoglobin expression program in ventricle and skeletal muscle, leading to specific physiological repercussions and alterations in other parameters in adulthood

  1. Neonatal hyper- and hypothyroidism alter the myoglobin gene expression program in adulthood

    Energy Technology Data Exchange (ETDEWEB)

    Picoli Souza, K. de [Faculdade de Ciências Biológicas e Ambientais, Universidade Federal da Grande Dourados, Dourados, MS (Brazil); Nunes, M.T. [Departamento de Fisiologia e Biofísica, Instituto de Ciências Biológicas, Universidade de São Paulo, São Paulo, SP (Brazil)

    2014-06-24

    Myoglobin acts as an oxygen store and a reactive oxygen species acceptor in muscles. We examined myoglobin mRNA in rat cardiac ventricle and skeletal muscles during the first 42 days of life and the impact of transient neonatal hypo- and hyperthyroidism on the myoglobin gene expression pattern. Cardiac ventricle and skeletal muscles of Wistar rats at 7-42 days of life were quickly removed, and myoglobin mRNA was determined by Northern blot analysis. Rats were treated with propylthiouracil (5-10 mg/100 g) and triiodothyronine (0.5-50 µg/100 g) for 5, 15, or 30 days after birth to induce hypo- and hyperthyroidism and euthanized either just after treatment or at 90 days. During postnatal (P) days 7-28, the ventricle myoglobin mRNA remained unchanged, but it gradually increased in skeletal muscle (12-fold). Triiodothyronine treatment, from days P0-P5, increased the skeletal muscle myoglobin mRNA 1.5- to 4.5-fold; a 2.5-fold increase was observed in ventricle muscle, but only when triiodothyronine treatment was extended to day P15. Conversely, hypothyroidism at P5 markedly decreased (60%) ventricular myoglobin mRNA. Moreover, transient hyperthyroidism in the neonatal period increased ventricle myoglobin mRNA (2-fold), and decreased heart rate (5%), fast muscle myoglobin mRNA (30%) and body weight (20%) in adulthood. Transient hypothyroidism in the neonatal period also permanently decreased fast muscle myoglobin mRNA (30%) and body weight (14%). These results indicated that changes in triiodothyronine supply in the neonatal period alter the myoglobin expression program in ventricle and skeletal muscle, leading to specific physiological repercussions and alterations in other parameters in adulthood.

  2. Neonatal hyper- and hypothyroidism alter the myoglobin gene expression program in adulthood

    Directory of Open Access Journals (Sweden)

    K. de Picoli Souza

    2014-08-01

    Full Text Available Myoglobin acts as an oxygen store and a reactive oxygen species acceptor in muscles. We examined myoglobin mRNA in rat cardiac ventricle and skeletal muscles during the first 42 days of life and the impact of transient neonatal hypo- and hyperthyroidism on the myoglobin gene expression pattern. Cardiac ventricle and skeletal muscles of Wistar rats at 7-42 days of life were quickly removed, and myoglobin mRNA was determined by Northern blot analysis. Rats were treated with propylthiouracil (5-10 mg/100 g and triiodothyronine (0.5-50 µg/100 g for 5, 15, or 30 days after birth to induce hypo- and hyperthyroidism and euthanized either just after treatment or at 90 days. During postnatal (P days 7-28, the ventricle myoglobin mRNA remained unchanged, but it gradually increased in skeletal muscle (12-fold. Triiodothyronine treatment, from days P0-P5, increased the skeletal muscle myoglobin mRNA 1.5- to 4.5-fold; a 2.5-fold increase was observed in ventricle muscle, but only when triiodothyronine treatment was extended to day P15. Conversely, hypothyroidism at P5 markedly decreased (60% ventricular myoglobin mRNA. Moreover, transient hyperthyroidism in the neonatal period increased ventricle myoglobin mRNA (2-fold, and decreased heart rate (5%, fast muscle myoglobin mRNA (30% and body weight (20% in adulthood. Transient hypothyroidism in the neonatal period also permanently decreased fast muscle myoglobin mRNA (30% and body weight (14%. These results indicated that changes in triiodothyronine supply in the neonatal period alter the myoglobin expression program in ventricle and skeletal muscle, leading to specific physiological repercussions and alterations in other parameters in adulthood.

  3. Bridging the gap between chemistry, physiology, and evolution: Quantifying the functionality of sperm whale myoglobin mutants

    DEFF Research Database (Denmark)

    Dasmeh, Pouria; Kepp, Kasper Planeta

    2011-01-01

    This work merges a large set of previously reported thermochemical data for myoglobin (Mb) mutants with a physiological model of O2-transport and -storage. The model allows a quantification of the functional proficiency of myoglobin (Mb) mutants under various physiological conditions, i.e. O2-con...

  4. Synthesis of iron nanoparticles from hemoglobin and myoglobin

    International Nuclear Information System (INIS)

    Sayyad, Arshad S; Ajayan, Pulickel M; Balakrishnan, Kaushik; Ci, Lijie; Kabbani, Ahmad T; Vajtai, Robert

    2012-01-01

    Stable iron nanoparticles have been synthesized from naturally occurring and abundant Fe-containing bio-precursors, namely hemoglobin and myoglobin. The formation of stable iron nanoparticles was achieved through a one-pot, single-phase chemical reduction approach. The reduction of iron ions present in the bio-precursors was carried out at room temperature and avoids the use of harsh chemical reagents. The size distribution of the product falls into the narrow 2–5 nm range and the particles were found to be crystalline. This method can be a valuable synthetic approach for producing bio-conjugated nanoparticle systems for biological applications. (paper)

  5. Positively selected sites in cetacean myoglobins contribute to protein stability

    DEFF Research Database (Denmark)

    Dasmeh, Pouria; Serohijos, Adrian W R; Kepp, Kasper P

    2013-01-01

    Since divergence ∼50 Ma ago from their terrestrial ancestors, cetaceans underwent a series of adaptations such as a ∼10-20 fold increase in myoglobin (Mb) concentration in skeletal muscle, critical for increasing oxygen storage capacity and prolonging dive time. Whereas the O2-binding affinity...... between Mb folding stability and protein abundance, suggesting that a selection pressure for stability acts proportionally to higher expression. We also identify a major divergence event leading to the common ancestor of whales, during which major stabilization occurred. Most of the positively selected...

  6. Picosecond thermometer in the amide I band of myoglobin

    DEFF Research Database (Denmark)

    Austin, R.H.; Xie, A.; Meer, L. van der

    2005-01-01

    The amide I and II bands in myoglobin show a heterogeneous temperature dependence, with bands at 6.17 and 6.43 mu m which are more intense at low temperatures. The amide I band temperature dependence is on the long wavelength edge of the band, while the short wavelength side has almost...... can be used to determine the time it takes vibrational energy to flow into the hydration shell. We determine that vibrational energy flow to the hydration shell from the amide I takes approximately 20 ps to occur....

  7. Ligand and proton exchange dynamics in recombinant human myoglobin mutants.

    Science.gov (United States)

    Lambright, D G; Balasubramanian, S; Boxer, S G

    1989-05-05

    Site-specific mutants of human myoglobin have been prepared in which lysine 45 is replaced by arginine (K45R) and aspartate 60 by glutamate (D60E), in order to examine the influence of these residues and their interaction on the dynamics of the protein. These proteins were studied by a variety of methods, including one and two-dimensional proton nuclear magnetic resonance spectroscopy, exchange kinetics for the distal and proximal histidine NH protons as a function of pH in the met cyano forms, flash photolysis of the CO forms, and ligand replacement kinetics. The electronic absorption and proton nuclear magnetic resonance spectra of the CO forms of these proteins are virtually identical, indicating that the structure of the heme pocket is unaltered by these mutations. There are, however, substantial changes in the dynamics of both CO binding and proton exchange for the mutant K45R, whereas the mutant D60E exhibits behavior indistinguishable from the reference human myoglobin. K45R has a faster CO bimolecular recombination rate and slower CO off-rate relative to the reference. The kinetics for CO binding are independent of pH (6.5 to 10) as well as ionic strength (0 to 1 M-NaCl). The exchange rate for the distal histidine NH is substantially lower for K45R than the reference, whereas the proximal histidine NH exchange rate is unaltered. The exchange behavior of the human proteins is similar to that reported for a comparison of the exchange rates for myoglobins having lysine at position 45 with sperm whale myoglobin, which has arginine at this position. This indicates that the differences in exchange rates reflects largely the Lys----Arg substitution. The lack of a simple correlation for the CO kinetics with this substitution means that these are sensitive to other factors as well. Specific kinetic models, whereby substitution of arginine for lysine at position 45 can affect ligand binding dynamics, are outlined. These experiments demonstrate that a relatively

  8. Value of radioimmunologic myoglobin determination in skeletal muscle disorders

    Energy Technology Data Exchange (ETDEWEB)

    Kiessling, W.R.; Beckmann, R.

    1981-12-01

    Using a sensitive radioimmunoassay (RIA) serum myoglobin (Mb) was measured in healthy controls, patients with skeletal muscle disorders (polymyositis, different types of progressive muscular dystrophy, hypokalemic myopathy and myopathy due to cortisone treatment) and as well in definite as possible carriers of Duchenne muscular dystrophy, DMD. The results indicate that Mb is a useful parameter in the assessment of muscle cell damage. Moreover, definite DMD-carriers had hypermyoglobine in 70% and in two of twenty possible DMD-carriers (all had normal CK activities) Mb was found to be markedly increased. The usefulness of an additional Mb determination in the detection of DMD-carriers is discussed.

  9. Influence of exercise on serum levels of myoglobin measured by radioimmunoassay.

    Science.gov (United States)

    Sabriá, M; Ruibal, A; Rey, C; Foz, M; Domenech, F M

    1983-01-01

    To determine the influence of exercise on serum levels of myoglobin, serum levels of this protein were determined by RIA in 90 healthy men, divided as follows: (1) Basal control (no exercise) 25 cases; (2) Moderate exercise (after subject had been working for 12 h in Medicine Emergency Service) 19 cases, and (3) Intensive exercise: (a) football professional (45-min match) 10 cases; (b) football amateur (45-min match) 10 cases; (c) basketball professional (45-min match) 10 cases, and (d) basketball professional (90-min training) 16 cases. Our results led us to the following conclusions. (1) Moderate exercise, such as the usual daily work, does not modify myoglobin levels; (2) Myoglobin serum levels after exercise increase in nearly all individuals. They are higher in untrained people; (3) There seems to be a correlation between exercise intensity and increase of myoglobin serum levels, and (4) The detection of serum myoglobin by RIA may have a wide field of application for sport medicine.

  10. Influence of exercise on serum levels of myoglobin measured by radioimmunoassay

    International Nuclear Information System (INIS)

    Sabria, M.; Rey, C.; Foz, M.; Ruibal, A.; Domenech, F.M.

    1983-01-01

    To determine the influence of exercise on serum levels of myoglobin, serum levels of this protein were determined by RIA in 90 healthy men, divided as follows: (1) Basal control (no exercise) 25 cases; (2) Moderate exercise (after subject had been working for 12 h in Medicine Emergency Service) 19 cases, and (3) Intensive exercise: (a) football professional (45-min match) 10 cases; (b) football amateur (45-min match) 10 cases; (c) basketball professional (45-min match) 10 cases, and (d) basketball professional (90-min training) 16 cases. Our results led us to the following conclusions. (1) Moderate exercise, such as the usual daily work, does not modify myoglobin levels; (2) Myoglobin serum levels after exercise increase in nearly all individuals. They are higher in untrained people; (3) There seems to be a correlation between exercise intensity and increase of myoglobin serum levels, and (4) The detection of serum myoglobin by RIA may have a wide field of application for sport medicine. (orig.)

  11. Influence of exercise on serum levels of myoglobin measured by radioimmunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Sabria, M; Rey, C; Foz, M; Ruibal, A; Domenech, F M

    1983-04-01

    To determine the influence of exercise on serum levels of myoglobin, serum levels of this protein were determined by RIA in 90 healthy men, divided as follows: (1) Basal control (no exercise) 25 cases; (2) Moderate exercise (after subject had been working for 12 h in Medicine Emergency Service) 19 cases, and (3) Intensive exercise: (a) football professional (45-min match) 10 cases; (b) football amateur (45-min match) 10 cases; (c) basketball professional (45-min match) 10 cases, and (d) basketball professional (90-min training) 16 cases. Our results led us to the following conclusions. (1) Moderate exercise, such as the usual daily work, does not modify myoglobin levels; (2) Myoglobin serum levels after exercise increase in nearly all individuals. They are higher in untrained people; (3) There seems to be a correlation between exercise intensity and increase of myoglobin serum levels, and (4) The detection of serum myoglobin by RIA may have a wide field of application for sport medicine.

  12. Effects of ionizing radiation on nitric oxide myoglobin

    International Nuclear Information System (INIS)

    Kamarei, A.R.; Karel, M.

    1983-01-01

    Bovine nitric oxide myoglobin (NOMb) was irradiated with 40-4000 krad of γ-radiation, and the effects on the haem studied using absorption spectroscopy and electron spin resonance (e.s.r.) spectroscopy. The results show the following behaviour: (a) The bright red colour of NOMb changes to brown upon irradiation. This is similar to changes observed in radiation sterilized, nitrite-containing meats. (b) NOMb becomes progressively denitrosylated, with met-myoglobin (metMb) as the immediate product. (c) Upon increasing doses of radiation (up to 800 krad) at O 0 C parallel to NOMb denitrosylation, metMb is gradually converted, by water radiolytic products, to other products, believed to be ferromyoglobin and ferrimyoglobin peroxide. A minor quantity of 'choleglobin-type' pigments may also be formed at the highest doses. (d) Freezing of NOMb has a substantial protective effect against radiation. (e) Native bovine NOMb behaves as a pentaco-ordinate (hfs of 3 peaks with equal intensity); the bond between iron and Nsub(epsilon) is thus dramatically stretched and weakened. (f) Using a thermal energy analyser, no NO could be detected over irradiated NOMb solution, indicating rapid reaction of NO liberated from NOMb by radiation, with radiolytic products of water. (author)

  13. Salt effects on ionization equilibria of histidines in myoglobin.

    Science.gov (United States)

    Kao, Y H; Fitch, C A; Bhattacharya, S; Sarkisian, C J; Lecomte, J T; García-Moreno E, B

    2000-09-01

    The salt dependence of histidine pK(a) values in sperm whale and horse myoglobin and in histidine-containing peptides was measured by (1)H-NMR spectroscopy. Structure-based pK(a) calculations were performed with continuum methods to test their ability to capture the effects of solution conditions on pK(a) values. The measured pK(a) of most histidines, whether in the protein or in model compounds, increased by 0.3 pH units or more between 0.02 M and 1.5 M NaCl. In myoglobin two histidines (His(48) and His(36)) exhibited a shallower dependence than the average, and one (His(113)) showed a steeper dependence. The (1)H-NMR data suggested that the salt dependence of histidine pK(a) values in the protein was determined primarily by the preferential stabilization of the charged form of histidine with increasing salt concentrations rather than by screening of electrostatic interactions. The magnitude and salt dependence of interactions between ionizable groups were exaggerated in pK(a) calculations with the finite-difference Poisson-Boltzmann method applied to a static structure, even when the protein interior was treated with arbitrarily high dielectric constants. Improvements in continuum methods for calculating salt effects on pK(a) values will require explicit consideration of the salt dependence of model compound pK(a) values used for reference in the calculations.

  14. Clinical significance of myoglobinuria and serum myoglobin in heroin-addicted patients

    International Nuclear Information System (INIS)

    Chen Xuehong; Zhong Ganping; Zhang Lan; Liu Jiangyan

    2001-01-01

    The authors study the relationship between myoglobinuria and acute rhabdomyolysis in heroin-addicted patients. The levels of myoglobin in serum and urine were determined by RIA in 106 heroin-addicted patients and 30 healthy volunteers who were selected as the controls. The levels of myoglobin in serum and urine increased significantly in heroin-addicted patients in 3 days after giving up heroin, and gradually decreased in 2 weeks but still higher than the levels of the controls (P 0.05). Urine myoglobin detection is a simple and effective method to find out acute rhabdomyolysis derived from heroin addiction early

  15. Detection of myoglobin desaturation in Mirounga angustirostris during apnea.

    Science.gov (United States)

    Ponganis, Paul J; Kreutzer, Ulrike; Sailasuta, Napapon; Knower, Torre; Hurd, Ralph; Jue, Thomas

    2002-01-01

    1H NMR solution-state study of elephant seal (Mirounga angustirostris) myoglobin (Mb) and hemoglobin (Hb) establishes the temperature-dependent chemical shifts of the proximal histidyl N(delta)H signal, which reflects the respective intracellular and vascular PO2 in vivo. Both proteins exist predominantly in one major isoform and do not exhibit any conformational heterogeneity. The Mb and Hb signals are detectable in M. angustirostris tissue in vivo. During eupnea M. angustirostris muscle maintains a well-saturated MbO2. However, during apnea, the deoxymyoglobin proximal histidyl N(delta)H signal becomes visible, reflecting a declining tissue PO2. The study establishes a firm methodological basis for using NMR to investigate the metabolic responses during sleep apnea of the elephant seal and to secure insights into oxygen regulation in diving mammals.

  16. Picosecond transient absorption study of photodissociated carboxy hemoglobin and myoglobin

    International Nuclear Information System (INIS)

    Janes, S.M.; Dalickas, G.A.; Eaton, W.A.; Hochstrasser, R.M.

    1988-01-01

    The optical transient absorption spectra at 30 ps and 6.5 ns after photolysis are compared for both carboxy hemoglobin (HbCO) and carboxy myoglobin (MbCO). Both 355- and 532-nm excitation pulses were used. In all cases the shapes of the optical difference spectra thus generated are stationary over the complete time-scale studied. The photolysis spectra for MbCO are not significantly different from the equilibrium difference spectra generated on the same picosecond spectrometer when measured to an accuracy of +/- 0.5 nm. In addition, spectral parameters for delegated HbCO generated on the same spectrometer but detected by two different techniques, either by a Vidicon detector or point by point with photomultiplier tubes, are reported; the results are different from some of the previously reported picosecond experiments

  17. Studies on the optical absorption of copper-dopped myoglobin: conformational changes

    International Nuclear Information System (INIS)

    Lamy, M.T.M.

    1976-03-01

    Optical absorption changes in the visible and near U.V. spectrum of myoglobin molecules are observed when copper ions are added to the macromolecule. The heme optical transitions are investigated through a theoretical simulation of the optical absorption spectrum. A study of the absorption band in the region of 700 nm associated with the copper - myoglobin complexes indicated the existence of two kinds of metal-protein complexes: one associated with the six or eitht first added copper ions and the other related with the higher concentrations. Conformational changes caused by thermal treatment are studied in myoglobin water solutions and solutions containing copper ions. The phenomenon named pre-denaturation is observed through the optical absorption at 245 nm. It is shown that interactions between myoglobin molecules occur in the pre-denaturation phenomenon. (Author) [pt

  18. Renal myoglobin in drug addicts: occurrence and significance in a postmortem study

    DEFF Research Database (Denmark)

    Kock, Kirsten Friis; Simonsen, Kirsten Wiese

    1994-01-01

    In a 3-year period (1989–1991) a non-selected, consecutive series of 62 deaths in drug addicts was autopsied at the Forensic Institute in Odense. The kidney sections from these addicts were examined for the presence of renal myoglobin using immunohistochemical methods. A reference group consisting......, immobilization, hypovolemia). In sufficient amounts, renal myoglobin may be of importance as a cause of death or a contributing factor to death in both drug addicts and non-addicts....

  19. Comparison of Creatine Kinase Activity and Myoglobin Blood Level in Acute Myocardial Infarction Patients

    Directory of Open Access Journals (Sweden)

    Sabaheta Hasić

    2008-02-01

    Full Text Available The aim of this prospective study was to evaluate and compare the relative increase of serum myoglobin level and total creatine kinase(CK activity in acute myocardial infarction (AMI patients (n=36. We measured serial changes in total CK activity and myoglobin serum level in three-time periods (6-9 hours, 24 hours and 6-7 days from chest pains onset. Myoglobin peaked during the first 6-9 hours but total CK reached its peak activity after 24 hours from AMI symptoms onset. Results of this study showed that as non-specific cardiac marker myoglobin had better sensitivity and earlier rise in serum than total CK activity in AMI patients. Rapid kinetic of myoglobin level is important for its utility as marker for re-infarction diagnosis. Early myoglobin increase in serum is important for early triage of AMI patients and early "ruling out" of AMI diagnosis if there is no evidence of its elevation in circulation.

  20. Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs.

    Directory of Open Access Journals (Sweden)

    Aristos Ioannou

    Full Text Available High performance liquid chromatography (HPLC coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb and Myoglobin (Mb at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

  1. Methylglyoxal-induced modification causes aggregation of myoglobin

    Science.gov (United States)

    Banerjee, Sauradipta; Maity, Subhajit; Chakraborti, Abhay Sankar

    2016-02-01

    Post-translational modification of proteins by Maillard reaction, known as glycation, is thought to be the root cause of different complications, particularly in diabetes mellitus and age-related disorders. Methylglyoxal (MG), a reactive α-oxoaldehyde, increases in diabetic condition and reacts with proteins to form advanced glycation end products (AGEs) following Maillard-like reaction. We have investigated the in vitro effect of MG (200 μM) on the monomeric heme protein myoglobin (Mb) (100 μM) in a time-dependent manner (7 to 18 days incubation at 25 °C). MG induces significant structural alterations of the heme protein, including heme loss, changes in tryptophan fluorescence, decrease of α-helicity with increased β-sheet content etc. These changes occur gradually with increased period of incubation. Incubation of Mb with MG for 7 days results in formation of the AGE adducts: carboxyethyllysine at Lys-16, carboxymethyllysine at Lys-87 and carboxyethyllysine or pyrraline-carboxymethyllysine at Lys-133. On increasing the period of incubation up to 14 days, additional AGEs namely, carboxyethyllysine at Lys-42 and hydroimidazolone or argpyrimidine at Arg-31 and Arg-139 have been detected. MG also induces aggregation of Mb, which is clearly evident with longer period of incubation (18 days), and appears to have amyloid nature. MG-derived AGEs may thus have an important role as the precursors of protein aggregation, which, in turn, may be associated with physiological complications.

  2. Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs).

    Science.gov (United States)

    Ioannou, Aristos; Varotsis, Constantinos

    2017-01-01

    High performance liquid chromatography (HPLC) coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs) formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb) and Myoglobin (Mb) at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR) spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

  3. Crosstalk between nitrite, myoglobin and reactive oxygen species to regulate vasodilation under hypoxia.

    Directory of Open Access Journals (Sweden)

    Matthias Totzeck

    Full Text Available The systemic response to decreasing oxygen levels is hypoxic vasodilation. While this mechanism has been known for more than a century, the underlying cellular events have remained incompletely understood. Nitrite signaling is critically involved in vessel relaxation under hypoxia. This can be attributed to the presence of myoglobin in the vessel wall together with other potential nitrite reductases, which generate nitric oxide, one of the most potent vasodilatory signaling molecules. Questions remain relating to the precise concentration of nitrite and the exact dose-response relations between nitrite and myoglobin under hypoxia. It is furthermore unclear whether regulatory mechanisms exist which balance this interaction. Nitrite tissue levels were similar across all species investigated. We then investigated the exact fractional myoglobin desaturation in an ex vivo approach when gassing with 1% oxygen. Within a short time frame myoglobin desaturated to 58±12%. Given that myoglobin significantly contributes to nitrite reduction under hypoxia, dose-response experiments using physiological to pharmacological nitrite concentrations were conducted. Along all concentrations, abrogation of myoglobin in mice impaired vasodilation. As reactive oxygen species may counteract the vasodilatory response, we used superoxide dismutase and its mimic tempol as well as catalase and ebselen to reduce the levels of reactive oxygen species during hypoxic vasodilation. Incubation of tempol in conjunction with catalase alone and catalase/ebselen increased the vasodilatory response to nitrite. Our study shows that modest hypoxia leads to a significant nitrite-dependent vessel relaxation. This requires the presence of vascular myoglobin for both physiological and pharmacological nitrite levels. Reactive oxygen species, in turn, modulate this vasodilation response.

  4. How different oxidation states of crystalline myoglobin are influenced by X-rays.

    Science.gov (United States)

    Hersleth, Hans-Petter; Andersson, K Kristoffer

    2011-06-01

    X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

  5. Radioimmunoassay of serum myoglobin and its signifance for diagnosis and therapy of musculoskeletal diseases

    International Nuclear Information System (INIS)

    Kiessling, W.R.

    1982-01-01

    A commercial test kit for radioimmunologic proof of myoglobin in serum was tested with regard to its specificty, sensitivity, precision, reproducibility, recovery and use in the diagnosis and therapy of musculoskeletal diseases. In the serum of 164 healthy control persons (age: 2-79 years) the individual myoglobin concentrations ranged from 4 to 60 ng/ml. Among 300 patients with muscular diseases extreme myoglobinaemia in acute rhabdomyolysis, polymyositis and dermatomyositis and different progressive muscular dystrophies could be detected. Slightly increased myoglobin concentrations could be proved in a number of patient with amyotrophic lateral sklerosis, neural muscular atrophy and in all cases of spinal muscular atrophy of the Kugelberg-Welander type. Confirmed DMD patients exhibited in about 80% of the cases hypermyoglobinaemia, and about 11% of 43 possible DMD patients showed an increase in myoglobin. Taking acute rhabdomyolysis and myositis as an example, it was found that myoglobin correlates well with the clinical course of these diseases and permits safe inferences as to the efficiency of the therapy chosen. (orig./MG) [de

  6. Synthetic food additive dye "Tartrazine" triggers amorphous aggregation in cationic myoglobin.

    Science.gov (United States)

    Al-Shabib, Nasser Abdulatif; Khan, Javed Masood; Khan, Mohd Shahnawaz; Ali, Mohd Sajid; Al-Senaidy, Abdulrahman M; Alsenaidy, Mohammad A; Husain, Fohad Mabood; Al-Lohedan, Hamad A

    2017-05-01

    Protein aggregation, a characteristic of several neurodegenerative diseases, displays vast conformational diversity from amorphous to amyloid-like aggregates. In this study, we have explored the interaction of tartrazine with myoglobin protein at two different pHs (7.4 and 2.0). We have utilized various spectroscopic techniques (turbidity, Rayleigh light scattering (RLS), intrinsic fluorescence, Congo Red and far-UV CD) along with microscopy techniques i.e. atomic force microscopy (AFM) and transmission electron microscopy (TEM) to characterize the tartrazine-induced aggregation in myoglobin. The results showed that higher concentrations of tartrazine (2.0-10.0mM) induced amorphous aggregation in myoglobin at pH 2.0 via electrostatic interactions. However, tartrazine was not able to induce aggregation in myoglobin at pH 7.4; because of strong electrostatic repulsion between myoglobin and tartrazine at this pH. The tartrazine-induced amorphous aggregation process is kinetically very fast, and aggregation occurred without the formation of a nucleus. These results proposed that the electrostatic interaction is responsible for tartrazine-induced amorphous aggregation. This study may help in the understanding of mechanistic insight of aggregation by tartrazine. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Myoglobin oxygen affinity in aquatic and terrestrial birds and mammals.

    Science.gov (United States)

    Wright, Traver J; Davis, Randall W

    2015-07-01

    Myoglobin (Mb) is an oxygen binding protein found in vertebrate skeletal muscle, where it facilitates intracellular transport and storage of oxygen. This protein has evolved to suit unique physiological needs in the muscle of diving vertebrates that express Mb at much greater concentrations than their terrestrial counterparts. In this study, we characterized Mb oxygen affinity (P50) from 25 species of aquatic and terrestrial birds and mammals. Among diving species, we tested for correlations between Mb P50 and routine dive duration. Across all species examined, Mb P50 ranged from 2.40 to 4.85 mmHg. The mean P50 of Mb from terrestrial ungulates was 3.72±0.15 mmHg (range 3.70-3.74 mmHg). The P50 of cetaceans was similar to terrestrial ungulates ranging from 3.54 to 3.82 mmHg, with the exception of the melon-headed whale, which had a significantly higher P50 of 4.85 mmHg. Among pinnipeds, the P50 ranged from 3.23 to 3.81 mmHg and showed a trend for higher oxygen affinity in species with longer dive durations. Among diving birds, the P50 ranged from 2.40 to 3.36 mmHg and also showed a trend of higher affinities in species with longer dive durations. In pinnipeds and birds, low Mb P50 was associated with species whose muscles are metabolically active under hypoxic conditions associated with aerobic dives. Given the broad range of potential globin oxygen affinities, Mb P50 from diverse vertebrate species appears constrained within a relatively narrow range. High Mb oxygen affinity within this range may be adaptive for some vertebrates that make prolonged dives. © 2015. Published by The Company of Biologists Ltd.

  8. The myoglobin of Emperor penguin (Aptenodytes forsteri): amino acid sequence and functional adaptation to extreme conditions.

    Science.gov (United States)

    Tamburrini, M; Romano, M; Giardina, B; di Prisco, G

    1999-02-01

    In the framework of a study on molecular adaptations of the oxygen-transport and storage systems to extreme conditions in Antarctic marine organisms, we have investigated the structure/function relationship in Emperor penguin (Aptenodytes forsteri) myoglobin, in search of correlation with the bird life style. In contrast with previous reports, the revised amino acid sequence contains one additional residue and 15 differences. The oxygen-binding parameters seem well adapted to the diving behaviour of the penguin and to the environmental conditions of the Antarctic habitat. Addition of lactate has no major effect on myoglobin oxygenation over a large temperature range. Therefore, metabolic acidosis does not impair myoglobin function under conditions of prolonged physical effort, such as diving.

  9. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  10. Electrochemical Aptasensor for Myoglobin-Specific Recognition Based on Porphyrin Functionalized Graphene-Conjugated Gold Nanocomposites

    Directory of Open Access Journals (Sweden)

    Guojuan Zhang

    2016-10-01

    Full Text Available In this work, a novel electrochemical aptasensor was developed for sensitive and selective detection of myoglobin based on meso-tetra (4-carboxyphenyl porphyrin-functionalized graphene-conjugated gold nanoparticles (TCPP–Gr/AuNPs. Due to its good electric conductivity, large specific surface area, and excellent mechanical properties, TCPP–Gr/AuNPs can act as an enhanced material for the electrochemical detection of myoglobin. Meanwhile, it provides an effective matrix for immobilizing myoglobin-binding aptamer (MbBA. The electrochemical aptasensor has a sensitive response to myoglobin in a linear range from 2.0 × 10−11 M to 7.7 × 10−7 M with a detection limit of 6.7 × 10−12 M (S/N = 3. Furthermore, the method has the merits of high sensitivity, low price, and high specificity. Our work will supply new horizons for the diagnostic applications of graphene-based materials in biomedicine and biosensors.

  11. Aggregation and conformational stability evaluation of myoglobin in the presence of ionic surfactant

    Directory of Open Access Journals (Sweden)

    Mohammad A. Alsenaidy

    2018-05-01

    Full Text Available Sodium lauroyl sarcosinate (SLS is frequently used for the solubilization of inclusion bodies in vitro due to its structural similarity to lipid plasma membrane. There are many factors that could influence protein aggregation propensity, including overall protein surface charge and hydrophobicity. Here, the aggregation pathway of myoglobin protein was studied under different conditions (pH 3.5 and 7.4 in the presence of varying concentrations of SLS to evaluate the underlying forces dictating protein aggregation. Data obtained from Rayleigh light scattering, ThT binding assay, and far-UV CD indicated that SLS have different effects on the protein depending on its concentration and environmental conditions. In the presence of low concentrations of SLS (0.05–0.1 mM, no aggregation was detected at both pH conditions tested. Whereas, as we reach higher SLS concentrations (0.5–10.0 mM, myoglobin started forming larger-sized aggregates at pH 3.5 and not pH 7.4. These results suggest that electrostatics interactions as well as hydrophobic forces play an important role in SLS-induced myoglobin aggregation. Keywords: Sodium lauroyl sarcosinate, Surfactant, Myoglobin, Protein aggregation, Amorphous aggregates, pH

  12. Photoexcitation dynamics of nitric oxide bound ferric myoglobin probed by femtosecond IR spectroscopy

    Directory of Open Access Journals (Sweden)

    Park Jaehun

    2013-03-01

    Full Text Available Time-resolved vibrational spectra show that photolysis quantum yield of NO bound ferric myoglobin is smaller than 0.86, the deligated NO geminately rebinds with subnanosecond time scale, and the rebinding kinetics depends on protein conformation.

  13. Factors correlating with significant differences between X-ray structures of myoglobin

    International Nuclear Information System (INIS)

    Rashin, Alexander A.; Domagalski, Marcin J.; Zimmermann, Michael T.; Minor, Wladek; Chruszcz, Maksymilian; Jernigan, Robert L.

    2014-01-01

    Conformational differences between myoglobin structures are studied. Most structural differences in whale myoglobin beyond the uncertainty threshold can be correlated with a few specific structural factors. There are always exceptions and a search for additional factors is needed. The results might have serious implications for biological insights from conformational differences. Validation of general ideas about the origins of conformational differences in proteins is critical in order to arrive at meaningful functional insights. Here, principal component analysis (PCA) and distance difference matrices are used to validate some such ideas about the conformational differences between 291 myoglobin structures from sperm whale, horse and pig. Almost all of the horse and pig structures form compact PCA clusters with only minor coordinate differences and outliers that are easily explained. The 222 whale structures form a few dense clusters with multiple outliers. A few whale outliers with a prominent distortion of the GH loop are very similar to the cluster of horse structures, which all have a similar GH-loop distortion apparently owing to intermolecular crystal lattice hydrogen bonds to the GH loop from residues near the distal histidine His64. The variations of the GH-loop coordinates in the whale structures are likely to be owing to the observed alternative intermolecular crystal lattice bond, with the change to the GH loop distorting bonds correlated with the binding of specific ‘unusual’ ligands. Such an alternative intermolecular bond is not observed in horse myoglobins, obliterating any correlation with the ligands. Intermolecular bonds do not usually cause significant coordinate differences and cannot be validated as their universal cause. Most of the native-like whale myoglobin structure outliers can be correlated with a few specific factors. However, these factors do not always lead to coordinate differences beyond the previously determined uncertainty

  14. Factors correlating with significant differences between X-ray structures of myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Rashin, Alexander A., E-mail: alexander-rashin@hotmail.com [BioChemComp Inc., 543 Sagamore Avenue, Teaneck, NJ 07666 (United States); Iowa State University, 112 Office and Lab Bldg, Ames, IA 50011-3020 (United States); Domagalski, Marcin J. [University of Virginia, 1340 Jefferson Park Avenue, Jordan Hall, Room 4223, Charlottesville, VA 22908 (United States); Zimmermann, Michael T. [Iowa State University, 112 Office and Lab Bldg, Ames, IA 50011-3020 (United States); Minor, Wladek [University of Virginia, 1340 Jefferson Park Avenue, Jordan Hall, Room 4223, Charlottesville, VA 22908 (United States); Chruszcz, Maksymilian [University of Virginia, 1340 Jefferson Park Avenue, Jordan Hall, Room 4223, Charlottesville, VA 22908 (United States); University of South Carolina, 631 Sumter Street, Columbia, SC 29208 (United States); Jernigan, Robert L. [Iowa State University, 112 Office and Lab Bldg, Ames, IA 50011-3020 (United States); BioChemComp Inc., 543 Sagamore Avenue, Teaneck, NJ 07666 (United States)

    2014-02-01

    Conformational differences between myoglobin structures are studied. Most structural differences in whale myoglobin beyond the uncertainty threshold can be correlated with a few specific structural factors. There are always exceptions and a search for additional factors is needed. The results might have serious implications for biological insights from conformational differences. Validation of general ideas about the origins of conformational differences in proteins is critical in order to arrive at meaningful functional insights. Here, principal component analysis (PCA) and distance difference matrices are used to validate some such ideas about the conformational differences between 291 myoglobin structures from sperm whale, horse and pig. Almost all of the horse and pig structures form compact PCA clusters with only minor coordinate differences and outliers that are easily explained. The 222 whale structures form a few dense clusters with multiple outliers. A few whale outliers with a prominent distortion of the GH loop are very similar to the cluster of horse structures, which all have a similar GH-loop distortion apparently owing to intermolecular crystal lattice hydrogen bonds to the GH loop from residues near the distal histidine His64. The variations of the GH-loop coordinates in the whale structures are likely to be owing to the observed alternative intermolecular crystal lattice bond, with the change to the GH loop distorting bonds correlated with the binding of specific ‘unusual’ ligands. Such an alternative intermolecular bond is not observed in horse myoglobins, obliterating any correlation with the ligands. Intermolecular bonds do not usually cause significant coordinate differences and cannot be validated as their universal cause. Most of the native-like whale myoglobin structure outliers can be correlated with a few specific factors. However, these factors do not always lead to coordinate differences beyond the previously determined uncertainty

  15. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  16. The structure and dynamics of the Fe-CO bond in myoglobin

    International Nuclear Information System (INIS)

    Rovira, Carme

    2003-01-01

    This paper is a review of our recent work on the structure and dynamics of the Fe-CO bond in carbonmonoxy myoglobin (MbCO), performed using density functional theory, Car-Parrinello molecular dynamics and hybrid quantum mechanics/molecular mechanics approaches. The results of these investigations have served to shed light onto one of the long standing questions in myoglobin research: whether the protein discriminates the CO ligand with respect to O 2 by distorting the FeCO bond. The calculations show that both in the gas phase and in the protein the Fe-CO bond is essentially linear and therefore exclude the hypothesis that the CO in MbCO is sterically hindered. In contrast, hydrogen bonding between the O 2 ligand and the His64 residue easily explains the protein discrimination for CO

  17. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  18. Detection of Myoglobin with an Open-Cavity-Based Label-Free Photonic Crystal Biosensor.

    Science.gov (United States)

    Zhang, Bailin; Tamez-Vela, Juan Manuel; Solis, Steven; Bustamante, Gilbert; Peterson, Ralph; Rahman, Shafiqur; Morales, Andres; Tang, Liang; Ye, Jing Yong

    2013-01-01

    The label-free detection of one of the cardiac biomarkers, myoglobin, using a photonic-crystal-based biosensor in a total-internal-reflection configuration (PC-TIR) is presented in this paper. The PC-TIR sensor possesses a unique open optical microcavity that allows for several key advantages in biomolecular assays. In contrast to a conventional closed microcavity, the open configuration allows easy functionalization of the sensing surface for rapid biomolecular binding assays. Moreover, the properties of PC structures make it easy to be designed and engineered for operating at any optical wavelength. Through fine design of the photonic crystal structure, biochemical modification of the sensor surface, and integration with a microfluidic system, we have demonstrated that the detection sensitivity of the sensor for myoglobin has reached the clinically significant concentration range, enabling potential usage of this biosensor for diagnosis of acute myocardial infarction. The real-time response of the sensor to the myoglobin binding may potentially provide point-of-care monitoring of patients and treatment effects.

  19. Roles of the creatine kinase system and myoglobin in maintaining energetic state in the working heart

    Directory of Open Access Journals (Sweden)

    Beard Daniel A

    2009-02-01

    Full Text Available Abstract Background The heart is capable of maintaining contractile function despite a transient decrease in blood flow and increase in cardiac ATP demand during systole. This study analyzes a previously developed model of cardiac energetics and oxygen transport to understand the roles of the creatine kinase system and myoglobin in maintaining the ATP hydrolysis potential during beat-to-beat transient changes in blood flow and ATP hydrolysis rate. Results The theoretical investigation demonstrates that elimination of myoglobin only slightly increases the predicted range of oscillation of cardiac oxygenation level during beat-to-beat transients in blood flow and ATP utilization. In silico elimination of myoglobin has almost no impact on the cytoplasmic ATP hydrolysis potential (ΔGATPase. In contrast, disabling the creatine kinase system results in considerable oscillations of cytoplasmic ADP and ATP levels and seriously deteriorates the stability of ΔGATPase in the beating heart. Conclusion The CK system stabilizes ΔGATPase by both buffering ATP and ADP concentrations and enhancing the feedback signal of inorganic phosphate in regulating mitochondrial oxidative phosphorylation.

  20. Size Polymorphism in Alleles of the Myoglobin Gene from Biomphalaria Mollusks

    Directory of Open Access Journals (Sweden)

    Marcelo M. Santoro

    2010-10-01

    Full Text Available Introns are common among all eukaryotes, while only a limited number of introns are found in prokaryotes. Globin and globin-like proteins are widely distributed in nature, being found even in prokaryotes and a wide range of patterns of intron-exon have been reported in several eukaryotic globin genes. Globin genes in invertebrates show considerable variation in the positions of introns; globins can be found without introns, with only one intron or with three introns in different positions. In this work we analyzed the introns in the myoglobin gene from Biomphalaria glabrata, B. straminea and B. tenagophila. In the Biomphalaria genus, the myoglobin gene has three introns; these were amplified by PCR and analyzed by PCR-RFLP. Results showed that the size (number or nucleotides and the nucleotide sequence of the coding gene of the myoglobin are variable in the three species. We observed the presence of size polymorphisms in intron 2 and 3; this characterizes a homozygous/heterozygous profile and it indicates the existence of two alleles which are different in size in each species of Biomphalaria. This polymorphism could be explored for specific identification of Biomphalaria individuals.

  1. A rapid method for myoglobin radioimmunoanalysis as a diagnostic tool in myocardial infarction

    International Nuclear Information System (INIS)

    Grachev, M.A.; Matveev, L.E.; Pressman, E.K.; Roschke, V.V.

    1982-01-01

    Stone et al. have elaborated a RIA-method for the determination of myoglobin, and found that increase of its concentration in serum is a reliable criterion for the diagnosis of myocardial infarction. However, the test took 24-28 h. Subsequently, the time of the analysis has been reduced to 5-6 h. Recently, a rapid method for the determination of myoglobin has been proposed based upon the use of antiserum immobilized on a powdered carrier. This method takes a little more than 1 h. The procedure according to Roxin et al. is fast due to its non-equilibrium character; after the incubation (30 min) the reaction of the antigen with the immobilized antibody still remains far from equilibrium. It is generally believed that non-equilibrium RIA procedures are less convenient than equilibrium ones for practical clinical applications. According to the RIA procedure proposed here, the time saving compared with the established methods is achieved by using relatively-high concentrations of radioactive myoglobin of moderate specific radioactivity. Under these conditions, the kinetic plateau is reached in 15-20 min. Hence, the total time of the analysis to obtain a standard curve and results for five unknown sera is 55 min. Therefore, the method becomes more useful as a guide in the treatment of myocardial infarction. (Auth.)

  2. Application of three-dimensional reduced graphene oxide-gold composite modified electrode for direct electrochemistry and electrocatalysis of myoglobin

    International Nuclear Information System (INIS)

    Shi, Fan; Xi, Jingwen; Hou, Fei; Han, Lin; Li, Guangjiu; Gong, Shixing; Chen, Chanxing; Sun, Wei

    2016-01-01

    In this paper a three-dimensional (3D) reduced graphene oxide (RGO) and gold (Au) composite was synthesized by electrodeposition and used for the electrode modification with carbon ionic liquid electrode (CILE) as the substrate electrode. Myoglobin (Mb) was further immobilized on the surface of 3D RGO–Au/CILE to obtain an electrochemical sensing platform. Direct electrochemistry of Mb on the modified electrode was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electron transfer of Mb with the modified electrode. The results can be ascribed to the presence of highly conductive 3D RGO–Au composite on the electrode surface that accelerate the electron transfer rate between the electroactive center of Mb and the electrode. The Mb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.2 to 36.0 mmol/L with the detection limit of 0.06 mmol/L (3σ). - Graphical abstract: Direct electrochemistry of myoglobin was realized on a three-dimensional reduced graphene oxide and gold nanocomposite modified carbon ionic liquid electrode. - Highlights: • A three-dimensional reduced graphene oxide and gold composite was synthesized by electrodeposition. • Myoglobin was immobilized on the modified electrode to obtain an electrochemical sensor. • Direct electrochemistry of myoglobin was realized on the modified electrode. • The myoglobin modified electrode showed excellent electrocatalytic reduction to trichloroacetic acid.

  3. Electron paramagnetic resonance in myoglobin single crystals doped with Cu(II) : conformational changes

    International Nuclear Information System (INIS)

    Nascimento, O.R.

    1976-03-01

    Single crystals of sperm whale met-Myoglobin were doped with Cu (II) by immersion in a saturaded solution of NH 3 (SO 4 ) containing diluted Cu (SO 4 ).Two isotropic EPR spectra with different parameters and three anisotropic EPR spectra corresponding to three distinct types of Cu(II) : Mb complexes were identified. A fitting of the angular variation of the EPR spectrum of one of the complexes named here Cu(II)A : Mb was done using a spin Hamiltonian with axial symmetry calculated up to second order which gave the EPR hyperfine parameters.A study of the thermal variation of the complex Cu (II)A : Mb EPR spectrum in the temperature range of 25 0 C to 55 0 C allowed an identification of a conformational variation of the molecule the spectrum evolved from the anisotropic to isotropic spectrum with different parameters. A model of the Cu(II)A : Mb complex is proposed to explain the conformational change of the molecule by means of EPR spectra before and after thermal treatment. The isotropic spectrum obtained with the crystal at 55 0 C presents the EPR parameters very similar to the same parameters obtained with the Cu (II) : Mb complex in aqueous solution at 77 0 K, whereas the isotropic spectra parameters obtained with the dried crystal are quite different. It was possible to identify two different tertiary structures of the myoglobin molecule : one corresponding to the molecule in the crystal at 55 0 C and other to the dry crystal. A slight difference in the crystalline and solution structure of the myoglobin mollecule is observed. (Author) [pt

  4. Endogenous myoglobin in human breast cancer is a hallmark of luminal cancer phenotype.

    Science.gov (United States)

    Kristiansen, G; Rose, M; Geisler, C; Fritzsche, F R; Gerhardt, J; Lüke, C; Ladhoff, A-M; Knüchel, R; Dietel, M; Moch, H; Varga, Z; Theurillat, J-P; Gorr, T A; Dahl, E

    2010-06-08

    We aimed to clarify the incidence and the clinicopathological value of non-muscle myoglobin (Mb) in a large cohort of non-invasive and invasive breast cancer cases. Matched pairs of breast tissues from 10 patients plus 17 breast cell lines were screened by quantitative PCR for Mb mRNA. In addition, 917 invasive and 155 non-invasive breast cancer cases were analysed by immunohistochemistry for Mb expression and correlated to clinicopathological parameters and basal molecular characteristics including oestrogen receptor-alpha (ERalpha)/progesteron receptor (PR)/HER2, fatty acid synthase (FASN), hypoxia-inducible factor-1alpha (HIF-1alpha), HIF-2alpha, glucose transporter 1 (GLUT1) and carbonic anhydrase IX (CAIX). The spatial relationship of Mb and ERalpha or FASN was followed up by double immunofluorescence. Finally, the effects of estradiol treatment and FASN inhibition on Mb expression in breast cancer cells were analysed. Myoglobin mRNA was found in a subset of breast cancer cell lines; in microdissected tumours Mb transcript was markedly upregulated. In all, 71% of tumours displayed Mb protein expression in significant correlation with a positive hormone receptor status and better prognosis. In silico data mining confirmed higher Mb levels in luminal-type breast cancer. Myoglobin was also correlated to FASN, HIF-2alpha and CAIX, but not to HIF-1alpha or GLUT1, suggesting hypoxia to participate in its regulation. Double immunofluorescence showed a cellular co-expression of ERalpha or FASN and Mb. In addition, Mb levels were modulated on estradiol treatment and FASN inhibition in a cell model. We conclude that in breast cancer, Mb is co-expressed with ERalpha and co-regulated by oestrogen signalling and can be considered a hallmark of luminal breast cancer phenotype. This and its possible new role in fatty acid metabolism may have fundamental implications for our understanding of Mb in solid tumours.

  5. Myocyte specific overexpression of myoglobin impairs angiogenesis after hind-limb ischemia.

    Science.gov (United States)

    Hazarika, Surovi; Angelo, Michael; Li, Yongjun; Aldrich, Amy J; Odronic, Shelley I; Yan, Zhen; Stamler, Jonathan S; Annex, Brian H

    2008-12-01

    In preclinical models of peripheral arterial disease the angiogenic response is typically robust, though it can be impaired in conditions such as hypercholesterolemia and diabetes where the endothelium is dysfunctional. Myoglobin (Mb) is expressed exclusively in striated muscle cells. We hypothesized that myocyte specific overexpression of myoglobin attenuates ischemia-induced angiogenesis even in the presence of normal endothelium. Mb overexpressing transgenic (MbTg, n=59) and wild-type (WT, n=56) C57Bl/6 mice underwent unilateral femoral artery ligation/excision. Perfusion recovery was monitored using Laser Doppler. Ischemia-induced changes in muscle were assessed by protein and immunohistochemistry assays. Nitrite/nitrate and protein-bound NO, and vasoreactivity was measured. Vasoreactivity was similar between MbTg and WT. In ischemic muscle, at d14 postligation, MbTg increased VEGF-A, and activated eNOS the same as WT mice but nitrate/nitrite were reduced whereas protein-bound NO was higher. MbTg had attenuated perfusion recovery at d21 (0.37+/-0.03 versus 0.47+/-0.02, P<0.05), d28 (0.40+/-0.03 versus 0.50+/-0.04, P<0.05), greater limb necrosis (65.2% versus 15%, P<0.001), a lower capillary density, and greater apoptosis versus WT. Increased Mb expression in myocytes attenuates angiogenesis after hind-limb ischemia by binding NO and reducing its bioavailability. Myoglobin can modulate the angiogenic response to ischemia even in the setting of normal endothelium.

  6. Vibrational dynamics of thiocyanate and selenocyanate bound to horse heart myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Maj, Michał; Oh, Younjun; Park, Kwanghee; Lee, Jooyong; Cho, Minhaeng, E-mail: mcho@korea.ac.kr [Department of Chemistry, Korea University, Seoul 136-713 (Korea, Republic of); Kwak, Kyung-Won [Department of Chemistry, Chung-Ang University, Seoul 156-756, SouthKorea (Korea, Republic of)

    2014-06-21

    The structure and vibrational dynamics of SCN- and SeCN-bound myoglobin have been investigated using polarization-controlled IR pump-probe measurements and quantum chemistry calculations. The complexes are found to be in low and high spin states, with the dominant contribution from the latter. In addition, the Mb:SCN high spin complex exhibits a doublet feature in the thiocyanate stretch IR absorption spectra, indicating two distinct molecular conformations around the heme pocket. The binding mode of the high spin complexes was assigned to occur through the nitrogen atom, contrary to the binding through the sulfur atom that was observed in myoglobin derived from Aplysia Limacina. The vibrational energy relaxation process has been found to occur substantially faster than those of free SCN{sup −} and SeCN{sup −} ions and neutral SCN- and SeCN-derivatized molecules reported previously. This supports the N-bound configurations of MbNCS and MbNCSe, because S- and Se-bound configurations are expected to have significantly long lifetimes due to the insulation effect by heavy bridge atom like S and Se in such IR probes. Nonetheless, even though their lifetimes are much shorter than those of corresponding free ions in water, the vibrational lifetimes determined for MbNCS and MbNCSe are still fairly long compared to those of azide and cyanide myoglobin systems studied before. Thus, thiocyanate and selenocyanate can be good local probes of local electrostatic environment in the heme pocket. The globin dependence on binding mode and vibrational dynamics is also discussed.

  7. An improved UPLC method for the detection of undeclared horse meat addition by using myoglobin as molecular marker.

    Science.gov (United States)

    Di Giuseppe, Antonella M A; Giarretta, Nicola; Lippert, Martina; Severino, Valeria; Di Maro, Antimo

    2015-02-15

    In 2013, following the scandal of the presence of undeclared horse meat in various processed beef products across the Europe, several researches have been undertaken for the safety of consumer health. In this framework, an improved UPLC separation method has been developed to detect the presence of horse myoglobin in raw meat samples. The separation of both horse and beef myoglobins was achieved in only seven minutes. The methodology was improved by preparing mixtures with different composition percentages of horse and beef meat. By using myoglobin as marker, low amounts (0.50mg/0.50g, w/w; ∼0.1%) of horse meat can be detected and quantified in minced raw meat samples with high reproducibility and sensitivity, thus offering a valid alternative to conventional PCR techniques. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. On the value of radioimmunologic myoglobin determination in skeletal muscle disorders

    International Nuclear Information System (INIS)

    Kiessling, W.R.; Beckmann, R.

    1981-01-01

    Using a sensitive radioimmunoassay (RIA) serum myoglobin (Mb) was measured in healthy controls, patients with skeletal muscle disorders (polymyositis, different types of progressive muscular dystrophy, hypokalemic myopathy and myopathy due to cortisone treatment) and as well in definite as possible carriers of Duchenne muscular dystrophy, DMD. The results indicate that Mb is a useful parameter in the assessment of muscle cell damage. Moreover, definite DMD-carriers had hypermyoglobine in 70% and in two of twenty possible DMD-carriers (all had normal CK activities) Mb was found to be markedly increased. The usefulness of an additional Mb determination in the detection of DMD-carriers is discussed. (orig.) [de

  9. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

  10. Motions and electrostatic interactions in natural and semisynthetic myoglobins: a carbon-13 nuclear magnetic resonance study

    International Nuclear Information System (INIS)

    Maskalick, D.G.

    1984-01-01

    It is expected that the internal motions of amino acid side chains and protein backbone segments influence and are in turn affected by charge-charge and related interactions, steric constraints, hydrophobic forces, and hydrogen bonding. As an initial test of this theory 13 C-enriched glycine, alanine, and isoleucine have been substituted for the amino terminal valine of sperm whale myoglobin using semisynthetic techniques. 13 C-NMR has been used to analyze the motions of the side chain and the protonation state of the alpha amino group as a function of pH. The addition of a single methyl group to the side chain can alter the alpha amino pK value by as much as 0.3 pH units indicating a delicately balanced set of change-charge interactions between the alpha amino group and the rest of the protein. Further evidence in support of the state theory was found upon examination of the internal motions of seven of nine isoleucine vectors. These motions were extracted from natural abundance 13 C-NMR relaxation data. The results suggest a strong possibility that concerted motions are important. Also, an increase in temperature from 32 0 C to 52 0 C leads to an electrostatically driven tightening of the myoglobin structure as evidenced by no significant increase in motion amplitude of most of the vectors

  11. Aerobic dive limits of seals with mutant myoglobin using combined thermochemical and physiological data

    DEFF Research Database (Denmark)

    Dasmeh, Pouria; Davis, Randall W.; Kepp, Kasper Planeta

    2013-01-01

    This paper presents an integrated model of convective O2-transport, aerobic dive limits (ADL), and thermochemical data for oxygen binding to mutant myoglobin (Mb), used to quantify the impact of mutations in Mb on the dive limits of Weddell seals (Leptonychotes weddellii). We find that wild-type ...... that such conditions are mostly selected upon in seals. The model is capable of roughly quantifying the physiological impact of single-protein mutations and thus bridges an important gap between animal physiology and molecular (protein) evolution.......This paper presents an integrated model of convective O2-transport, aerobic dive limits (ADL), and thermochemical data for oxygen binding to mutant myoglobin (Mb), used to quantify the impact of mutations in Mb on the dive limits of Weddell seals (Leptonychotes weddellii). We find that wild-type Mb...... traits are only superior under specific behavioral and physiological conditions that critically prolong the ADL, action radius, and fitness of the seals. As an extreme example, the mutations in the conserved His-64 reduce ADL up to 14±2 min for routine aerobic dives, whereas many other mutations...

  12. Effect of fatty acid interaction on myoglobin oxygen affinity and triglyceride metabolism.

    Science.gov (United States)

    Jue, Thomas; Simond, Gregory; Wright, Traver J; Shih, Lifan; Chung, Youngran; Sriram, Renuka; Kreutzer, Ulrike; Davis, Randall W

    2016-08-01

    Recent studies have suggested myoglobin (Mb) may have other cellular functions in addition to storing and transporting O 2 . Indeed, NMR experiments have shown that the saturated fatty acid (FA) palmitate (PA) can interact with myoglobin (Mb) in its ligated state (MbCO and MbCN) but does not interact with Mb in its deoxygenated state. The observation has led to the hypothesis that Mb can also serve as a fatty acid transporter. The present study further investigates fatty acid interaction with the physiological states of Mb using the more soluble but unsaturated fatty acid, oleic acid (OA). OA binds to MbCO but does not bind to deoxy Mb. OA binding to Mb, however, does not alter its O 2 affinity. Without any Mb, muscle has a significantly lower level of triglyceride (TG). In Mb knock-out (MbKO) mice, both heart and skeletal muscles have lower level of TG relative to the control mice. Training further decreases the relative TG in the MbKO skeletal muscle. Nevertheless, the absence of Mb and lower TG level in muscle does not impair the MbKO mouse performance as evidenced by voluntary wheel running measurements. The results support the hypothesis of a complex physiological role for Mb, especially with respect to fatty acid metabolism.

  13. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  14. Reactions of metal-substituted myoglobins with excess electrons studied by pulse radiolysis and low-temperature gamma-radiolysis

    International Nuclear Information System (INIS)

    Miki, Hideho; Nakajima, Atushi; Ogasawara, Masaaki; Tamura, Mamoru

    1990-01-01

    Reactions of metal-substituted myoglobins with excess electrons in electron-pulse-irradiated aqueous solutions at room temperature and γ-irradiated aqueous matrices at 77 K were studied for the purpose of probing the functional role of heme iron. The rate constants for the reactions of various myoglobins with hydrated electrons were not much different from each other, and were close to those of diffusion-controlled reactions. In contrast, the reduction rates of myoglobins with dithionite depended markedly on the kind of central metals in the myoglobins. The difference was interpreted in terms of Marcus' theory for electron-transfer reactions. Effects of the 6-coordinate structure of the cobalt(III) species on the reaction with dithionite was also discussed. The steady-state optical-absorption measurements of γ-irradiated matrices containing cobaltimyoglobin at 77 K demonstrated the reduction of cobalt(III) species by excess electrons produced by the action of ionizing radiation. It was shown, by electron-spin resonance spectroscopy, that a 6-coordinated cobalt(II) species produced at 77 K transformed to a 5-coordinate one at higher temperatures, as reported previously. However, structural relaxation was not observed by optical spectroscopy either in the solutions or in the low-temperature matrices. It was concluded, therefore, that the intermediate 6-coordinate cobalt(II) species gave an optical absorption spectrum which was indistinguishable from that of the relaxed 5-coordinate cobalt(II) species. (author)

  15. Tracking evolution of myoglobin stability in cetaceans using experimentally calibrated computational methods that account for generic protein relaxation

    DEFF Research Database (Denmark)

    Holm, Jeppe; Dasmeh, Pouria; Kepp, Kasper Planeta

    2016-01-01

    The evolution of cetaceans (whales, dolphins, and porpoises) from land to water is one of the most spectacular events in mammal evolution. It has been suggested that selection for higher myoglobin stability (ΔG of folding) allowed whales to conquer the deep-diving niche. The stability of multi-si...

  16. IGF-1 attenuates hypoxia-induced atrophy but inhibits myoglobin expression in C2C12 skeletal muscle myotubes

    NARCIS (Netherlands)

    Peters, Eva L.; van der Linde, Sandra M.; Vogel, Ilse S.P.; Haroon, Mohammad; Offringa, Carla; de Wit, Gerard M.J.; Koolwijk, Pieter; van der Laarse, Willem J.; Jaspers, Richard T.

    2017-01-01

    Chronic hypoxia is associated with muscle wasting and decreased oxidative capacity. By contrast, training under hypoxia may enhance hypertrophy and increase oxidative capacity as well as oxygen transport to the mitochondria, by increasing myoglobin (Mb) expression. The latter may be a feasible

  17. (R)-α-Lipoic acid inhibits fructose-induced myoglobin fructation and the formation of advanced glycation end products (AGEs) in vitro.

    Science.gov (United States)

    Ghelani, Hardik; Razmovski-Naumovski, Valentina; Pragada, Rajeswara Rao; Nammi, Srinivas

    2018-01-15

    Fructose-mediated protein glycation (fructation) has been linked to an increase in diabetic and cardiovascular complications due to over consumption of high-fructose containing diets in recent times. The objective of the present study is to evaluate the protective effect of (R)-α-lipoic acid (ALA) against fructose-induced myoglobin fructation and the formation of advanced glycation end products (AGEs) in vitro. The anti-glycation activity of ALA was determined using the formation of AGEs fluorescence intensity, iron released from the heme moiety of myoglobin and the level of fructosamine. The fructation-induced myoglobin oxidation was examined using the level of protein carbonyl content and thiol group estimation. The results showed that co-incubation of myoglobin (1 mg/mL), fructose (1 M) and ALA (1, 2 and 4 mM) significantly inhibited the formation of AGEs during the 30 day study period. ALA markedly decreased the levels of fructosamine, which is directly associated with the reduction of AGEs formation. Furthermore, ALA significantly reduced free iron release from myoglobin which is attributed to the protection of myoglobin from fructose-induced glycation. The results also demonstrated a significant protective effect of ALA on myoglobin oxidative damages, as seen from decreased protein carbonyl content and increased protein thiols. These findings provide new insights into the anti-glycation properties of ALA and emphasize that ALA supplementation is beneficial in the prevention of AGEs-mediated diabetic and cardiovascular complications.

  18. Myoglobin Test

    Science.gov (United States)

    ... article. Available online at http://emedicine.medscape.com/article/982711-overview. Accessed October 2011. See More See Less Ask a Laboratory Scientist Your questions will be answered by a laboratory ...

  19. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Cudina, Ivana; Jovanovic, S.V.

    1988-01-01

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  20. Modelling the autoxidation of myoglobin in fresh meat under modified atmosphere packing conditions

    DEFF Research Database (Denmark)

    Tofteskov, Jon; Hansen, Jesper Schmidt; Bailey, Nicholas

    2017-01-01

    pigment concentration data is obtained, but only by substantially increasing the value of the oxygen consumption rate. Application of the model to meat stored at 5 °C shows that the metmyoglobin layer forms under the surface over a time scale of 24 h; The metmyoglobin layer forms deeper inside the meat......Modified atmosphere packing (MAP) is a technique to increase the shelf life of fresh meat. Continuing development of MAP requires better understanding of the physical and chemical processes taking place, in particular the diffusion of oxygen and its reaction with myoglobin. We model these processes...... proportional to the logarithm of the headspace oxygen partial pressure, thus improving the colour appearance of the meat....

  1. Rapid Myoglobin Aggregation through Glucosamine-Induced α-Dicarbonyl Formation.

    Science.gov (United States)

    Hrynets, Yuliya; Ndagijimana, Maurice; Betti, Mirko

    2015-01-01

    The extent of glycation and conformational changes of horse myoglobin (Mb) upon glycation with N-acetyl-glucosamine (GlcNAc), glucose (Glc) and glucosamine (GlcN) were investigated. Among tested sugars, the rate of glycation with GlcN was the most rapid as shown by MALDI and ESI mass spectrometries. Protein oxidation, as evaluated by the amount of carbonyl groups present on Mb, was found to increase exponentially in Mb-Glc conjugates over time, whereas in Mb-GlcN mixtures the carbonyl groups decreased significantly after maximum at 3 days of the reaction. The reaction between GlcN and Mb resulted in a significantly higher amount of α-dicarbonyl compounds, mostly glucosone and 3-deoxyglucosone, ranging from and 27 to 332 mg/L and from 14 to 304 mg/L, respectively. Already at 0.5 days, tertiary structural changes of Mb-GlcN conjugate were observed by altered tryptophan fluorescence. A reduction of metmyoglobin to deoxy-and oxymyoglobin forms was observed on the first day of reaction, coinciding with the greatest amount of glucosone produced. In contrast to native α-helical myoglobin, 41% of the glycated protein sequence was transformed into a β-sheet conformation, as determined by circular dichroism spectropolarimetry. Transmission electron microscopy demonstrated that Mb glycation with GlcN causes the formation of amorphous or fibrous aggregates, started already at 3 reaction days. These aggregates bind to an amyloid-specific dye thioflavin T. With the aid of α-dicarbonyl compounds and advanced products of reaction, this study suggests that the Mb glycation with GlcN induces the unfolding of an initially globular protein structure into amyloid fibrils comprised of a β-sheet structure.

  2. PNW cetacean muscle biochemistry - Muscle Myoglobin Content and Acid Buffering Capacity of Cetaceans from the Pacific Northwest to Assess Dive Capacity and the Development of Diving Capabilities

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This project assesses the development of two important skeletal muscle adaptations for diving (enhanced myoglobin content and acid buffering capacities) in a range...

  3. The Nernst equation applied to oxidation-reduction reactions in myoglobin and hemoglobin. Evaluation of the parameters.

    Science.gov (United States)

    Saroff, Harry A

    Analyses of the binding of oxygen to monomers such as myoglobin employ the Mass Action equation. The Mass Action equation, as such, is not directly applicable for the analysis of the binding of oxygen to oligomers such as hemoglobin. When the binding of oxygen to hemoglobin is analyzed, models incorporating extensions of mass action are employed. Oxidation-reduction reactions of the heme group in myoglobin and hemoglobin involve the binding and dissociation of electrons. This reaction is described with the Nernst equation. The Nernst equation is applicable only to a monomeric species even if the number of electrons involved is greater than unity. To analyze the oxidation-reduction reaction in a molecule such as hemoglobin a model is required which incorporates extensions of the Nernst equation. This communication develops models employing the Nernst equation for oxidation-reduction reactions analogous to those employed for hemoglobin in the analysis of the oxygenation (binding of oxygen) reaction.

  4. The roles of tissue nitrate reductase activity and myoglobin in securing nitric oxide availability in deeply hypoxic crucian carp

    DEFF Research Database (Denmark)

    Hansen, Marie Niemann; Lundberg, Jon O; Filice, Mariacristina

    2016-01-01

    . We also tested whether liver, muscle and heart tissue possess nitrate reductase activity that supplies nitrite to the tissues during severe hypoxia. Crucian carp exposed to deep hypoxia (1nitrite in red musculature to more than double the value in normoxic fish......In mammals, treatment with low doses of nitrite has a cytoprotective effect in ischemia/reperfusion events, as a result of nitric oxide formation and S-nitrosation of proteins. Interestingly, anoxia-tolerant lower vertebrates possess an intrinsic ability to increase intracellular nitrite...... concentration during anoxia in tissues with high myoglobin and mitochondria content, such as the heart. Here, we tested the hypothesis that red and white skeletal muscles develop different nitrite levels in crucian carp exposed to deep hypoxia and assessed whether this correlates with myoglobin concentration...

  5. Moessbauer spectroscopic evidence on the heme binding to the proximal histidine in unfolded carbonmonoxy myoglobin by guanidine hydrochloride

    Energy Technology Data Exchange (ETDEWEB)

    Harami, Taikan, E-mail: harami.taikan@jaea.go.jp [Japan Atomic Energy Agency (Japan); Kitao, Shinji; Kobayashi, Yasuhiro [Kyoto University, Research Reactor Institute (Japan); Mitsui, Takaya [Japan Atomic Energy Agency (Japan)

    2008-01-15

    The unfolded heme structure in myoglobin is controversial because of no chance of direct X-ray structure analyses. The unfolding of carbonmonoxy myoglobin (MbCO) by guanidine hydrochloride (GdnHCl) was studied by the Moessbauer spectroscopy. The spectra show the presence of a sort of spectrum in the unfolded MbCO, independent on the concentration of GdnHCl from 1 to 6 M and the increase of the fraction of unfolded MbCO, depending on the GdnHCl concentration. The isomer shift of the iron of heme in the unfolded MbCO was identified to be different from that of the native MbCO as the globin structure in Mb collapses under the unfolded conditions. This result and the existing related Moessbauer data proved that the heme in the unfolded MbCO may remain coordinated to the proximal histidine.

  6. Amphitrite ornata Dehaloperoxidase (DHP): Investigations of Structural Factors That Influence the Mechanism of Halophenol Dehalogenation Using ;Peroxidase-like; Myoglobin Mutants and ;Myoglobin-like; DHP Mutants

    Energy Technology Data Exchange (ETDEWEB)

    Du, Jing; Huang, Xiao; Sun, Shengfang; Wang, Chunxue; Lebioda, Lukasz; Dawson, John H. (SC)

    2012-05-14

    Dehaloperoxidase (DHP), discovered in the marine terebellid polychaete Amphitrite ornata, is the first heme-containing globin with a peroxidase activity. The sequence and crystal structure of DHP argue that it evolved from an ancient O{sub 2} transport and storage globin. Thus, DHP retains an oxygen carrier function but also has the ability to degrade halophenol toxicants in its living environment. Sperm whale myoglobin (Mb) in the ferric state has a peroxidase activity {approx}10 times lower than that of DHP. The catalytic activity enhancement observed in DHP appears to have been generated mainly by subtle changes in the positions of the proximal and distal histidine residues that appeared during DHP evolution. Herein, we report investigations into the mechanism of action of DHP derived from examination of 'peroxidase-like' Mb mutants and 'Mb-like' DHP mutants. The dehalogenation ability of wild-type Mb is augmented in the peroxidase-like Mb mutants (F43H/H64L, G65T, and G65I Mb) but attenuated in the Mb-like T56G DHP variant. X-ray crystallographic data show that the distal His residues in G65T Mb and G65I are positioned {approx}0.3 and {approx}0.8 {angstrom}, respectively, farther from the heme iron compared to that in the wild-type protein. The H93K/T95H double mutant Mb with the proximal His shifted to the 'DHP-like' position has an increased peroxidase activity. In addition, a better dehaloperoxidase (M86E DHP) was generated by introducing a negative charge near His89 to enhance the imidazolate character of the proximal His. Finally, only minimal differences in dehalogenation activities are seen among the exogenous ligand-free DHP, the acetate-bound DHP, and the distal site blocker L100F DHP mutant. Thus, we conclude that binding of halophenols in the internal binding site (i.e., distal cavity) is not essential for catalysis. This work provides a foundation for a new structure-function paradigm for peroxidases and for the

  7. Amphitrite ornata dehaloperoxidase (DHP): investigations of structural factors that influence the mechanism of halophenol dehalogenation using "peroxidase-like" myoglobin mutants and "myoglobin-like" DHP mutants.

    Science.gov (United States)

    Du, Jing; Huang, Xiao; Sun, Shengfang; Wang, Chunxue; Lebioda, Lukasz; Dawson, John H

    2011-09-27

    Dehaloperoxidase (DHP), discovered in the marine terebellid polychaete Amphitrite ornata, is the first heme-containing globin with a peroxidase activity. The sequence and crystal structure of DHP argue that it evolved from an ancient O(2) transport and storage globin. Thus, DHP retains an oxygen carrier function but also has the ability to degrade halophenol toxicants in its living environment. Sperm whale myoglobin (Mb) in the ferric state has a peroxidase activity ∼10 times lower than that of DHP. The catalytic activity enhancement observed in DHP appears to have been generated mainly by subtle changes in the positions of the proximal and distal histidine residues that appeared during DHP evolution. Herein, we report investigations into the mechanism of action of DHP derived from examination of "peroxidase-like" Mb mutants and "Mb-like" DHP mutants. The dehalogenation ability of wild-type Mb is augmented in the peroxidase-like Mb mutants (F43H/H64L, G65T, and G65I Mb) but attenuated in the Mb-like T56G DHP variant. X-ray crystallographic data show that the distal His residues in G65T Mb and G65I are positioned ∼0.3 and ∼0.8 Å, respectively, farther from the heme iron compared to that in the wild-type protein. The H93K/T95H double mutant Mb with the proximal His shifted to the "DHP-like" position has an increased peroxidase activity. In addition, a better dehaloperoxidase (M86E DHP) was generated by introducing a negative charge near His89 to enhance the imidazolate character of the proximal His. Finally, only minimal differences in dehalogenation activities are seen among the exogenous ligand-free DHP, the acetate-bound DHP, and the distal site blocker L100F DHP mutant. Thus, we conclude that binding of halophenols in the internal binding site (i.e., distal cavity) is not essential for catalysis. This work provides a foundation for a new structure-function paradigm for peroxidases and for the molecular evolution of the dual-function enzyme DHP.

  8. Physiological and endocrino-metabolic factors affecting serum myoglobin levels assayed by a radioimmunological method

    International Nuclear Information System (INIS)

    Clerico, A.; Giampietro, O.; Del Chicca, M.G.

    1984-01-01

    Only recently with the introduction of accurate and sensitive RIA methods it has been possible to detect significant amounts of myoglobin (M) in human sera. We studied serum M levels by a RIA in normal subjects and athletes with different age, sex and muscle mass, at rest and in different hours of the day, and after physical training, in hypothyroid and acromegalic patients before and after therapy, with the aim to evidentiate the possible factors affecting serum M levels. We used for M assay a very sensitive RIA method. We studied 62 normal adult persons (32 men and 30 women, 16-62 years of age), 93 children (0-12 year old), 15 neonates and 9 athletes. In addition, in 21 normal adult subjects (11 men, 10 women) circadian profiles of M concentrations were studied at rest. A significant circadian rhythm was found in 18 out 21 subjects studied, with higher M levels in the morning hours. Children showed low M concentrations (10.8 - 6.1 ng/ml), while in neonates higher M levels were found. Adult men showed significantly higher M levels (26.2 +- 10.3 ng/ml) than women (19.1 +- 7.3 ng/ml) at 8-10 a.m. A significant correlation between body mass and M levels was found in nonobese-adult men, women and athletes (r=0.7195, n=60, p<0.001) at 8-10 a.m. This correlation was also clearly evident at every hour of the day in the 21 subjects studied for circadian profiles. Myoglobin levels greatly increased after physical training. In 6 of 10 hypothyroid patients M was cleary elevated before substitutive therapy; a significant inverse correlation was found between serum M levels and circulating peripheral (free and total) thyroid hormones. Before treatment, in all acromegalics basal M levels were found to be slightly higher than normal, with significant circadian rhythm, as in normals. In addition, a 'biphasic' pattern of M levels in relation to the behaviour of serum GH concentrations was observed. (Author)

  9. Molecular characterization of Clonorchis sinensis secretory myoglobin: Delineating its role in anti-oxidative survival

    Science.gov (United States)

    2014-01-01

    Background Clonorchiasis is a globally important, neglected food-borne disease caused by Clonorchis sinensis (C. sinensis), and it is highly related to cholangiocarcinoma and hepatocellular carcinoma. Increased molecular evidence has strongly suggested that the adult worm of C. sinensis continuously releases excretory-secretory proteins (ESPs), which play important roles in the parasite-host interactions, to establish successful infection and ensure its own survival. Myoglobin, a hemoprotein, is present in high concentrations in trematodes and ESPs. To further understand the biological function of CsMb and its putative roles in the interactions of C. sinensis with its host, we explored the molecular characterization of CsMb in this paper. Methods We expressed CsMb and its mutants in E. coli BL21 and identified its molecular characteristics using bioinformatics analysis and experimental approaches. Reverse transcription PCR analysis was used to measure myoglobin transcripts of C. sinensis with different culture conditions. The peroxidase activity of CsMb was confirmed by spectrophotometry. We co-cultured RAW264.7 cells with recombinant CsMb (rCsMb), and we then measured the production of hydrogen peroxide (H2O2) and nitric oxide (NO) in addition to the mRNA levels of inducible nitric oxide synthase (iNOS), Cu-Zn superoxide dismutase (SOD1) and Mn superoxide dismutase (SOD2) in activated RAW264.7 cells. Results In the in vitro culture of adult worms, the transcripts of CsMb increased with the increase of oxygen content. Oxidative stress conditions induced by H2O2 increased the levels of CsMb transcripts in a dose-dependent manner. Furthermore, CsMb catalyzed oxidation reactions in the presence of H2O2, and amino acid 34 of CsMb played an essential role in its reaction with H2O2. In addition, CsMb significantly reduced H2O2 and NO levels in LPS-activated macrophages, and CsMb downregulated iNOS and SOD expression in activated macrophages. Conclusion The present study

  10. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  11. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  12. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  13. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  14. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  15. Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films.

    Science.gov (United States)

    Chen, Guiying; Sun, Hong; Hou, Shifeng

    2016-06-01

    In this study, sulfonated graphene oxide (SGO) was synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was used to make Mb-SGO-Nafion composite films by coating myoglobin (Mb) on the glassy carbon electrodes (GCE). Positions of the Soret absorption bands suggested that Mb retained its native conformation in the films. Mb-SGO-Nafion film modified electrode showed a pair of well-defined and nearly reversible cyclic voltammetry peaks at around -0.39 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of heme Fe(III)/Fe(II) redox couples. Electrochemical parameters such as electron transfer rate constant (ks) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry with nonlinear regression analysis. Experimental data demonstrated that the electron transfer between Mb and electrode was greatly facilitated and showed good electrocatalytic properties toward various substrates, such as H2O2 and NaNO2, with significant lowering of reduction overpotential. Copyright © 2016. Published by Elsevier Inc.

  16. Direct electrochemistry and electrocatalysis of myoglobin immobilized on zirconia/multi-walled carbon nanotube nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Ruping; Deng, Minqiang; Cui, Sanguan; Chen, Hong [Department of Chemistry and Institute for Advanced Study, Nanchang University, Nanchang 330031 (China); Qiu, Jianding, E-mail: jdqiu@ncu.edu.cn [Department of Chemistry and Institute for Advanced Study, Nanchang University, Nanchang 330031 (China)

    2010-12-15

    Zirconia/multi-walled carbon nanotube (ZrO{sub 2}/MWCNT) nanocomposite was prepared by hydrothermal treatment of MWCNTs in ZrOCl{sub 2}.8H{sub 2}O aqueous solution. The morphology and structure of the synthesized ZrO{sub 2}/MWCNT nanocomposite were characterized by transmission electron microscopy and X-ray diffraction analysis. It was found that ZrO{sub 2} nanoparticles homogeneously distributed on the sidewall of MWCNTs. Myoglobin (Mb), as a model protein to investigate the nanocomposite, was immobilized on ZrO{sub 2}/MWCNT nanocomposite. Ultraviolet-visible spectroscopy and electrochemical measurements showed that the nanocomposite could retain the bioactivity of the immobilized Mb to a large extent. The Mb immobilized in the composite showed excellent direct electrochemistry and electrocatalytic activity to the reduction of hydrogen peroxide (H{sub 2}O{sub 2}). The linear response range of the biosensor to H{sub 2}O{sub 2} concentration was from 1.0 to 116.0 {mu}M with the limit of detection of 0.53 {mu}M (S/N = 3). The ZrO{sub 2}/MWCNT nanocomposite provided a good biocompatible matrix for protein immobilization and biosensors preparation.

  17. Elastic neutron scattering of dry and rehydrated trehalose coated carboxy-myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Librizzi, Fabio; Vitrano, Eugenio [Dipartimento di Scienze Fisiche e Astronomiche and CNISM, Universita di Palermo, Via Archirafi 36, I-90123 Palermo (Italy); Paciaroni, Alessandro [Dipartimento di Fisica dell' Universita di Perugia, INFM-CRS SOFT and CEMIN - Centro di Eccellenza per i Materiali Innovativi e Nanostrutturati, Via A. Pascoli, I-06123 Perugia (Italy); Cordone, Lorenzo [Dipartimento di Scienze Fisiche e Astronomiche and CNISM, Universita di Palermo, Via Archirafi 36, I-90123 Palermo (Italy)], E-mail: cordone@fisica.unipa.it

    2008-04-18

    We report here a comparison between the hydrogen atoms mean square displacements measured by elastic neutron scattering on trehalose coated carboxy-myoglobin, at ILL on the backscattering spectrometers IN13 and IN16. An inconsistency is observed when comparing the mean square displacements measured on the two spectrometer, on samples of identical composition, since they resulted of larger amplitude on IN13 (either in condition of drought or after overnight rehydration under 75% D{sub 2}O atmosphere), notwithstanding the lower time window accessible on this instrument with respect to IN16. Such inconsistency disappears when the data obtained on this last spectrometer are analyzed in two separate ranges of the exchanged wave vector q. The analysis of the data collected on IN13 in terms of the two-well model [W. Doster, S. Cusak, W. Petry, Nature 337 (1989) 754] gives relevant information on the enthalpy and entropy values involved in the interconversion among substates in dry and rehydrated trehalose coated protein samples.

  18. Roles of Glutamates and Metal ions in a Rationally Designed Nitric Oxide Reductase Based on Myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Y Lin; N Yeung; Y Gao; K Miner; S Tian; H Robinson; Y Lu

    2011-12-31

    A structural and functional model of bacterial nitric oxide reductase (NOR) has been designed by introducing two glutamates (Glu) and three histidines (His) in sperm whale myoglobin. X-ray structural data indicate that the three His and one Glu (V68E) residues bind iron, mimicking the putative FeB site in NOR, while the second Glu (I107E) interacts with a water molecule and forms a hydrogen bonding network in the designed protein. Unlike the first Glu (V68E), which lowered the heme reduction potential by {approx}110 mV, the second Glu has little effect on the heme potential, suggesting that the negatively charged Glu has a different role in redox tuning. More importantly, introducing the second Glu resulted in a {approx}100% increase in NOR activity, suggesting the importance of a hydrogen bonding network in facilitating proton delivery during NOR reactivity. In addition, EPR and X-ray structural studies indicate that the designed protein binds iron, copper, or zinc in the FeB site, each with different effects on the structures and NOR activities, suggesting that both redox activity and an intermediate five-coordinate heme-NO species are important for high NOR activity. The designed protein offers an excellent model for NOR and demonstrates the power of using designed proteins as a simpler and more well-defined system to address important chemical and biological issues.

  19. Determination of myoglobin based on its enzymatic activity by stopped-flow spectrophotometry

    Science.gov (United States)

    Zheng, Qi; Liu, Zhihong; Cai, Ruxiu

    2005-04-01

    A new method has been developed for the determination of myoglobin (Mb) based on its enzymatic activity for the oxidation of o-phenylenediamine (OPDA) with hydrogen peroxide. Stopped-flow spectrophotometry was used to study the kinetic behavior of the oxidation reaction. The catalytic activity of Mb was compared to other three kinds of catalyst. The time dependent absorbance of the reaction product, 2,3-diamimophenazine (DAPN), at a wavelength of 426 nm was recorded. The initial reaction rate obtained at 40 °C was found to be proportional to the concentration of Mb in the range of 1.0 × 10 -6 to 4.0 × 10 -9 mol L -1. The detection limit of Mb was found to be 9.93 × 10 -10 mol L -1. The relative standard deviations were within 5% for the determination of different concentrations of Mb. Excess of bovine serum albumin (BSA), Ca(II), Mg(II), Cu(II), glucose, caffeine, lactose and uric acid did not interfere.

  20. Myoglobin plasma level related to muscle mass and fiber composition: a clinical marker of muscle wasting?

    Science.gov (United States)

    Weber, Marc-André; Kinscherf, Ralf; Krakowski-Roosen, Holger; Aulmann, Michael; Renk, Hanna; Künkele, Annette; Edler, Lutz; Kauczor, Hans-Ulrich; Hildebrandt, Wulf

    2007-08-01

    Progressive muscle wasting is a central feature of cancer-related cachexia and has been recognized as a determinant of poor prognosis and quality of life. However, until now, no easily assessable clinical marker exists that allows to predict or to track muscle wasting. The present study evaluated the potential of myoglobin (MG) plasma levels to indicate wasting of large locomotor muscles and, moreover, to reflect the loss of MG-rich fiber types, which are most relevant for daily performance. In 17 cancer-cachectic patients (weight loss 22%) and 27 age- and gender-matched healthy controls, we determined plasma levels of MG and creatine kinase (CK), maximal quadriceps muscle cross-sectional area (CSA) by magnetic resonance imaging, muscle morphology and fiber composition in biopsies from the vastus lateralis muscle, body cell mass (BCM) by impedance technique as well as maximal oxygen uptake (VO(2)max). In cachectic patients, plasma MG, muscle CSA, BCM, and VO(2)max were 30-35% below control levels. MG showed a significant positive correlation to total muscle CSA (r = 0.65, p max as an important functional readout. CK plasma levels appear to be less reliable because prolonged increases are observed in even subclinical myopathies or after exercise. Notably, cancer-related muscle wasting was not associated with increases in plasma MG or CK in this study.

  1. Graphene-CNT nanohybrid aptasensor for label free detection of cardiac biomarker myoglobin.

    Science.gov (United States)

    Kumar, Vinod; Shorie, Munish; Ganguli, Ashok K; Sabherwal, Priyanka

    2015-10-15

    We report a label free electrochemical detection of cardiac bio-marker myoglobin (Mb) on aptamer functionalized rGO/CNT nanostructured electrodes by measuring its direct electron transfer (DET). Configured as a highly responsive aptasensor, the newly developed biosensing platform exhibits synergistic effect of the nano-hybrid functional construct by combining good electrical properties and the facile chemical functionality of nanohybrid for the compatible bio-interface development. The specific anti-Mb aptamer was generated by five iterative SELEX (Systematic evolution of ligands by exponential enrichment) rounds, showing high senstivity (KD ~65 pM). The aptamer functionalized rGO/CNT nanostructured electrodes demonstrated a significant increase in signal response with a detection limit of ~0.34 ng/mL in the dynamic response range between 1 ng/mL and 4 µg/mL for Mb. The newly developed DET assay format presents a promising candidate in point-of-care diagnosis for routine screening of Mb in patient's samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Initiating fibro-proliferation through interfacial interactions of myoglobin colloids with collagen in solution.

    Science.gov (United States)

    Dhanasekaran, Madhumitha; Dhathathreyan, Aruna

    2017-08-01

    This work examines fibro-proliferation through interaction of myoglobin (Mb), a globular protein with collagen, an extracellular matrix fibrous protein. Designed colloids of Mb at pH 4.5 and 7.5 have been mixed with collagen solution at pH 7.5 and 4.5 in different concentrations altering their surface charges. For the Mb colloids, 100-200nm sizes have been measured from Transmission electron micrographs and zeta sizer. CD spectra shows a shift to beta sheet like structure for the protein in the colloids. Interaction at Mb/Collagen interface studied using Dilational rheology, Quartz crystal microbalance with dissipation and Differential Scanning calorimetry show that the perturbation is not only by the charge compensation arising from the difference in pH of the colloids and collagen, but also by the organized assembly of collagen at that particular pH. Results demonstrate that positive Mb colloids at pH 4.5, having more% of entrained water stabilize the collagen fibrils (pH 7.5) around them. Ensuing dehydration leads to effective cross-linking and inherently anisotropic growth of fibrils/fibres of collagen. In the case of Mb colloids at pH 7.5, the fibril formation seems to supersede the clustering of Mb suggesting that the fibro-proliferation is both pH and hydrophilic-hydrophobic balance dependent at the interface. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Endurance training facilitates myoglobin desaturation during muscle contraction in rat skeletal muscle.

    Science.gov (United States)

    Takakura, Hisashi; Furuichi, Yasuro; Yamada, Tatsuya; Jue, Thomas; Ojino, Minoru; Hashimoto, Takeshi; Iwase, Satoshi; Hojo, Tatsuya; Izawa, Tetsuya; Masuda, Kazumi

    2015-03-24

    At onset of muscle contraction, myoglobin (Mb) immediately releases its bound O2 to the mitochondria. Accordingly, intracellular O2 tension (PmbO2) markedly declines in order to increase muscle O2 uptake (mVO2). However, whether the change in PmbO2 during muscle contraction modulates mVO2 and whether the O2 release rate from Mb increases in endurance-trained muscles remain unclear. The purpose of this study was, therefore, to determine the effect of endurance training on O2 saturation of Mb (SmbO2) and PmbO2 kinetics during muscle contraction. Male Wistar rats were subjected to a 4-week swimming training (Tr group; 6 days per week, 30 min × 4 sets per day) with a weight load of 2% body mass. After the training period, deoxygenated Mb kinetics during muscle contraction were measured using near-infrared spectroscopy under hemoglobin-free medium perfusion. In the Tr group, the VmO2peak significantly increased by 32%. Although the PmbO2 during muscle contraction did not affect the increased mVO2 in endurance-trained muscle, the O2 release rate from Mb increased because of the increased Mb concentration and faster decremental rate in SmbO2 at the maximal twitch tension. These results suggest that the Mb dynamics during muscle contraction are contributing factors to faster VO2 kinetics in endurance-trained muscle.

  4. Elastic neutron scattering of dry and rehydrated trehalose coated carboxy-myoglobin

    International Nuclear Information System (INIS)

    Librizzi, Fabio; Vitrano, Eugenio; Paciaroni, Alessandro; Cordone, Lorenzo

    2008-01-01

    We report here a comparison between the hydrogen atoms mean square displacements measured by elastic neutron scattering on trehalose coated carboxy-myoglobin, at ILL on the backscattering spectrometers IN13 and IN16. An inconsistency is observed when comparing the mean square displacements measured on the two spectrometer, on samples of identical composition, since they resulted of larger amplitude on IN13 (either in condition of drought or after overnight rehydration under 75% D 2 O atmosphere), notwithstanding the lower time window accessible on this instrument with respect to IN16. Such inconsistency disappears when the data obtained on this last spectrometer are analyzed in two separate ranges of the exchanged wave vector q. The analysis of the data collected on IN13 in terms of the two-well model [W. Doster, S. Cusak, W. Petry, Nature 337 (1989) 754] gives relevant information on the enthalpy and entropy values involved in the interconversion among substates in dry and rehydrated trehalose coated protein samples

  5. Isolation of heat-tolerant myoglobin from Asian swamp eel Monopterus albus.

    Science.gov (United States)

    Chotichayapong, Chatrachatchaya; Wiengsamut, Kittipong; Chanthai, Saksit; Sattayasai, Nison; Tamiya, Toru; Kanzawa, Nobuyuki; Tsuchiya, Takahide

    2012-10-01

    Myoglobin from Asian swamp eel Monopterus albus was purified from fish muscle using salt fractionation followed by column chromatography and molecular filtration. The purified Mb of 0.68 mg/g wet weight of muscle was determined for its molecular mass by MALDI-TOF-MS to be 15,525.18 Da. Using isoelectric focusing technique, the purified Mb showed two derivatives with pI of 6.40 and 7.12. Six peptide fragments of this protein identified by LC-MS/MS were homologous to Mbs of sea raven Hemitripterus americanus, yellowfin tuna Thunnus albacores, blue marlin Makaira nigicans, common carp Cyprinus carpio, and goldfish Carassius auratus. According to the Mb denaturation, the swamp eel Mb had thermal stability higher than walking catfish Clarias batrachus Mb and striped catfish Pangasius hypophthalmus Mb, between 30 and 60 (°)C. For the thermal stability of Mb, the swamp eel Mb showed a biphasic behavior due to the O(2) dissociation and the heme orientation disorder, with the lowest increase in both Kd(f) and Kd(s). The thermal sensitivity of swamp eel Mb was lower than those of the other Mbs for both of fast and slow reaction stages. These results suggest that the swamp eel Mb globin structure is thermally stable, which is consistent with heat-tolerant behavior of the swamp eel particularly in drought habitat.

  6. Nutritional profiling of Eurasian woodcock meat: chemical composition and myoglobin characterization.

    Science.gov (United States)

    Landi, Nicola; Ragucci, Sara; Di Giuseppe, Antonella Ma; Russo, Rosita; Poerio, Elia; Severino, Valeria; Di Maro, Antimo

    2018-04-10

    Meat from birds is a rich source of proteins for the human diet. In this framework, Eurasian woodcock (Scolopax rusticola L.), a medium-small wading bird hunted as game in many Eurasian countries, is considered one of the best meats for culinary purposes. Since the nutritional composition of Eurasian woodcock meat has not yet been reported, we decided to determine the nutritional profile of S. rusticola meat. Macronutrient components (proteins, lipids and fatty acids) were determined, as well as free and total amino acids, and compared with those of the common pheasant. Eurasian woodcock meat contains high levels of proteins and essential amino acids. The levels of unsaturated fatty acids represent a great contribution to the total lipid amount. Among polyunsaturated fatty acids, linoleic acid (C18:2, n-6) is the major essential fatty acid. Finally, we report the characterization of myoglobin (Mb) from Eurasian woodcock. The data revealed that meat from this bird could be a good source of quality raw proteins because of its amino acid composition, and it had a low lipid content. On the other hand, Mb characterization might be of benefit to the meat industry, by providing useful information for the determination of species-specific differences in meat from birds. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

  7. Functional properties of myoglobins from five whale species with different diving capacities.

    Science.gov (United States)

    Helbo, Signe; Fago, Angela

    2012-10-01

    Whales show an exceptionally wide range of diving capabilities and many express high amounts of the O(2) carrier protein myoglobin (Mb) in their muscle tissues, which increases their aerobic diving capacity. Although previous studies have mainly focused on the muscle Mb concentration and O(2) carrying capacity as markers of diving behavior in whales, it still remains unexplored whether whale Mbs differ in their O(2) affinities and nitrite reductase and peroxidase enzymatic activities, all functions that could contribute to differences in diving capacities. In this study, we have measured the functional properties of purified Mbs from five toothed whales and two baleen whales and have examined their correlation with average dive duration. Results showed that some variation in functional properties exists among whale Mbs, with toothed whale Mbs having higher O(2) affinities and nitrite reductase activities (similar to those of horse Mb) compared with baleen whale Mbs. However, these differences did not correlate with average dive duration. Instead, a significant correlation was found between whale Mb concentration and average duration and depth of dives, and between O(2) affinity and nitrite reductase activity when including horse Mb. Despite the fact that the functional properties showed little species-specific differences in vitro, they may still contribute to enhancing diving capacity as a result of the increased muscle Mb concentration found in extreme divers. In conclusion, Mb concentration rather than specific functional reactivities may support whale diving performance.

  8. Kinetics and mechanisms of photoinduced electron-transfer reaction of zinc myoglobin

    International Nuclear Information System (INIS)

    Tsukahara, Keiichi; Asami, Satoko; Okada, Mihoko; Sakurai, Takeshi.

    1994-01-01

    Photoinduced electron transfer (ET) between zinc myoglobin (ZnPPMb) and a variety of quenchers, such as hexacyanoferrate(III)([Fe(CN) 6 ] 3- ) and hexaammineruthenium(III)(Ru(NH 3 ) 6 ] 3+ ions, cationic viologens, copper(II) protein (stellacyanin), and metmyoglobins, has been studied in aqueous degassed solutions. The excited triplet state of ZnPPMb( * ZnPPMb) was quenched by [Fe(CN) 6 ] 3- in a self-associated complex. Both quenching rate constant and formation constant of the self-associated complex decrease with increasing ionic strengths. The thermal backward ET reaction for this system was not observed; it is most likely that the backward ET step is much faster than the quenching reaction. All of the cationic quenchers examined in this work did not form a self-associated complex with * ZnPPMb, and the intermolecular quenching occurred. The thermal backward ET reaction was observed for these cationic quenchers. Not only photoinduced ET but also thermal backward ET reactions were insensitive to the driving force of the reactions, suggesting that the reactions are controlled by conformational changes in ZnPPMb. The quenching rate constants increase with increasing ionic strength for the cationic quenchers. The effects of poly-L-lysine hydrochloride, sodium poly-L-glutamate, and sodium cyclo-hexaphosphate were also examined. The active site of the * ZnPPMb toward both anionic and cationic quenchers is assumed to be the positively charged site near the heme pocket. (author)

  9. A hierarchy of functionally important relaxations within myoglobin based on solvent effects, mutations and kinetic model.

    Science.gov (United States)

    Dantsker, David; Samuni, Uri; Friedman, Joel M; Agmon, Noam

    2005-06-01

    Geminate CO rebinding in myoglobin is studied for two viscous solvents, trehalose and sol-gel (bathed in 100% glycerol) at several temperatures. Mutations in key distal hemepocket residues are used to eliminate or enhance specific relaxation modes. The time-resolved data are analyzed with a modified Agmon-Hopfield model which is capable of providing excellent fits in cases where a single relaxation mode is dominant. Using this approach, we determine the relaxation rate constants of specific functionally important modes, obtaining also their Arrhenius activation energies. We find a hierarchy of distal pocket modes controlling the rebinding kinetics. The "heme access mode" (HAM) is responsible for the major slow-down in rebinding. It is a solvent-coupled cooperative mode which restricts ligand return from the xenon cavities. Bulky side-chains, like those His64 and Trp29 (in the L29W mutant), operate like overdamped pendulums which move over and block the binding site. They may be either unslaved (His64) or moderately slaved (Trp29) to the solvent. Small side-chain relaxations, most notably of leucines, are revealed in some mutants (V68L, V68A). They are conjectured to facilitate inter-cavity ligand motion. When all relaxations are arrested (H64L in trehalose), we observe pure inhomogeneous kinetics with no temperature dependence, suggesting that proximal relaxation is not a factor on the investigated timescale.

  10. Fabrication of graphene–platinum nanocomposite for the direct electrochemistry and electrocatalysis of myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wei, E-mail: swyy26@hotmail.com [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Li, Linfang [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Lei, Bingxin [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); Li, Tongtong; Ju, Xiaomei; Wang, Xiuzheng; Li, Guangjiu [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Sun, Zhenfan [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China)

    2013-05-01

    In this paper a platinum (Pt) nanoparticle decorated graphene (GR) nanosheet was synthesized and used for the investigation on direct electrochemistry of myoglobin (Mb). By integrating GR–Pt nanocomposite with Mb on the surface of carbon ionic liquid electrode (CILE), a new electrochemical biosensor was fabricated. UV-Vis absorption and FT-IR spectra indicated that Mb remained its native structure in the nanocomposite film. Electrochemical behaviors of Nafion/Mb–GR–Pt/CILE were investigated with a pair of well-defined redox peak appeared, which indicated that direct electron transfer of Mb was realized on the underlying electrode with the usage of the GR–Pt nanocomposite. The fabricated electrode showed good electrocatalytic activity to the reduction of trichloroacetic acid in the linear range from 0.9 to 9.0 mmol/L with the detection limit as 0.32 mmol/L (3σ), which showed potential application for fabricating novel electrochemical biosensors and bioelectronic devices. - Highlights: ► The GR–Pt nanocomposite was synthesized and employed for the fabrication of electrochemical biosensor. ► Direct electrochemistry of Mb in the nanocomposite was realized. ► The prepared biosensor exhibited excellent electrochemical response to the reduction of TCA.

  11. Fabrication of graphene-platinum nanocomposite for the direct electrochemistry and electrocatalysis of myoglobin.

    Science.gov (United States)

    Sun, Wei; Li, Linfang; Lei, Bingxin; Li, Tongtong; Ju, Xiaomei; Wang, Xiuzheng; Li, Guangjiu; Sun, Zhenfan

    2013-05-01

    In this paper a platinum (Pt) nanoparticle decorated graphene (GR) nanosheet was synthesized and used for the investigation on direct electrochemistry of myoglobin (Mb). By integrating GR-Pt nanocomposite with Mb on the surface of carbon ionic liquid electrode (CILE), a new electrochemical biosensor was fabricated. UV-Vis absorption and FT-IR spectra indicated that Mb remained its native structure in the nanocomposite film. Electrochemical behaviors of Nafion/Mb-GR-Pt/CILE were investigated with a pair of well-defined redox peak appeared, which indicated that direct electron transfer of Mb was realized on the underlying electrode with the usage of the GR-Pt nanocomposite. The fabricated electrode showed good electrocatalytic activity to the reduction of trichloroacetic acid in the linear range from 0.9 to 9.0 mmol/L with the detection limit as 0.32 mmol/L (3σ), which showed potential application for fabricating novel electrochemical biosensors and bioelectronic devices. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  13. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  14. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  15. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2011-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  16. Radical chemistry of artemisinin

    Science.gov (United States)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  17. Radical chemistry of artemisinin

    International Nuclear Information System (INIS)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G

    2010-01-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  18. Radical's view of sciences

    International Nuclear Information System (INIS)

    Mittal, J.P.

    2004-01-01

    Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

  19. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  20. Moderate and Radical Islam

    National Research Council Canada - National Science Library

    Rabasa, Angel

    2005-01-01

    This report presents the statement of Angel Rabasa, PhD, Senior Policy Analyst, The RAND Corporation, to the Committee on Armed Services, Defense Review Terrorism and Radical Islam Gap Panel, United...

  1. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...... within this field and to answer the question: From an empirical point of view, what is known and what is not known about radicalization connected to militant Islamism in Europe?...

  2. Towards a "Golden Standard" for computing globin stability: Stability and structure sensitivity of myoglobin mutants.

    Science.gov (United States)

    Kepp, Kasper P

    2015-10-01

    Fast and accurate computation of protein stability is increasingly important for e.g. protein engineering and protein misfolding diseases, but no consensus methods exist for important proteins such as globins, and performance may depend on the type of structural input given. This paper reports benchmarking of six protein stability calculators (POPMUSIC 2.1, I-Mutant 2.0, I-Mutant 3.0, CUPSAT, SDM, and mCSM) against 134 experimental stability changes for mutations of sperm-whale myoglobin. Six different high-resolution structures were used to test structure sensitivity that may impair protein calculations. The trend accuracy of the methods decreased as I-Mutant 2.0 (R=0.64-0.65), SDM (R=0.57-0.60), POPMUSIC2.1 (R=0.54-0.57), I-Mutant 3.0 (R=0.53-0.55), mCSM (R=0.35-0.47), and CUPSAT (R=0.25-0.48). The mean signed errors increased as SDMMean absolute errors increased as I-Mutant 2.0

  3. Clay-chitosan-gold nanoparticle nanohybrid: Preparation and application for assembly and direct electrochemistry of myoglobin

    International Nuclear Information System (INIS)

    Zhao Xiaojuan; Mai Zhibin; Kang Xinhuang; Dai Zong; Zou Xiaoyong

    2008-01-01

    A biocompatible nanohybrid material (clay/AuCS) based on clay, chitosan and gold nanoparticles was explored. The material could provide a favorable microenvironment for proteins to realize the direct electron transfer on glassy carbon electrodes (GCE). Myoglobin (Mb), as a model protein to investigate the nanohybrid, was immobilized between the clay/AuCS film and another clay layer. Mb in the system exhibited a pair of well-defined and quasi-reversible redox peaks at -0.160 V (vs. saturated Ag/AgCl electrode) in 0.1 M PBS (pH 7.0), corresponding to its heme Fe III /Fe II redox couples. UV-vis spectrum suggested that Mb retained its native conformation in the system. Basal plane spacing of clay obtained by X-ray diffraction (XRD) indicated that there was an intercalation-exfoliation-restacking process among Mb, AuCS and clay during the modified film drying. Excellent biocatalytic activity of Mb in the modified system was exemplified by the reduction of hydrogen peroxide and nitrite. The linear range of H 2 O 2 determination was from 3.9 x 10 -5 to 3.0 x 10 -3 M with a detection limit of 7.5 μM based on the signal to noise ratio of 3. The kinetic parameters such as α (charge transfer coefficient), k s (electron transfer rate constant) and K m (Michaelis-Menten constant) were evaluated to be 0.55, 2.66 ± 0.15 s -1 and 5.10 mM, respectively

  4. Reversible and irreversible conformational transitions in myoglobin: role of hydrated amino acid ionic liquid.

    Science.gov (United States)

    Sankaranarayanan, Kamatchi; Sathyaraj, Gopal; Nair, B U; Dhathathreyan, A

    2012-04-12

    Hydrated phenylalanine ionic liquid (Phe-IL) has been used to solubilize myoglobin (Mb). Structural stability of Mb in Phe-IL analyzed using fluorescence and circular dichroism spectroscopy shows that for low levels of hydration of Phe-IL there is a large red shift in the fluorescence emission wavelength and the protein transforms to complete β sheet from its native helical conformation. Rehydration or dilution reverses the β sheet to an α helix which on aging organizes to micrometer-sized fibrils. At concentrations higher than 200 μM, the protein changes from β to a more random coiled structure. Organization of the protein in Phe-IL in a Langmuir film at the air/water interface has been investigated using the surface pressure-molecular area isotherm and shows nearly the same surface tension for both pure Mb and Mb in Phe-IL. Scanning electron microscopy of the films of Mb in Phe-IL transferred using the Langmuir-Blodgett film technique show layered morphology. This study shows that the conformation of Mb is completely reversible going from β → helix → β sheet up to 200 μM of Phe-IL. Similar surface tension values for Mb in water and in Phe-IL suggests that direct ion binding interactions with the protein coupled with the change in local viscosity from the IL seems to not only alter the secondary structure of individual proteins but also drives the self-assembly of the protein molecules leading finally to fibril formation.

  5. Mode of bindings of zinc oxide nanoparticles to myoglobin and horseradish peroxidase: A spectroscopic investigations

    Science.gov (United States)

    Mandal, Gopa; Bhattacharya, Sudeshna; Ganguly, Tapan

    2011-07-01

    The interactions between two heme proteins myoglobin (HMb) and horseradish peroxidase (HRP) with zinc oxide (ZnO) nanoparticles are investigated by using UV-vis absorption, steady state fluorescence, synchronous fluorescence, time-resolved fluorescence, FT-IR, atomic force microscopy (AFM) and circular dichroism (CD) techniques under physiological condition of pH˜7.4. The presence of mainly static mode in fluorescence quenching mechanism of HMb and HRP by ZnO nanoparticle indicates the possibility of formation of ground state complex. The processes of bindings of ZnO nanoparticles with the two proteins are spontaneous molecular interaction procedures. In both cases hydrogen bonding plays a major role. The circular dichroism (CD) spectra reveal that a helicity of the proteins is reduced by increasing ZnO nanoparticle concentration although the α-helical structures of HMb and HRP retain their identity. On binding to the ZnO nanoparticles the secondary structure of HRP molecules (or HMb molecules) remains unchanged while there is a substantial change in the environment of the tyrosin active site in case of HRP molecules and tryptophan active site in case of HMb molecules. Tapping mode atomic force microscopy (AFM) was applied for the investigation the structure of HRP adsorbed in the environment of nanoparticles on the silicon and on the bare silicon. HRP molecules adsorb and aggregate on the mica with ZnO nanoparticle. The aggregation indicates an attractive interaction among the adsorbed molecules. The molecules are randomly distributed on the bare silicon wafer. The adsorption of HRP in the environment of ZnO nanoparticle changes drastically the domains due to a strong interaction between HRP and ZnO nanoparticles. Similar situation is observed in case of HMb molecules. These findings demonstrate the efficacy of biomedical applications of ZnO nanoparticles as well as in elucidating their mechanisms of action as drugs in both human and plant systems.

  6. Myoglobin as a prognostic indicator for outcome in dogs with gastric dilatation-volvulus.

    Science.gov (United States)

    Adamik, Katja N; Burgener, Iwan A; Kovacevic, Alan; Schulze, Sebastian P; Kohn, Barbara

    2009-06-01

    To determine whether myoglobin (Mb) is a useful prognostic indicator for outcome and to investigate any relationship between Mb and mortality in dogs with gastric dilatation-volvulus (GDV). Prospective study. Veterinary teaching hospital. Seventy-two dogs with GDV. Blood sampling. Mb levels were measured at the time of diagnosis (Mbt0), 24 hours (Mbt1), and 48 hours (Mbt2) after signs of GDV were recognized. Fifty-seven dogs survived (group I) and 15 dogs did not survive (group II). Mbt0 differed significantly between groups (P=0.04). Mbt0 in group I ranged from 700 ng/mL (n=57, median 74 ng/mL), and in group II from 34 to >700 ng/mL (n=15, median 238 ng/mL). Analysis of a receiver operating characteristic curve of Mbt0 suggested that the best single cutpoint would be 168 ng/mL (sensitivity 60.0%, specificity 84.2%). Fifty percent of dogs with Mbt0>168 ng/mL were euthanized, while 88.9% with Mbt0700 ng/mL (n=55, median 123 ng/mL), and Mbt1 in group II ranged from 131 to 643 ng/mL (n=7, median 343 ng/mL) (P=0.006). Mbt2 in group I ranged from 30 to 597 ng/mL (n=54, median 101 ng/mL), and in group II from 141 to >700 ng/mL (n=8, median 203 ng/mL) (P=0.02). In this study, Mbt0 is a moderately sensitive and specific prognostic indicator. Almost 90% of the dogs below the cutpoint survived to discharge, whereas 50% with Mbt0 above the cutpoint did not survive.

  7. Increased oxidative metabolism and myoglobin expression in zebrafish muscle during chronic hypoxia

    Directory of Open Access Journals (Sweden)

    Richard T. Jaspers

    2014-07-01

    Full Text Available Fish may be extremely hypoxia resistant. We investigated how muscle fibre size and oxidative capacity in zebrafish (Danio rerio adapt during severe chronic hypoxia. Zebrafish were kept for either 3 or 6 weeks under chronic constant hypoxia (CCH (10% air/90%N2 saturated water. We analyzed cross-sectional area (CSA, succinate dehydrogenase (SDH activity, capillarization, myonuclear density, myoglobin (Mb concentration and Mb mRNA expression of high and low oxidative muscle fibres. After 3 weeks of CCH, CSA, SDH activity, Mb concentration, capillary and myonuclear density of both muscle fibre types were similar as under normoxia. In contrast, staining intensity for Mb mRNA of hypoxic high oxidative muscle fibres was 94% higher than that of normoxic controls (P<0.001. Between 3 and 6 weeks of CCH, CSA of high and low oxidative muscle fibres increased by 25 and 30%, respectively. This was similar to normoxic controls. Capillary and myonuclear density were not changed by CCH. However, in high oxidative muscle fibres of fish maintained under CCH, SDH activity, Mb concentration as well as Mb mRNA content were higher by 86%, 138% and 90%, respectively, than in muscle fibres of fish kept under normoxia (P<0.001. In low oxidative muscle fibres, SDH activity, Mb and Mb mRNA content were not significantly changed. Under normoxia, the calculated interstitial oxygen tension required to prevent anoxic cores in muscle fibres (PO2crit of high oxidative muscle fibres was between 1.0 and 1.7 mmHg. These values were similar at 3 and 6 weeks CCH. We conclude that high oxidative skeletal muscle fibres of zebrafish continue to grow and increase oxidative capacity during CCH. Oxygen supply to mitochondria in these fibres may be facilitated by an increased Mb concentration, which is regulated by an increase in Mb mRNA content per myonucleus.

  8. Fusion protein-based biofilm fabrication composed of recombinant azurin–myoglobin for dual-level biomemory application

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Taek [Research Institute for Basic Science, Sogang University, Heukseok-dong, Dongjak-gu, Seoul 156-756 (Korea, Republic of); Chung, Yong-Ho; Yoon, Jinho [Department of Chemical and Biomolecular Engineering, Sogang University, Heukseok-dong, Dongjak-gu, 35 Baekbeom-ro (Sinsu-dong), Mapo-gu, Seoul 121-742 (Korea, Republic of); Min, Junhong [School of Integrative Engineering, Chung-Ang University, Heukseok-dong, Dongjak-gu, Seoul 156-756 (Korea, Republic of); Choi, Jeong-Woo, E-mail: jwchoi@sogang.ac.kr [Department of Chemical and Biomolecular Engineering, Sogang University, Heukseok-dong, Dongjak-gu, 35 Baekbeom-ro (Sinsu-dong), Mapo-gu, Seoul 121-742 (Korea, Republic of)

    2014-11-30

    Graphical abstract: - Highlights: • We developed the fusion protein-based biofilm on the inorganic surface. • For making the fusion protein, the recombinant azurin and the myoglobin was conjugated by the native chemical ligation method. • The developed fusion protein shows unique electrochemical property. • The proposed fusion protein biofilm appears to be a good method for dual-level biomemory device. - Abstract: In the present study, a fusion protein-based biofilm composed of a recombinant azurin–myoglobin (Azu-Myo) has been developed and confirmed its original electrochemical property for dual-level biomemory device application. For this purpose, the azurin was modified with cysteine residues for direct immobilization and conjugation. Then, the recombinant azurin was conjugated with the myoglobin via a sulfo-SMCC bifunctional linker using the chemical ligation method (CLM). The SDS-PAGE and UV–vis spectroscopy were performed to examine the fusion protein conjugates. The prepared Azu-Myo fusion protein was self-assembled onto Au substrate for the biofilm fabrication. Then, the atomic force microscopy (AFM) was used to confirm the immobilization and the surface-enhanced Raman spectroscopy (SERS) was carried out to the surface analysis. Also, the cyclic voltammetry (CV) was carried out to observe an electrochemical property of fabricated biofilm. As a result, the two pair of redox potential values was obtained for dual-level biomemory device application. Then, the dual-level biomemory function was verified by the multi-potential chronoamperometry (MPCA). The results indicate a new fabrication method and material combination for advances in bioelectronic device development.

  9. Fusion protein-based biofilm fabrication composed of recombinant azurin–myoglobin for dual-level biomemory application

    International Nuclear Information System (INIS)

    Lee, Taek; Chung, Yong-Ho; Yoon, Jinho; Min, Junhong; Choi, Jeong-Woo

    2014-01-01

    Graphical abstract: - Highlights: • We developed the fusion protein-based biofilm on the inorganic surface. • For making the fusion protein, the recombinant azurin and the myoglobin was conjugated by the native chemical ligation method. • The developed fusion protein shows unique electrochemical property. • The proposed fusion protein biofilm appears to be a good method for dual-level biomemory device. - Abstract: In the present study, a fusion protein-based biofilm composed of a recombinant azurin–myoglobin (Azu-Myo) has been developed and confirmed its original electrochemical property for dual-level biomemory device application. For this purpose, the azurin was modified with cysteine residues for direct immobilization and conjugation. Then, the recombinant azurin was conjugated with the myoglobin via a sulfo-SMCC bifunctional linker using the chemical ligation method (CLM). The SDS-PAGE and UV–vis spectroscopy were performed to examine the fusion protein conjugates. The prepared Azu-Myo fusion protein was self-assembled onto Au substrate for the biofilm fabrication. Then, the atomic force microscopy (AFM) was used to confirm the immobilization and the surface-enhanced Raman spectroscopy (SERS) was carried out to the surface analysis. Also, the cyclic voltammetry (CV) was carried out to observe an electrochemical property of fabricated biofilm. As a result, the two pair of redox potential values was obtained for dual-level biomemory device application. Then, the dual-level biomemory function was verified by the multi-potential chronoamperometry (MPCA). The results indicate a new fabrication method and material combination for advances in bioelectronic device development

  10. Temperature- and pH-dependent effect of lactate on in vitro redox stability of red meat myoglobins.

    Science.gov (United States)

    Nair, M N; Suman, S P; Li, S; Ramanathan, R; Mancini, R A

    2014-01-01

    Our objective was to evaluate the influence of lactate on in vitro redox stability and thermostability of beef, horse, pork, and sheep myoglobins. Lactate (200 mM) had no effect (P>0.05) on redox stability at physiological (pH7.4, 37°C) and meat (pH 5.6, 4°C) conditions. However, lactate increased (Pmeat conditions was species-specific (Pmeat condition suggests that the color stability of lactate-enhanced fresh meat is not due to direct interactions between the ingredient and the heme protein. © 2013.

  11. Resonance surface enhanced Raman optical activity of myoglobin as a result of optimized resonance surface enhanced Raman scattering conditions

    DEFF Research Database (Denmark)

    Abdali, Salim; Johannessen, Christian; Nygaard, Jesper

    2007-01-01

    at single molecule level. The results of this work, using silver nanoparticles and a laser excitation of 532 nm, became only feasible when the concentrations of nanoparticles, aggregation agent NaCl and the studied molecule were optimized in a series of systematic optimization steps. The spectral analysis...... has shown that the SERS effect behaves consequently, depending on the concentration ratio of each component, i.e., myoglobin, Ag colloids and NaCl. Accordingly, it is shown here that SERS intensity has its maximum at certain concentration of these components, whereas below or above this value...

  12. Laparoscopic radical trachelectomy.

    Science.gov (United States)

    Rendón, Gabriel J; Ramirez, Pedro T; Frumovitz, Michael; Schmeler, Kathleen M; Pareja, Rene

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  13. Radical dematerialization and degrowth

    Science.gov (United States)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  14. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  15. Experimental methods in cryogenic spectroscopy: Stark effect measurements in substituted myoglobin

    Science.gov (United States)

    Moran, Bradley M.

    Dawning from well-defined tertiary structure, the active regions of enzymatic proteins exist as specifically tailored electrostatic microenvironments capable of facilitating chemical interaction. The specific influence these charge distributions have on ligand binding dynamics, and their impact on specificity, reactivity, and biological functionality, have yet to be fully understood. A quantitative determination of these intrinsic fields would offer insight towards the mechanistic aspects of protein functionality. This work seeks to investigate the internal molecular electric fields that are present at the oxygen binding site of myoglobin. Experiments are performed at 1 K on samples located within a glassy matrix, using the high-resolution technique spectral hole-burning. The internal electric field distributions can be explored by implementing a unique mathematical treatment for analyzing the effect that externally applied electric fields have on the spectral hole profiles. Precise control of the light field, the temperature, and the externally applied electric field at the site of the sample is crucial. Experimentally, the functionality of custom cryogenic temperature confocal scanning microscope was extended to allow for collection of imaging and spectral data with the ability to modulate the polarization of the light at the sample. Operation of the instrumentation was integrated into a platform allowing for seamless execution of input commands with high temporal inter-instrument resolution for collection of data streams. For the regulated control and cycling of the sample temperature. the thermal characteristics of the research Dewar were theoretically modeled to systematically predict heat flows throughout the system. A high voltage feedthrough for delivering voltages of up to 5000 V to the sample as positioned within the Dewar was developed. The burning of spectral holes with this particular experimental setup is highly repeatable. The quantum mechanical

  16. Electrochemical detection of cardiac biomarker myoglobin using polyphenol as imprinted polymer receptor.

    Science.gov (United States)

    Ribeiro, J A; Pereira, C M; Silva, A F; Sales, M Goreti F

    2017-08-15

    An electrochemical biosensor was developed by merging the features of Molecular Imprinting technique and Screen-Printed Electrode (SPE) for the simple and fast screening of cardiac biomarker myoglobin (Myo) in point-of-care (POC). The MIP artificial receptor for Myo was prepared by electrooxidative polymerization of phenol (Ph) on a AuSPE in the presence of Myo as template molecule. The choice of the most effective protein extraction procedure from the various extraction methods tested (mildly acidic/basic solutions, pure/mixed organic solvents, solutions containing surfactants and enzymatic digestion methods), and the optimization of the thickness of the polymer film was carefully undertaken in order to improve binding characteristics of Myo to the imprinted polymer receptor and increase the sensitivity of the MIP biosensor. The film thickness was optimized by adjusting scan rate and the number of cycles during cyclic voltammetric electropolymerization of Ph. The thickness of the polyphenol nanocoating of only few nanometres (∼4.4 nm), and similar to the protein diameter, brought in significant improvements in terms of sensor sensitivity. The binding affinity of MIP receptor film was estimated by fitting the experimental data to Freundlich isotherm and a ∼8 fold increase in the binding affinity of Myo to the imprinted polymer (K F = 0.119 ± 0.002 ng -1  mL) when compared to the non-imprinted polymer (K F  = 0.015 ± 0.002 ng -1  mL) which demonstrated excellent (re)binding affinity for the imprinted protein. The incubation of the Myo MIP receptor modified electrode with increasing concentration of protein (from 0.001 ng mL -1 to 100 μg mL -1 ) resulted in a decrease of the ferro/ferricyanide redox current. LODs of 2.1 and 14 pg mL -1 were obtained from calibration curves built in neutral buffer and diluted artificial serum, respectively, using SWV technique, enabling the detection of the protein biomarker at clinically relevant levels. The

  17. Counter radicalization development assistance

    OpenAIRE

    van Hippel, Karin

    2006-01-01

    The paper reviews current research and practice and recommends strategies for development agencies working in the Arab and Muslim world. It builds on the basic assumption that the realization of the Millennium Development Goals will be vital to reduce support for terrorism in the long term. Within this overall framework, emphasis is placed on particular programs that could be specifically applied to counter radicalization.

  18. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  19. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten

    2017-01-01

    incontinence in relation to sexual activity after surgery. This can present at the time of orgasm (ie, climacturia) or arise during arousal. In general, the problem subsides with time and pelvic floor training and tension penile loops can be used as treatments. Orgasmic disturbances after radical prostatectomy...

  20. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  1. Online Radicalization: Bangladesh Perspective

    Science.gov (United States)

    2017-06-09

    radicalization through cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom...cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom of speech...67 An Organizational Approach to Implement the Measures........................................ 69 Formation of

  2. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  3. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  4. Clinical evaluation of the CARDIAC STATus, a rapid immunochromatographic assay for simultaneous detection of elevated concentrations of CK-MB and myoglobin in whole blood

    NARCIS (Netherlands)

    Schouten, Y.; de Winter, R. J.; Gorgels, J. P.; Koster, R. W.; Adams, R.; Sanders, G. T.

    1998-01-01

    We studied the performance of the CARDIAC STATus, a new rapid, easy to perform qualitative whole blood bedside test for detection of elevated CK-MB and myoglobin in the emergency room. Blood samples from 182 consecutive patients with chest pain were drawn on admission and at five and seven hours

  5. What Is the True Color of Fresh Meat? A Biophysical Undergraduate Laboratory Experiment Investigating the Effects of Ligand Binding on Myoglobin Using Optical, EPR, and NMR Spectroscopy

    Science.gov (United States)

    Linenberger, Kimberly; Bretz, Stacey Lowery; Crowder, Michael W.; McCarrick, Robert; Lorigan, Gary A.; Tierney, David L.

    2011-01-01

    With an increased focus on integrated upper-level laboratories, we present an experiment integrating concepts from inorganic, biological, and physical chemistry content areas. Students investigate the effects of ligand strength on the spectroscopic properties of the heme center in myoglobin using UV-vis, [superscript 1]H NMR, and EPR…

  6. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  7. Structure-function paradigm in human myoglobin: how a single-residue substitution affects NO reactivity at low pO2.

    Science.gov (United States)

    Scorciapino, Mariano Andrea; Spiga, Enrico; Vezzoli, Alessandra; Mrakic-Sposta, Simona; Russo, Rosaria; Fink, Bruno; Casu, Mariano; Gussoni, Maristella; Ceccarelli, Matteo

    2013-05-22

    This work is focused on the two more expressed human myoglobin isoforms. In the literature, their different overexpression in high-altitude natives was proposed to be related to alternative/complementary functions in hypoxia. Interestingly, they differ only at residue-54, lysine or glutamate, which is external and far from the main binding site. In order to ascertain whether these two almost identical myoglobins might exert different functions and to contribute to a deeper understanding about myoglobin's oxygen-level dependent functioning, they have been compared with respect to dynamics, heme electronic structure, and NO reactivity at different O2 levels. Electron paramagnetic resonance (EPR) spectroscopy was employed to investigate the electronic structure of the nitrosyl-form, obtaining fundamental clues about a different bond interaction between the heme-iron and the proximal histidine and highlighting striking differences in NO reactivity, especially at a very low pO2. The experimental results well matched with the information provided by molecular dynamics simulations, which showed a significantly different dynamics for the two proteins only in the absence of O2. The single mutation differentiating the two myoglobins resulted in strongly affecting the plasticity of the CD-region (C-helix-loop-D-helix), whose fluctuations, being coupled to the solvent, were found to be correlated with the dynamics of the distal binding site. In the absence of O2, on the one hand a significantly different probability for the histidine-gate opening has been shown by MD simulations, and on the other a different yield of myoglobin-NO formation was experimentally observed through EPR.

  8. Free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  9. Trends in radical prostatectomy.

    Science.gov (United States)

    Eastham, James; Tokuda, Yuji; Scardino, Peter

    2009-02-01

    The surgical treatment of prostate cancer ideally removes the entire cancer, avoids excessive blood loss or serious perioperative complications, and results in complete recovery of continence and potency. To achieve this, the surgeon must excise sufficient periprostatic tissue to cure the cancer while preserving the cavernosal nerves required for erectile function and the neuromusculature required for normal urinary and bowel function. Here we will examine recent trends in radical prostatectomy, focusing on surgical technique.

  10. Zinc-Substituted Myoglobin Is a Naturally Occurring Photo-antimicrobial Agent with Potential Applications in Food Decontamination.

    Science.gov (United States)

    Delcanale, Pietro; Montali, Chiara; Rodríguez-Amigo, Beatriz; Abbruzzetti, Stefania; Bruno, Stefano; Bianchini, Paolo; Diaspro, Alberto; Agut, Montserrat; Nonell, Santi; Viappiani, Cristiano

    2016-11-16

    Zinc-substituted myoglobin (ZnMb) is a naturally occurring photosensitizer that generates singlet oxygen with a high quantum yield. Using a combination of photophysical and fluorescence imaging techniques, we demonstrate the interaction of ZnMb with Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. An efficient antibacterial action against S. aureus was observed, with a reduction up to 99.9999% in the number of colony-forming units, whereas no sizable effect was detected against E. coli. Because ZnMb is known to form during the maturation of additive-free not-cooked cured ham, the use of this protein as a built-in photodynamic agent may constitute a viable method for the decontamination of these food products from Gram-positive bacteria.

  11. MWCNT-cysteamine-Nafion modified gold electrode based on myoglobin for determination of hydrogen peroxide and nitrite.

    Science.gov (United States)

    Canbay, Erhan; Şahin, Berika; Kıran, Müge; Akyilmaz, Erol

    2015-02-01

    In this work, a novel amperometric biosensor of hydrogen peroxide (H2O2) was developed based on the immobilization of myoglobin (Mb) on the surface of the multi-walled carbon nanotube (MWCNT) -Nafion-cysteamine (CA) modified gold electrode (Au) and its electrocatalytic activity was used for the determination of nitrite (NO2(-)). In the optimization studies, the best MWCNT and myoglobin amount were investigated. It was discovered at the experiments for the optimization of the working conditions that the buffer at this study as 50.0mM, pH7.0 phosphate buffer (PBS) and working temperature as 30°C for the H2O2 biosensor. It was determined at the characterization studies on the biosensor that linear results are obtained between the ranges of 0.1μM to 70.0μM for H2O2 concentration and 1-250μM for NO2(-). The reproducibility of the biosensor was determined both H2O2 and nitrite. From the experiments, average value, standard deviation (SD) and coefficients of variation (CV%) were calculated to be 10.02±0.43μM, and 4.29% for 10.0μM H2O2 (n=6) and 52.0±2.1μM, and 3.89% for 50.0μM nitrite (n=8), respectively. At the same time the sample was analyzed for NO2(-) in drinking and mineral waters. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  13. Studies on meat color, myoglobin content, enzyme activities, and genes associated with oxidative potential of pigs slaughtered at different growth stages

    Science.gov (United States)

    Yu, Qin Ping; Feng, Ding Yuan; Xiao, Juan; Wu, Fan; He, Xiao Jun; Xia, Min Hao; Dong, Tao; Liu, Yi Hua; Tan, Hui Ze; Zou, Shi Geng; Zheng, Tao; Ou, Xian Hua; Zuo, Jian Jun

    2017-01-01

    Objective This experiment investigated meat color, myoglobin content, enzyme activities, and expression of genes associated with oxidative potential of pigs slaughtered at different growth stages. Methods Sixty 4-week-old Duroc×Landrace×Yorkshire pigs were assigned to 6 replicate groups, each containing 10 pigs. One pig from each group was sacrificed at day 35, 63, 98, and 161 to isolate longissimus dorsi and triceps muscles. Results Meat color scores were higher in pigs at 35 d than those at 63 d and 98 d (pMeat color scores were correlated to the proportion of oxymyoglobin (r = 0.59, pmeat color, myoglobin content, enzyme activities, and genes associated with oxidative potential varied at different stages. PMID:28728400

  14. Hydroxyl radical-modified fibrinogen as a marker of thrombosis: the role of iron.

    Science.gov (United States)

    Lipinski, B; Pretorius, E

    2012-07-01

    Excessive free iron in blood and in organ tissues (so called iron overload) has been observed in degenerative diseases such as atherosclerosis, cancer, neurological, and certain autoimmune diseases, in which fibrin-like deposits are also found. Although most of the body iron is bound to hemoglobin and myoglobin in a divalent ferrous form, a certain amount of iron exists in blood as a trivalent (ferric) ion. This particular chemical state of iron has been shown to be toxic to the human body when not controlled by endogenous and/or dietary chelating agents. Experiments described in this paper show for the first time that ferric ions (Fe(3+)) can generate hydroxyl radicals without participation of any redox agent, thus making it a special case of the Fenton reaction. Ferric chloride was also demonstrated to induce aggregation of purified fibrinogen at the same molar concentrations that were used for the generation of hydroxyl radicals. Iron-aggregated fibrinogen, by contrast to native molecule, could not be dissociated into polypeptide subunit chains as shown in a polyacrylamide gel electrophoresis. The mechanism of this phenomenon is very likely based on hydroxyl radical-induced modification of fibrinogen tertiary structure with the formation of insoluble aggregates resistant to enzymatic and chemical degradations. Soluble modified fibrinogen species can be determined in blood of thrombotic patients by the reaction with protamine sulfate and/or by scanning electron microscopy. In view of these findings, it is postulated that iron-induced alterations in fibrinogen structure is involved in pathogenesis of certain degenerative diseases associated with iron overload and persistent thrombosis. It is concluded that the detection of hydroxyl radical-modified fibrinogen may be utilized as a marker of a thrombotic condition in human subjects.

  15. High-level expression and deuteration of sperm whale myoglobin: A study of its solvent structure by X-ray and neutron diffraction methods

    Energy Technology Data Exchange (ETDEWEB)

    Shu, F. [State Univ. of New York, Stony Brook, NY (United States); Ramakrishnan, V. [Brookhaven National Laboratory, Upton, NY (United States); Schoenborn, B.P. [Los Alamos National Laboratory, NM (United States)

    1994-12-31

    Neutron diffraction has become one of the best ways to study light atoms, such as hydrogens. Hydrogen however has a negative coherent scattering factor, and a large incoherent scattering factor, while deuterium has virtually no incoherent scattering, but a large positive coherent scattering factor. Beside causing high background due to its incoherent scattering, the negative coherent scattering of hydrogen tends to cancel out the positive contribution from other atoms in a neutron density map. Therefore a fully deuterated sample will yield better diffraction data with stronger density in the hydrogen position. On this basis, a sperm whale myoglobin gene modified to include part of the A cII protein gene has been cloned into the T7 expression system. Milligram amounts of fully deuterated holo-myoglobin have been obtained and used for crystallization. The synthetic sperm whale myoglobin crystallized in P2{sub 1} space group isomorphous with the native protein crystal. A complete X-ray diffraction dataset at 1.5{Angstrom} has been collected. This X-ray dataset, and a neutron data set collected previously on a protonated carbon-monoxymyoglobin crystal have been used for solvent structure studies. Both X-ray and neutron data have shown that there are ordered hydration layers around the protein surface. Solvent shell analysis on the neutron data further has shown that the first hydration layer behaves differently around polar and apolar regions of the protein surface. Finally, the structure of per-deuterated myoglobin has been refined using all reflections to a R factor of 17%.

  16. High-level expression and deuteration of sperm whale myoglobin: A study of its solvent structure by X-ray and neutron diffraction methods

    International Nuclear Information System (INIS)

    Shu, F.; Ramakrishnan, V.; Schoenborn, B.P.

    1994-01-01

    Neutron diffraction has become one of the best ways to study light atoms, such as hydrogens. Hydrogen however has a negative coherent scattering factor, and a large incoherent scattering factor, while deuterium has virtually no incoherent scattering, but a large positive coherent scattering factor. Beside causing high background due to its incoherent scattering, the negative coherent scattering of hydrogen tends to cancel out the positive contribution from other atoms in a neutron density map. Therefore a fully deuterated sample will yield better diffraction data with stronger density in the hydrogen position. On this basis, a sperm whale myoglobin gene modified to include part of the A cII protein gene has been cloned into the T7 expression system. Milligram amounts of fully deuterated holo-myoglobin have been obtained and used for crystallization. The synthetic sperm whale myoglobin crystallized in P2 1 space group isomorphous with the native protein crystal. A complete X-ray diffraction dataset at 1.5 Angstrom has been collected. This X-ray dataset, and a neutron data set collected previously on a protonated carbon-monoxymyoglobin crystal have been used for solvent structure studies. Both X-ray and neutron data have shown that there are ordered hydration layers around the protein surface. Solvent shell analysis on the neutron data further has shown that the first hydration layer behaves differently around polar and apolar regions of the protein surface. Finally, the structure of per-deuterated myoglobin has been refined using all reflections to a R factor of 17%

  17. Proteomic based approach for characterizing 4-hydroxy-2-nonenal induced oxidation of buffalo (Bubalus bubalis) and goat (Capra hircus) meat myoglobins

    OpenAIRE

    Maheswarappa, Naveena B.; Rani, K. Usha; Kumar, Y. Praveen; Kulkarni, Vinayak V.; Rapole, Srikanth

    2016-01-01

    Background Myoglobin (Mb) is a sarcoplasmic heme protein primarily responsible for meat color and its chemistry is species specific. 4-hydroxy-2-nonenal (HNE) is a cytotoxic lipid derived aldehyde detected in meat and was reported to covalently adduct with nucleophilic histidine residues of Mb and predispose it to greater oxidation. However, no literature is available on characterization of lipid oxidation induced oxidation of Indian water buffalo (Bubalus bubalis) and goat (Capra hircus) myo...

  18. Hydroxyl radical reactivity with diethylhydroxylamine

    International Nuclear Information System (INIS)

    Gorse, R.A. Jr.; Lii, R.R.; Saunders, B.B.

    1977-01-01

    Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals

  19. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and 14 N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and 14 N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy

  20. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  1. Cathodic detection of H2O2 based on nanopyramidal gold surface with enhanced electron transfer of myoglobin.

    Science.gov (United States)

    Xia, Peipei; Liu, Haiqing; Tian, Yang

    2009-04-15

    Direct and reversible electron transfer of myoglobin (Mb), for the first time, is achieved at nanopyramidal gold surface, which was fabricated by one-step electrodeposition, with redox formal potential of 0.21+/-0.01 V (vs. Ag/AgCl) and an apparent heterogeneous electron-transfer rate constant (k(s)) of 1.6+/-0.2 s(-1). Electrochemical investigation indicates that Mb is stably confined on the nanopyramidal gold surface and maintains electrocatalytic activity toward hydrogen peroxide (H(2)O(2)). The facilitated electron transfer combined with the intrinsic catalytical activity of Mb substantially construct the third-generation biosensor for H(2)O(2). The positive redox potential of Mb at the nanostructured gold electrode gives a strong basis for determination of H(2)O(2) with high selectivity. Besides this advantage, the present biosensor also exhibits quick response time, broad linear range, and good sensitivity. The dynamic detection linear range is from 1 microM to 1.4 mM with a detection limit of 0.5 microM at 3sigma. The striking analytical performance of the present biosensor, as well as the biocompatibility of gold nanostructures provided a potential for continuous, on-line detection of H(2)O(2) in the biological system.

  2. Ontogenetic changes in skeletal muscle fiber type, fiber diameter and myoglobin concentration in the Northern elephant seal (Mirounga angustirostris

    Directory of Open Access Journals (Sweden)

    Colby eMoore

    2014-06-01

    Full Text Available Northern elephant seals (Mirounga angustirostris (NES are known to be deep, long-duration divers and to sustain long-repeated patterns of breath-hold, or apnea. Some phocid dives remain within the bounds of aerobic metabolism, accompanied by physiological responses inducing lung compression, bradycardia and peripheral vasoconstriction. Current data suggest an absence of type IIb fibers in pinniped locomotory musculature. To date, no fiber type data exist for NES, a consummate deep diver. In this study, NES were biopsied in the wild. Ontogenetic changes in skeletal muscle were revealed through succinate dehydrogenase (SDH based fiber typing. Results indicated a predominance of uniformly shaped, large type I fibers and elevated myoglobin (Mb concentrations in the longissimus dorsi (LD muscle of adults. No type II muscle fibers were detected in any adult sampled. This was in contrast to the juvenile animals that demonstrated type II myosin in Western Blot analysis, indicative of an ontogenetic change in skeletal muscle with maturation. These data support previous hypotheses that the absence of type II fibers indicates reliance on aerobic metabolism during dives, as well as a depressed metabolic rate and low energy locomotion. We also suggest that the lack of type IIb fibers (adults may provide a protection against ischemia reperfusion (IR injury in vasoconstricted peripheral skeletal muscle.

  3. Electron Transfer of Myoglobin Immobilized in Au Electrodes Modified with a RAFT PMMA-Block-PDMAEMA Polymer

    Directory of Open Access Journals (Sweden)

    Carla N. Toledo

    2014-01-01

    Full Text Available Myoglobin was immobilized with poly(methyl methacrylate-block-poly[(2-dimethylaminoethyl methacrylate]PMMA-block-PDMAEMA polymer synthesized by reversible addition-fragmentation chain transfer technique (RAFT. Cyclic voltammograms gave direct and slow quasireversible heterogeneous electron transfer kinetics between Mb-PMMA-block-PDMAEMA modified electrode and the redox center of the protein. The values for electron rate constant (Ks and transfer coefficient (α were 0.055±0.01·s−1 and 0.81±0.08, respectively. The reduction potential determined as a function of temperature (293–328 K revealed a value of reaction center entropy of ΔS0 of 351.3±0.0002 J·mol−1·K−1 and enthalpy change of -76.8±0.1 kJ·mol−1, suggesting solvent effects and charge ionization atmosphere involved in the reaction parallel to hydrophobic interactions with the copolymer. The immobilized protein also exhibits an electrocatalytical response to reduction of hydrogen peroxide, with an apparent Km of 114.7±58.7 μM. The overall results substantiate the design and use of RAFT polymers towards the development of third-generation biosensors.

  4. EPR analysis of cyanide complexes of wild-type human neuroglobin and mutants in comparison to horse heart myoglobin.

    Science.gov (United States)

    Van Doorslaer, Sabine; Trandafir, Florin; Harmer, Jeffrey R; Moens, Luc; Dewilde, Sylvia

    2014-06-01

    Electron paramagnetic resonance (EPR) data reveal large differences between the ferric ((13)C-)cyanide complexes of wild-type human neuroglobin (NGB) and its H64Q and F28L point mutants and the cyanide complexes of mammalian myo- and haemoglobin. The point mutations, which involve residues comprising the distal haem pocket in NGB, induce smaller, but still significant changes, related to changes in the stabilization of the cyanide ligand. Furthermore, for the first time, the full (13)C hyperfine tensor of the cyanide carbon of cyanide-ligated horse heart myoglobin (hhMb) was determined using Davies ENDOR (electron nuclear double resonance). Disagreement of these experimental data with earlier predictions based on (13)C NMR data and a theoretical model reveal significant flaws in the model assumptions. The same ENDOR procedure allowed also partial determination of the corresponding (13)C hyperfine tensor of cyanide-ligated NGB and H64QNGB. These (13)C parameters differ significantly from those of cyanide-ligated hhMb and challenge our current theoretical understanding of how the haem environment influences the magnetic parameters obtained by EPR and NMR in cyanide-ligated haem proteins. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Structural studies of the 'Aplysia Brasiliana' and 'Dermochelis Coriacea' myoglobins by optical and electron paramagnetic resonance techniques

    International Nuclear Information System (INIS)

    Baffa Filho, O.

    1984-01-01

    The myoglobins of 'Applysia Brasiliana' (MbApB) and of the sea turtle 'Dermochelis Coriacea' (MbT) are studied with special attention devoted to the acid-alkalyne transition (AAT), the interaction with transition metals and temperature induced conformational changes in order to characterize structural differences in these proteins. The AAT of MbApB has a pK = 7.2 obtained from the EPR spectra of Fe 3+ at g (perpendicular) = 5.83 and a pK = 7.5 obtained from optical absorption (lambda = 590 nm). The EPR Spectrum of Fe 3+ at alkalyne pH shows a rhombic distortion of the ion crystal field which is in agreement with the absence in this protein of the distal histidine residue. The ESR lines associated with the low spin configuration are considerably broadened. This effect can be explained by fluctuations on the heme position relative to the symmetry axis. MbApB forms complexes with both Cu 2+ and Mn 2+ only one binding site is obtained for both metals in the protein. This site probably has common ligands for mN 2+ and Cu 2+ as the binding is competitive, suggesting also the at the Cu 2+ complex is more stable than the Mn 2+ one (K sub(A) sup(M) sub(n 2+ )) = (11,5 + - 0,8).10 3 M -1 . (Author) [pt

  6. Application of three-dimensional reduced graphene oxide-gold composite modified electrode for direct electrochemistry and electrocatalysis of myoglobin.

    Science.gov (United States)

    Shi, Fan; Xi, Jingwen; Hou, Fei; Han, Lin; Li, Guangjiu; Gong, Shixing; Chen, Chanxing; Sun, Wei

    2016-01-01

    In this paper a three-dimensional (3D) reduced graphene oxide (RGO) and gold (Au) composite was synthesized by electrodeposition and used for the electrode modification with carbon ionic liquid electrode (CILE) as the substrate electrode. Myoglobin (Mb) was further immobilized on the surface of 3D RGO-Au/CILE to obtain an electrochemical sensing platform. Direct electrochemistry of Mb on the modified electrode was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electron transfer of Mb with the modified electrode. The results can be ascribed to the presence of highly conductive 3D RGO-Au composite on the electrode surface that accelerate the electron transfer rate between the electroactive center of Mb and the electrode. The Mb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.2 to 36.0 mmol/L with the detection limit of 0.06 mmol/L (3σ). Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Radical production in biological systems

    International Nuclear Information System (INIS)

    Johnson, J.R.; Akabani, G.

    1994-10-01

    This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

  8. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  9. Redox properties of free radicals

    International Nuclear Information System (INIS)

    Neta, P.

    1981-01-01

    Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

  10. Hot wire radicals and reactions

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2006-01-01

    Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

  11. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2013-01-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  12. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2014-07-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  13. Radioimmunoassay of serum myoglobin and its signifance for diagnosis and therapy of musculoskeletal diseases. Der radioimmunologische Myoglobinnachweis im Serum und seine Bedeutung bei der Diagnostik und Therapie von Skelettmuskelerkrankungen

    Energy Technology Data Exchange (ETDEWEB)

    Kiessling, W.R.

    1982-01-01

    A commercial test kit for radioimmunologic proof of myoglobin in serum was tested with regard to its specificty, sensitivity, precision, reproducibility, recovery and use in the diagnosis and therapy of musculoskeletal diseases. In the serum of 164 healthy control persons (age: 2-79 years) the individual myoglobin concentrations ranged from 4 to 60 ng/ml. Among 300 patients with muscular diseases extreme myoglobinaemia in acute rhabdomyolysis, polymyositis and dermatomyositis and different progressive muscular dystrophies could be detected. Slightly increased myoglobin concentrations could be proved in a number of patient with amyotrophic lateral sklerosis, neural muscular atrophy and in all cases of spinal muscular atrophy of the Kugelberg-Welander type. Confirmed DMD patients exhibited in about 80% of the cases hypermyoglobinaemia, and about 11% of 43 possible DMD patients showed an increase in myoglobin. Taking acute rhabdomyolysis and myositis as an example, it was found that myoglobin correlates well with the clinical course of these diseases and permits safe inferences as to the efficiency of the therapy chosen.

  14. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... Radical change by entrepreneurial design then becomes the focal point, in order to acquaint the reader with the strategies and tactics of well-known entrepreneurs who have been successful in molding...

  15. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David

    2013-01-01

    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programmes...

  16. Radical prostatectomy. Results and indications

    International Nuclear Information System (INIS)

    Jacqmin, D.

    1997-01-01

    Radical prostatectomy is the surgical curative treatment of localized prostate cancer. The survival is good in young patients (<70) with T2 N0M0 tumors and more than 10 year's life expectancy. Side-effects are urinary incontinence, impotence and anastomosis stricture. Quality of life should be considered as an important factor for the choice of the patient between radical prostatectomy, radiotherapy and follow-up. (author)

  17. Radical Islamism and Failed Developmentalism

    OpenAIRE

    Rahnema, Saeed

    2008-01-01

    The rise of radical Islamism in recent years does not limit the applicability of the concept of cultural nationalism. Rather the two are intertwined in ways which this article will attempt to highlight. Islam took specific national forms as modern nation-states arose and the contemporary resurgence of radical Islamism also follows that modern pattern. I examine the emergence of the three most important movements in the Islamic world, namely, the Muslim Brotherhood in Egypt, Jama'at-e Islami i...

  18. Laparoscopic radical cystectomy: key points

    Directory of Open Access Journals (Sweden)

    D. V. Perlin

    2018-01-01

    Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

  19. Significance of myoglobin as an oxygen store and oxygen transporter in the intermittently perfused human heart: a model study.

    Science.gov (United States)

    Endeward, Volker; Gros, Gerolf; Jürgens, Klaus D

    2010-07-01

    The mechanisms by which the left ventricular wall escapes anoxia during the systolic phase of low blood perfusion are investigated, especially the role of myoglobin (Mb), which can (i) store oxygen and (ii) facilitate intracellular oxygen transport. The quantitative role of these two Mb functions is studied in the maximally working human heart. Because discrimination between Mb functions has not been achieved experimentally, we use a Krogh cylinder model here. At a heart rate of 200 beats/min and a 1:1 ratio of diastole/systole, the systole lasts for 150 ms. The basic model assumption is that, with mobile Mb, the oxygen stored in the end-diastolic left ventricle wall exactly meets the demand during the 150 ms of systolic cessation of blood flow. The coronary blood flow necessary to achieve this agrees with literature data. By considering Mb immobile or setting its concentration to zero, respectively, we find that, depending on Mb concentration, Mb-facilitated O(2) transport maintains O(2) supply to the left ventricle wall during 22-34 of the 150 ms, while Mb storage function accounts for a further 12-17 ms. When Mb is completely absent, anoxia begins to develop after 116-99 ms. While Mb plays no significant role during diastole, it supplies O(2) to the left ventricular wall for < or = 50 ms of the 150 ms systole, whereas capillary haemoglobin is responsible for approximately 80 ms. Slight increases in haemoglobin concentration, blood flow, or capillary density can compensate the absence of Mb, a finding which agrees well with the observations using Mb knockout mice.

  20. Electrochemical H2O2 biosensor composed of myoglobin on MoS2 nanoparticle-graphene oxide hybrid structure.

    Science.gov (United States)

    Yoon, Jinho; Lee, Taek; Bapurao G, Bharate; Jo, Jinhee; Oh, Byung-Keun; Choi, Jeong-Woo

    2017-07-15

    In this research, the electrochemical biosensor composed of myoglobin (Mb) on molybdenum disulfide nanoparticles (MoS 2 NP) encapsulated with graphene oxide (GO) was fabricated for the detection of hydrogen peroxide (H 2 O 2 ). Hybrid structure composed of MoS 2 NP and GO (GO@MoS 2 ) was fabricated for the first time to enhance the electrochemical signal of the biosensor. As a sensing material, Mb was introduced to fabricate the biosensor for H 2 O 2 detection. Formation and immobilization of GO@MoS 2 was confirmed by transmission electron microscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, and scanning tunneling microscopy. Immobilization of Mb, and electrochemical property of biosensor were investigated by cyclic voltammetry and amperometric i-t measurements. Fabricated biosensor showed the electrochemical signal enhanced redox current as -1.86μA at an oxidation potential and 1.95μA at a reduction potential that were enhanced relative to those of electrode prepared without GO@MoS 2 . Also, this biosensor showed the reproducibility of electrochemical signal, and retained the property until 9 days from fabrication. Upon addition of H 2 O 2 , the biosensor showed enhanced amperometric response current with selectivity relative to that of the biosensor prepared without GO@MoS 2 . This novel hybrid material-based biosensor can suggest a milestone in the development of a highly sensitive detecting platform for biosensor fabrication with highly sensitive detection of target molecules other than H 2 O 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Spectroscopic Study of the Interaction between Horse Heart Myoglobin and Zirconium(IV)-Substituted Polyoxometalates as Artificial Proteases.

    Science.gov (United States)

    Ly, Hong Giang T; Parac-Vogt, Tatjana N

    2017-09-20

    A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and 1 H and 31 P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr IV -Keggin, exhibits the strongest interaction with HHM. 31 P NMR spectroscopy studies show that this POM dissociates in solution, resulting in the formation of a monomeric 1:1 Zr IV -Keggin structure, which is likely to be a catalytically active species. In the presence of Zr IV -POMs, HHM does not undergo complete denaturation, as evidenced by CD, UV/Vis, tryptophan fluorescence, and 1 H NMR spectroscopy. CD spectroscopy shows a gradual decrease in the α-helical content of HHM upon addition of Zr IV -POMs. The largest effect is observed in the presence of a large Zr IV -Wells-Dawson structure, whereas small Zr IV -Lindqvist POM has the least influence on the decrease in the α-helical content of HHM. In all cases, the Soret band at λ=409 nm is maintained in the presence of all examined Zr-POMs, which indicates that no conformational changes in the protein occur near the heme group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The games radicals play : special issue on free radicals and radical ions

    OpenAIRE

    Walton, J.C.; Williams, F.

    2015-01-01

    Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

  3. Studies on meat color, myoglobin content, enzyme activities, and genes associated with oxidative potential of pigs slaughtered at different growth stages

    Directory of Open Access Journals (Sweden)

    Qin Ping Yu

    2017-12-01

    Full Text Available Objective This experiment investigated meat color, myoglobin content, enzyme activities, and expression of genes associated with oxidative potential of pigs slaughtered at different growth stages. Methods Sixty 4-week-old Duroc×Landrace×Yorkshire pigs were assigned to 6 replicate groups, each containing 10 pigs. One pig from each group was sacrificed at day 35, 63, 98, and 161 to isolate longissimus dorsi and triceps muscles. Results Meat color scores were higher in pigs at 35 d than those at 63 d and 98 d (p<0.05, and those at 98 d were lower than those at 161 d (p<0.05. The total myoglobin was higher on 161 d compared with those at 63 d and 98 d (p<0.05. Increase in the proportions of metmyoglobin and deoxymyoglobin and a decrease in oxymyoglobin were observed between days 35 and 161 (p<0.05. Meat color scores were correlated to the proportion of oxymyoglobin (r = 0.59, p<0.01, and negatively correlated with deoxymyoglobin and metmyoglobin content (r = −0.48 and −0.62, p<0.05. Malate dehydrogenase (MDH activity at 35 d and 98 d was higher than that at 161 d (p<0.05. The highest lactate dehydrogenase/MDH ratio was achieved at 161 d (p<0.05. Calcineurin mRNA expression decreased at 35 d compared to that at 63 d and 98 d (p<0.05. Myocyte enhancer factor 2 mRNA results indicated a higher expression at 161 d than that at 63 d and 98 d (p<0.05. Conclusion Porcine meat color, myoglobin content, enzyme activities, and genes associated with oxidative potential varied at different stages.

  4. Aliphatic semisynthetic amino terminal variants of myoglobin: enrichment with carbon-13, determination and interpretation of terminal pK values and motions

    International Nuclear Information System (INIS)

    Busch, M.R.

    1985-01-01

    The synthesis of a series of myoglobins substituted in the amino terminal residue to provide variation in the aliphatic nature of the side chain and enrichment in 13 C was accomplished by semisynthetic methods. The replacements of valine, the native first residue, included 13 C enriched glycine, alanine, valine, leucine, and isoleucine. The products were extensively characterized and found to be virtually indistinguishable by most physical methods. 13 C NMR spectroscopy showed significant differences in the amino terminal pK value, ranging from 7.72 for myoglobin to 7.15 for myoglobin. Consideration of the electrostatic effects of the charge array indicated a balance of interactions at this site not significantly altered by variations in the side chain. By examination of the crystal structure, consideration of earlier work regarding the interactions of the side chain of Leu-2, and data regarding the motions of the terminal residue, it was concluded that the interaction of the side chain of the first residue with the hydrophobic cluster formed primarily by close contact of invariant residues Leu-2 and Leu-137 was the primary cause for the reduction in the terminal pK values seen for the larger aliphatics. By restricting the freedom of the residue, this interaction limits the available hydration volume, and consequently favors the unprotonated form of the amine. The concurrent observation of both functional elements in the series of α amino terminal residues brings out the interrelated consequences for the two categories of solvent interactions controlling structural and functional properties in a graded way

  5. Radioimmunoassay of serum myoglobin: evaluation and modification of a commercial kit and assessment of its usefulness for detecting acute myocardial infarction

    International Nuclear Information System (INIS)

    Kubasik, N.P.; Guiney, W.; Warren, K.; D'Souza, J.P.; Sine, H.E.; Brody, B.B.

    1978-01-01

    We evaluated a modified procedure for a commercially available myoglobin radioimmunoassay kit (Nuclear Medical Systems). Within-run and run-to-run precision was acceptable. Normal ranges were established and parallelism studies performed. Clinical usefulness was assessed in 100 consecutive patients admitted to our coronary-care facility. The determinations were done daily, along with creatine kinase and its isoenzymes, and lactate dehydrogenase and its isoenzymes. Fifty of the 100 patients ultimately were shown to have had acute myocardial infarction. Myoglobinemia was present in most of the patients with acute myocardial infarction, but information on its presence was less useful clinically than was detection of creatine kinase isoenzyme MB

  6. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  7. 17.9.3 Radical cations of diazo compounds

    Science.gov (United States)

    Davies, A. G.

    This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  8. Photoionization of the OH radical

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1985-01-01

    The hydroxyl radical (OH) is one of the most thoroughly studied free radicals because of its importance in atmospheric chemistry, combustion processes, and the interstellar medium. Detailed experimental and theoretical studies have been performed on the ground electronic state (X 2 PI/sub i/) and on the four lowest bound excited electronic states (A 2 Σ + , B 2 Σ + , D 2 Σ - , and C 2 Σ + ). However, because it is difficult to distinguish the spectrum of OH from the spectra of the various radical precursors, the absorption spectrum in the wavelength region below 1200 A has not been well characterized. In the present work, the spectrum of OH has been determined in the wavelength region from 750 to 950 A using the technique of photoionization mass spectrometry. This technique allows complete separation of the spectrum of OH from that of the other components of the discharge and permits the unambiguous determination of the spectrum of OH

  9. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  10. Donor free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  11. Radical feminists & trans activists truce

    OpenAIRE

    Mackay, F.

    2014-01-01

    #GenderWeek: Truce! When radical feminists and trans feminists empathise\\ud Feminist Times\\ud By Finn Mackay \\ud read all #GenderWeek articles.\\ud We wanted to explore the ground between the polarised, entrenched positions in the so-called “TERF-war”. Radical feminists on one pole, trans-inclusionary feminists and trans activists on the other. The disputed territory being women-only space, language and the ever changing legal framework surrounding gender.\\ud Entrenchment leads to stalemate. S...

  12. Influence of Diet and Postmortem Ageing on Oxidative Stability of Lipids, Myoglobin and Myofibrillar Proteins and Quality Attributes of Gluteus Medius Muscle in Goats

    Science.gov (United States)

    Adeyemi, Kazeem Dauda; Shittu, Rafiat Morolayo; Sabow, Azad Behnan; Ebrahimi, Mahdi; Sazili, Awis Qurni

    2016-01-01

    This study appraised the effects of dietary blend of 80% canola oil and 20% palm oil and postmortem ageing on oxidative stability, fatty acids and quality attributes of gluteus medius (GM) muscle in goats. Twenty-four Boer bucks were randomly allotted to diet supplemented with 0, 4 and 8% oil blend, fed for 100 days and slaughtered, and the GM muscle was subjected to a 7 d chill storage (4±1°C). Diet had no effect (P> 0.05) on the colour, drip loss, thiobarbituric acid-reactive substances (TBARS) value, free thiol, carbonyl, myoglobin and metmyoglobin contents, metmyoglobin reducing activity (MRA), antioxidant enzyme activities and abundance of myosin heavy chain (MHC) and actin in the GM muscle in goats. The meat from goats fed 4 and 8% oil blend had higher (Pgoats. The GM muscle from the oil-supplemented goats had lower (Pgoats. Nonetheless, diet did not affect (Pgoats. Regardless of the diet, the free thiol and myoglobin contents, concentration of tocopherol and total carotenoids, MHC and MRA in the GM muscle decreased (P< 0.05) while carbonyl content, TBARS, drip loss and metmyoglobin content increased over storage. Dietary blend of 80% canola oil and 20% palm oil beneficially altered tissue lipids without hampering the oxidative stability of chevon. PMID:27138001

  13. Roles of nitric oxide, nitrite and myoglobin on myocardial efficiency in trout (Oncorthynchus mykiss) and goldfish (Carassius auratus): implications for hypoxia tolerance

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Faggiano, Serena; Helbo, Signe

    2010-01-01

    The roles of nitric oxide synthase activity (NOS), nitrite and myoglobin (Mb) in the regulation of myocardial function during hypoxia were examined in trout and goldfish, a hypoxia-intolerant and hypoxia-tolerant species, respectively. We measured the effect of NOS inhibition, adrenaline and nitr......The roles of nitric oxide synthase activity (NOS), nitrite and myoglobin (Mb) in the regulation of myocardial function during hypoxia were examined in trout and goldfish, a hypoxia-intolerant and hypoxia-tolerant species, respectively. We measured the effect of NOS inhibition, adrenaline...... in both trout and goldfish myocardium, with trout showing a significant increase in the O2 utilization efficiency, i.e. the ratio of twitch force to O2 consumption, suggesting an increased anaerobic metabolism. NOS inhibition enhanced myocardial O2 consumption and decreased efficiency, indicating...... that mitochondrial respiration is under a tone of NOS-produced NO. When trout myocardial twitch force and O2 consumption are enhanced by adrenaline, this NO tone disappears. Consistent with its conversion to NO, nitrite reduced O2 consumption and increased myocardial efficiency in trout but not in goldfish...

  14. Interfacial hydration, dynamics and electron transfer: multi-scale ET modeling of the transient [myoglobin, cytochrome b5] complex.

    Science.gov (United States)

    Keinan, Shahar; Nocek, Judith M; Hoffman, Brian M; Beratan, David N

    2012-10-28

    Formation of a transient [myoglobin (Mb), cytochrome b(5) (cyt b(5))] complex is required for the reductive repair of inactive ferri-Mb to its functional ferro-Mb state. The [Mb, cyt b(5)] complex exhibits dynamic docking (DD), with its cyt b(5) partner in rapid exchange at multiple sites on the Mb surface. A triple mutant (Mb(3M)) was designed as part of efforts to shift the electron-transfer process to the simple docking (SD) regime, in which reactive binding occurs at a restricted, reactive region on the Mb surface that dominates the docked ensemble. An electrostatically-guided brownian dynamics (BD) docking protocol was used to generate an initial ensemble of reactive configurations of the complex between unrelaxed partners. This ensemble samples a broad and diverse array of heme-heme distances and orientations. These configurations seeded all-atom constrained molecular dynamics simulations (MD) to generate relaxed complexes for the calculation of electron tunneling matrix elements (T(DA)) through tunneling-pathway analysis. This procedure for generating an ensemble of relaxed complexes combines the ability of BD calculations to sample the large variety of available conformations and interprotein distances, with the ability of MD to generate the atomic level information, especially regarding the structure of water molecules at the protein-protein interface, that defines electron-tunneling pathways. We used the calculated T(DA) values to compute ET rates for the [Mb(wt), cyt b(5)] complex and for the complex with a mutant that has a binding free energy strengthened by three D/E → K charge-reversal mutations, [Mb(3M), cyt b(5)]. The calculated rate constants are in agreement with the measured values, and the mutant complex ensemble has many more geometries with higher T(DA) values than does the wild-type Mb complex. Interestingly, water plays a double role in this electron-transfer system, lowering the tunneling barrier as well as inducing protein interface

  15. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  16. Laparoscopically assisted vaginal radical trachelectomy

    International Nuclear Information System (INIS)

    Bielik, T.; Karovic, M.; Trska, R.

    2013-01-01

    Purpose: Radical trachelectomy is a fertility-sparing procedure with the aim to provide adequate oncological safety to patients with cervical cancer while preserving their fertility. The purpose of this study was to retrospectively evaluate, in a series of 3 patients, the feasibility, morbidity, and safety of laparoscopically assisted vaginal radical trachelectomy for early cervical cancer. Patients and Methods: Three non consecutive patients with FIGO stage IA1 and IB1 cervical cancer was evaluated in a period of years 2008 - 2011. The patients underwent a laparoscopic pelvic lymphadenectomy and radical parametrectomy class II procedure according to the Piver classification. The section of vaginal cuff, trachelectomy, permanent cerclage and isthmo-vaginal anastomosis ware realised by vaginal approach. Results: The median operative time, the median blood loss and the mean number of resected pelvic nodes was comparable with published data. Major intraoperative complications did not occur and no patient required a blood transfusion. The median follow-up time was 33 (38-59) months. One vaginal recurrence occurred in 7 months after primary surgery. The patient was underwent a radicalisation procedure and adjuvant oncologic therapy and now is free of disease. Conclusions: Laparoscopically assisted vaginal radical trachelectomy (LAVRT)may be an alternative in fertility-preserving surgery for early cervical cancer. The procedure offers patients potential benefits of minimally invasive surgery with adequate oncological safety, but it should be reserved for oncologic surgeons trained in advanced laparoscopic procedures. (author)

  17. Is Radical Innovation Management Misunderstood?

    DEFF Research Database (Denmark)

    Kristiansen, Jimmi Normann; Gertsen, Frank

    2015-01-01

    This paper poses a critical view on radical innovation (RI) management research and practice. The study investigates how expected RI performance influences firms’ under- standing of their RI capability. RI performance is often based on output measures such as market shares or fiscal return...

  18. Exploring the Theories of Radicalization

    Directory of Open Access Journals (Sweden)

    Maskaliūnaitė Asta

    2015-12-01

    Full Text Available After the London bombings in July 2005, the concern of terrorism scholars and policy makers has turned to “home-grown” terrorism and potential for political violence from within the states. “Radicalization” became a new buzz word. This article follows a number of reviews of the literature on radicalization and offers another angle for looking at this research. First, it discusses the term “radicalization” and suggests the use of the following definition of radicalization as a process by which a person adopts belief systems which justify the use of violence to effect social change and comes to actively support as well as employ violent means for political purposes. Next, it proposes to see the theories of radicalization focusing on the individual and the two dimensions of his/her motivation: whether that motivation is internal or external and whether it is due to personal choice or either internal (due to some psychological traits or external compulsion. Though not all theories fall neatly within these categories, they make it possible to make comparisons of contributions from a variety of different areas thus reflecting on the interdisciplinary nature of the study of terrorism in general and radicalization as a part of it.

  19. Ultrasound-induced radical polymerization

    NARCIS (Netherlands)

    Kuijpers, M.W.A.; Kemmere, M.F.; Keurentjes, J.T.F.

    2004-01-01

    Sonochemistry comprises all chemical effects that are induced by ultrasound. Most of these effects are caused by cavitations, ie, the collapse of microscopic bubbles in a liquid. The chemical effects of ultrasound include the formation of radicals and the enhancement of reaction rates at ambient

  20. Erectile function after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Frey, Anders; Jakobsen, Henrik

    2016-01-01

    collected database and a cross-sectional, questionnaire-based study in patients following radical prostatectomy. Erectile function was assessed with the IIEF-5 and the question "Is your erectile function as good as before the surgery (yes/no)". Patients were included if they were sexually active before...

  1. Flavonoids as scavengers of nitric oxide radical.

    NARCIS (Netherlands)

    van Acker, S.A.B.E.; Tromp, M.N.J.L.; Haenen, G.R.M.M.; van der Vijgh, W.J.F.; Bast, A.

    1995-01-01

    Flavonoids are a group of naturally occurring compounds used, e.g., in the treatment of vascular endothelial damage. They are known to be excellent scavengers of oxygen free radicals. Since the nitric oxide radical (

  2. O conceito de mal radical The concept of radical evil

    Directory of Open Access Journals (Sweden)

    Adriano Correia

    2005-01-01

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  3. Free radicals in chemical carcinogenesis.

    Science.gov (United States)

    Clemens, M R

    1991-12-15

    During the past decade, remarkable progress has been made in our understanding of cancer-causing agents, mechanisms of cancer formation and the behavior of cancer cells. Cancer is characterized primarily by an increase in the number of abnormal cells derived from a given normal tissue, invasion of adjacent tissues by these abnormal cells, and lymphatic or blood-borne spread of malignant cells to regional lymph nodes and to distant sites (metastasis). It has been estimated that about 75-80% of all human cancers are environmentally induced, 30-40% of them by diet. Only a small minority, possibly no more than 2% of all cases, result purely from inherent genetic changes. Several lines of evidence confirm that the fundamental molecular event or events that cause a cell to become malignant occur at the level of the DNA and a variety of studies indicate that the critical molecular event in chemical carcinogenesis is the interaction of the chemical agent with DNA. The demonstration that DNA isolated from tumor cells can transfect normal cells and render them neoplastic provides direct proof that an alteration of the DNA is responsible for cancer. The transforming genes, or oncogenes, have been identified by restriction endonuclease mapping. One of the characteristics of tumor cells generated by transformation with viruses, chemicals, or radiation is their reduced requirement for serum growth factors. A critical significance of electrophilic metabolites of carcinogenes in chemical carcinogenesis has been demonstrated. A number of "proximate" and "ultimate" metabolites, especially those of aromatic amines, were described. The "ultimate" forms of carcinogens actually interact with cellular constituents to cause neoplastic transformation and are the final metabolic products in most pathways. Recent evidence indicates that free radical derivatives of chemical carcinogens may be produced both metabolically and nonenzymatically during their metabolism. Free radicals carry no

  4. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

    1984-01-01

    Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  5. Free radicals in health and disease

    International Nuclear Information System (INIS)

    Gonet, B.

    1993-01-01

    Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

  6. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  7. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  8. A muoniated radical in selenium

    International Nuclear Information System (INIS)

    Reid, I.D.; Cox, S.F.J.; Jayasooriya, U.A.; Zimmermann, U.

    2003-01-01

    We report new 0.3 T transverse-field μSR experiments in crystalline Se which show only a small, slowly relaxing muon signal at 300 K, accounting for about 30% of the incoming muon polarization. However, at 90 K signals are observed around 74 and 157 MHz, characteristic of a radical with a hyperfine coupling of 231 MHz. Very fast relaxation which increases with temperature makes these signals impossible to follow beyond 200 K. Above 400 K a quickly relaxing diamagnetic signal becomes visible, its relaxation falling with increasing temperature. In the melt (>490 K) just a single non-relaxing diamagnetic signal is seen. These observations may be explained by electron spin-exchange with a muoniated radical

  9. Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

    Science.gov (United States)

    Postnikova, G B; Shekhovtsova, E A

    2016-12-01

    In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence

  10. DNA Binding Hydroxyl Radical Probes

    OpenAIRE

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different c...

  11. Anatomical landmarks of radical prostatecomy.

    Science.gov (United States)

    Stolzenburg, Jens-Uwe; Schwalenberg, Thilo; Horn, Lars-Christian; Neuhaus, Jochen; Constantinides, Costantinos; Liatsikos, Evangelos N

    2007-03-01

    In the present study, we review current literature and based on our experience, we present the anatomical landmarks of open and laparoscopic/endoscopic radical prostatectomy. A thorough literature search was performed with the Medline database on the anatomy and the nomenclature of the structures surrounding the prostate gland. The correct handling of puboprostatic ligaments, external urethral sphincter, prostatic fascias and neurovascular bundle is necessary for avoiding malfunction of the urogenital system after radical prostatectomy. When evaluating new prostatectomy techniques, we should always take into account both clinical and final oncological outcomes. The present review adds further knowledge to the existing "postprostatectomy anatomical hazard" debate. It emphasizes upon the role of the puboprostatic ligaments and the course of the external urethral sphincter for urinary continence. When performing an intrafascial nerve sparing prostatectomy most urologists tend to approach as close to the prostatic capsula as possible, even though there is no concurrence regarding the nomenclature of the surrounding fascias and the course of the actual neurovascular bundles. After completion of an intrafascial technique the specimen does not contain any periprostatic tissue and thus the detection of pT3a disease is not feasible. This especially becomes problematic if the tumour reaches the resection margin. Nerve sparing open and laparoscopic radical prostatectomy should aim in maintaining sexual function, recuperating early continence after surgery, without hindering the final oncological outcome to the procedure. Despite the different approaches for radical prostatectomy the key for better results is the understanding of the anatomy of the bladder neck and the urethra.

  12. Radical Smiles Rearrangement: An Update

    Directory of Open Access Journals (Sweden)

    Ingrid Allart-Simon

    2016-07-01

    Full Text Available Over the decades the Smiles rearrangement and its variants have become essential synthetic tools in modern synthetic organic chemistry. In this mini-review we summarized some very recent results of the radical version of these rearrangements. The selected examples illustrate the synthetic power of this approach, especially if it is incorporated into a domino process, for the preparation of polyfunctionalized complex molecules.

  13. Free radical reactions of daunorubicin

    International Nuclear Information System (INIS)

    Houee-Levin, C.

    1991-01-01

    Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

  14. Geoscientists and the Radical Middle

    Science.gov (United States)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  15. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...... examples of radical formation on proteins....

  16. Nuclear magnetic resonance studies of amino acids and proteins. Side-chain mobility of methionine in the crystalline amonio acid and in crystallne sperm whale (Physeter catodon) myoglobin

    International Nuclear Information System (INIS)

    Keniry, M.A.; Rothgeb, T.M.; Smith, R.L.; Gutowsky, H.S.; Oldfield, E.

    1983-01-01

    Deuterium ( 2 H) nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation times (T 1 ) were obtained of L-[epsilon- 2 H 3 ]methionine, L-[epsilon- 2 H 3 ]methionine in a D,L lattice, and [S-methyl- 2 H 3 ]methionine in the crystalline solid state, as a function of temperature, in addition to obtaining 2 H T 1 and line-width results as a function of temperature on [epsilon- 2 H 3 ]methionine-labeled sperm whale (Physeter catodon) myoglobins by using the method of magnetic ordering. Also recorded were 13 C cross-polarization ''magic-angle'' sample-spinning NMR spectra of [epsilon- 13 C]methionine-labeled crystalline cyanoferrimyoglobin (at 37.7 MHz, corresponding to a magnetic field strength of 3.52 T) and of the same protein in aqueous solution

  17. Assignment of hyperfine shifted haem methyl carbon resonances in paramagnetic low-spin met-cyano complex of sperm whale myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Yasuhiko

    1987-09-28

    The hyperfine shifted resonances arising from all four individual haem carbons of the paramagnetic low-spin met-cyano complex of sperm whale myoglobin have been clearly identified and assigned for the first time with the aid of /sup 1/H-/sup 13/C heteronuclear chemical shift correlated spectroscopy. Alteration of the in-plane symmetry of the electronic structure of haem induced by the ligation of proximal histidyl imidazole spreads the haem carbon resonances to 32 ppm at 22/sup 0/C, indicating the sensitivity of those resonances to the haem electronic/molecular structure. Those resonances are potentially powerful probes in characterizing the nature of haem electronic structure. 25 refs.; 2 figs.; 1 table.

  18. Direct electrochemistry and electrocatalysis of myoglobin using an ionic liquid-modified carbon paste electrode coated with Co3O4 nanorods and gold nanoparticles

    International Nuclear Information System (INIS)

    Wang, Xiaofeng; You, Zheng; Sha, Hailiang; Gong, Shixing; Niu, Qingjuan; Sun, Wei

    2014-01-01

    A nanohybrid biomaterial was fabricated by mixing Co 3 O 4 nanorods, gold nanoparticles (Au-NPs) and myoglobin (Mb), and depositing it on the surface of a carbon paste electrode containing the ionic liquid N-hexylpyridinium hexafluorophosphate as the binder. UV–vis and FT-IR revealed the Mb in the composite film to have remained in its native structure. A pair of well-defined redox peaks appears in cyclic voltammograms and indicates direct electron transfer from the Mb to the underlying electrode. The results are attributed to the favorable orientation of Mb in the composite film, to the synergistic effects of Co 3 O 4 nanorods and Au-NPs. The modified electrode shows excellent electrocatalytic ability towards the reduction of substrates such as trichloroacetic acid and nitrite, and displays good stability and reproducibility. (author)

  19. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  20. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  1. FAR RIGHT RADICALIZATION AND SOCIALIST RADICALIZATION IN INTERWAR ROMANIA

    Directory of Open Access Journals (Sweden)

    IONUŢ BUTOI

    2017-03-01

    Full Text Available In his comments on Mircea Vulcănescu. O microistorie a interbelicului românesc (Eikon, 2015, Emanuel Copilaş states that, regarding the cause of the far right radicalization manifested in the interwar Romania, I share the same historical explanation about fascism as Ernst Nolte. In this concise answer, I explain why this is an unsuitable comparison by summarizing the historiographical perspective I use in the cited volume. Nevertheless, Copilaş’s comments are reopening a debate about how to explain the Romanian fascism

  2. Radical probing of spliceosome assembly.

    Science.gov (United States)

    Grewal, Charnpal S; Kent, Oliver A; MacMillan, Andrew M

    2017-08-01

    Here we describe the synthesis and use of a directed hydroxyl radical probe, tethered to a pre-mRNA substrate, to map the structure of this substrate during the spliceosome assembly process. These studies indicate an early organization and proximation of conserved pre-mRNA sequences during spliceosome assembly. This methodology may be adapted to the synthesis of a wide variety of modified RNAs for use as probes of RNA structure and RNA-protein interaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Iron and iron derived radicals

    International Nuclear Information System (INIS)

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fast! Think small! In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab

  4. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi Lorenz

    2016-01-01

    This article examines memory politics in relation to radical actions of young Dutch-Moluccans, more specifically a train hijacking in 1977 at the village of De Punt in the Netherlands. The article examines how these historical events were remembered in the drama-documentary television film, De Punt...... of the web debate examines how viewers reacted to this interpretation. The web debate functioned as a participatory forum, where collective and national memories and postcolonial history were intensely discussed, and the debate made room for some degree of reconciliation between viewers of Dutch......-Moluccan and of Dutch majority background...

  5. Laser spectroscopy of hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Chen, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  6. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Glassman, I.; Brezinsky, K. [Princeton Univ., NJ (United States)

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  7. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

    This paper criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. These contradictions manifest themselves in a frequent oscillation between solipsism and realism, despite constructivist claims to be an anti-realist theory. The paper also points out the contradiction between the relativism of the radical constructivist principles and the constructivist exclusion of other epistemological or educational paradigms. It also disputes the originality and importance of the radical constructivist paradigm, suggesting the idea of an isomorphism between radical constructivist theory and contemplative realism. In addition, some pedagogical and scientific methodological aspects of the radical constructivist model are examined. Although radical constructivism claims to be a rational theory and advocates deductive thinking, it is argued that there is no logical deductive connection between the radical principles of constructivism and the radical constructivist ideas about scientific research and learning. The paper suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism and, finally, briefly advances an alternative realist model to epistemological and educational radical constructivism.

  8. Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

    International Nuclear Information System (INIS)

    Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

    2000-01-01

    One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

  9. Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

    Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

  10. Fluorescence lifetime measurement of radical ions

    International Nuclear Information System (INIS)

    Ichinose, Nobuyuki; Kinugasa, Jun-ichiro; Hagiri, Masahide; Nakayama, Toshihiro; Murakami, Hiroshi; Kishimoto, Maki; Daido, Hiroyuki

    2004-01-01

    One-photonic excitation of a charge transfer complex of hexamethoxybenzene (HMB) and nitrosonium tetrafluoroborate (NO + BF 4 - ) in acetonitrile afforded fluorescences emission from excited radical cation of HMB (HMB + *). Lifetime of the excited radical ion species was measured to be 7 ps by the pump-probe transient absorption technique. The lifetime was much shorter than that of free radical ion (63 ps), indicating the presence of an interaction between HMB + * and NO in the excited complex. (author)

  11. Reorientation dynamics of cyclohexadienyl radicals in zeolites

    International Nuclear Information System (INIS)

    Stolmar, M.; Roduner, E.; Dilger, H.; Himmer, U.; Shelley, M.; Reid, I.D.

    1997-01-01

    The dynamics of the muonium substituted cyclohexadienyl radical adsorbed on silicalite and NaZSM-5 is investigated by means of avoided level crossing muon spin resonance. The influence of benzene loading on the mobility of the radical is studied. At low loadings the radicals were found to be located on a single adsorption site where they undergo a wobbling type of motion. With increasing loading an additional species adsorbed on a different site is observed

  12. The Rise of Radicals in Bioinorganic Chemistry

    OpenAIRE

    Gray, Harry B.; Winkler, Jay R.

    2016-01-01

    Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O_2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) a...

  13. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  14. 2-Aminobenzamide and 2-Aminobenzoic Acid as New MALDI Matrices Inducing Radical Mediated In-Source Decay of Peptides and Proteins

    Science.gov (United States)

    Smargiasso, Nicolas; Quinton, Loic; de Pauw, Edwin

    2012-03-01

    One of the mechanisms leading to MALDI in-source decay (MALDI ISD) is the transfer of hydrogen radicals to analytes upon laser irradiation. Analytes such as peptides or proteins may undergo ISD and this method can therefore be exploited for top-down sequencing. When performed on peptides, radical-induced ISD results in production of c- and z-ions, as also found in ETD and ECD activation. Here, we describe two new compounds which, when used as MALDI matrices, are able to efficiently induce ISD of peptides and proteins: 2-aminobenzamide and 2-aminobenzoic acid. In-source reduction of the disulfide bridge containing peptide Calcitonin further confirmed the radicalar mechanism of the ISD process. ISD of peptides led, in addition to c- and z-ions, to the generation of a-, x-, and y-ions both in positive and in negative ion modes. Finally, good sequence coverage was obtained for the sequencing of myoglobin (17 kDa protein), confirming the effectiveness of both 2-aminobenzamide and 2-aminobenzoic acid as MALDI ISD matrices.

  15. Students' Ideas and Radical Constructivism

    Science.gov (United States)

    Sánchez Gómez, Pedro J.

    2016-08-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  16. DNA Binding Hydroxyl Radical Probes.

    Science.gov (United States)

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different chromophores which produce fluorescent products when hydroxylated. Of these, the coumarin system suffers from the fewest disadvantages. We have therefore examined its behavior when linked to a cationic peptide ligand designed to bind strongly to DNA.

  17. Photoionisation of the tropyl radical

    Directory of Open Access Journals (Sweden)

    Kathrin H. Fischer

    2013-04-01

    Full Text Available We present a study on the photoionisation of the cycloheptatrienyl (tropyl radical, C7H7, using tunable vacuum ultraviolet synchrotron radiation. Tropyl is generated by flash pyrolysis from bitropyl. Ions and electrons are detected in coincidence, permitting us to record mass-selected photoelectron spectra. The threshold photoelectron spectrum of tropyl, corresponding to the X+ 1A1’ ← X 2E2” transition, reveals an ionisation energy of 6.23 ± 0.02 eV, in good agreement with Rydberg extrapolations, but slightly lower than the value derived from earlier photoelectron spectra. Several vibrations can be resolved and are reassigned to the C–C stretch mode ν16+ and to a combination of ν16+ with the ring breathing mode ν2+. Above 10.55 eV dissociative photoionisation of tropyl is observed, leading to the formation of C5H5+ and C2H2.

  18. Free radicals in biology. Volume II

    International Nuclear Information System (INIS)

    Pryor, W.A.

    1976-01-01

    This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

  19. Measuring Atmospheric Free Radicals Using Chemical Amplification

    Science.gov (United States)

    1988-05-01

    CH 3Br, H2S, and SO2 [Logan et al., 1981]. Recently, the OH radical has been determined as the dominant loss mechanism for isoprene and monoterpenes ...W. Heaps, D. Philen, and T. McGee, Bondary Layer Measurements of the OH Radical in the Vicinity of an Isolated Power Plant Plume: SO2 and NO2

  20. Allylthioketone Mediated Free Radical Polymerization of Methacrylates

    Directory of Open Access Journals (Sweden)

    Feng Zhong

    2017-11-01

    Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

  1. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

    2013-01-01

    htmlabstractIn this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and

  2. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    Lasserre, J.B.; Laurent, M.; Mourrain, B.; Rostalski, P.; Trébuchet, P.

    2013-01-01

    In this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming its complex (resp. real) variety is finite. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and semi-definite

  3. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

    2011-01-01

    htmlabstractIn this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and

  4. Quantification of hydroxyl radical produced during phacoemulsification.

    Science.gov (United States)

    Gardner, Jonathan M; Aust, Steven D

    2009-12-01

    To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

  5. Self-Terminating, Oxidative Radical Cyclizations

    Directory of Open Access Journals (Sweden)

    Uta Wille

    2004-05-01

    Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

  6. An Appreciation of Free Radical Chemistry

    Indian Academy of Sciences (India)

    ... Lecture Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Resonance – Journal of Science Education; Volume 10; Issue 9. An Appreciation of Free Radical Chemistry - 6. Experiments Involving Free Radicals. G Nagendrappa. Classroom Volume 10 Issue 9 September 2005 pp 79-84 ...

  7. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    Science.gov (United States)

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their…

  8. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  9. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  10. Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin.

    Science.gov (United States)

    Anjum, Saima; Qi, Wenjing; Gao, Wenyue; Zhao, Jianming; Hanif, Saima; Aziz-Ur-Rehman; Xu, Guobao

    2015-03-15

    Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1-600μM with a detection limit of 0.3μM. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Molecular evolution of myoglobin in the Tibetan Plateau endemic schizothoracine fish (Cyprinidae, Teleostei) and tissue-specific expression changes under hypoxia.

    Science.gov (United States)

    Qi, Delin; Chao, Yan; Zhao, Yongli; Xia, Mingzhe; Wu, Rongrong

    2018-04-01

    Myoglobin (Mb) is an oxygen-binding hemoprotein that was once thought to be exclusively expressed in oxidative myocytes of skeletal and cardiac muscle where it serves in oxygen storage and facilitates intracellular oxygen diffusion. In this study, we cloned the coding sequence of the Mb gene from four species, representing three groups, of the schizothoracine fish endemic to the Qinghai-Tibetan Plateau (QTP), then conducted molecular evolution analyses. We also investigated tissue expression patterns of Mb and the expression response to moderate and severe hypoxia at the mRNA and protein levels in a representative of the highly specialized schizothoracine fish species, Schizopygopsis pylzovi. Molecular evolution analyses showed that Mb from the highly specialized schizothoracine fish have undergone positive selection and one positively selected residue (81L) was identified, which is located in the F helix, close to or in contact with the heme. We present tentative evidence that the Mb duplication event occurred in the ancestor of the schizothoracine and Cyprininae fish (common carp and goldfish), and that the Mb2 paralog was subsequently lost in the schizothoracine fish. In S. pylzovi, Mb mRNA is expressed in various tissues with the exception of the intestine and gill, but all such tissues, including the liver, muscle, kidney, brain, eye, and skin, expressed very low levels of Mb mRNA (Tibetan Plateau fish.

  12. Voltammetric determination of nitric oxide using a glassy carbon electrode modified with a nanohybrid consisting of myoglobin, gold nanorods, and reduced graphene oxide

    International Nuclear Information System (INIS)

    Marlinda, Ab Rahman; Jayabal, Subramaniam; Yusoff, Norazriena; Huang, Nay Ming; Pandikumar, Alagarsamy; Suriani, Abu Bakar

    2016-01-01

    Myoglobin-modified gold nanorods incorporating reduced graphene oxide (rGO) were fabricated and deposited on a glassy carbon electrode (GCE) to obtain a sensor for nitric oxide (NO). The Mb-AuNR/rGO nanohybrid showed a transverse localized surface plasmon resonance (LSPR) band with a peak at 508 nm, and a longitudinal LSPR band at 724 nm. The AuNRs have an average length of 38 ± 3 nm and a width of 11 ± 1 nm. The GCE modified with the nanohybrid is shown to be a viable sensor for the determination of NO by linear sweep voltammetry. Its electrocatalytic response toward the oxidation of NO is distinctly enhanced compared to other electrodes. The sensor, best operated at a working voltage of 0.85 V (vs. SCE), showed two linear response ranges (from 10 to 100 μM, and from 100 to 1000 μM), with a detection limit of 5.5 μM. Furthermore, it exhibits excellent selectivity for NO over common interferents such as NaNO 3 , and also over electroactive species such as ascorbate, dopamine, glucose, and uric acid. These properties make it a promising tool for the detection of NO in situations such as capillary and pulmonary hypertension and embolism, and during vasodilation. (author)

  13. Direct electrochemistry of myoglobin in a layer-by-layer film on an ionic liquid modified electrode containing CeO2 nanoparticles and hyaluronic acid

    International Nuclear Information System (INIS)

    Gao, R.; Zheng, J.; Zheng, X.

    2011-01-01

    We describe an ionic liquid modified electrode (CPE-IL) for sensing hydrogen peroxide (HP) that was modified by the layer-by-layer technique with myoglobin (Mb). In addition, the surface of the electrode was modified with CeO 2 nanoparticles (nano-CeO 2 ) and hyaluronic acid. UV-vis and FTIR spectroscopy confirmed that Mb retains its native structure in the composite film. Scanning electron microscopy showed that the nano-CeO 2 closely interact with Mb to form an inhomogeneously distributed film. Cyclic voltammetry reveals a pair of quasi-reversible redox peaks of Mb, with the cathodic peak at -0. 357 V and the anodic peak at -0. 269 V. The peak separation (ΔE p ) and the formal potential (E σ ) are 88 mV and -0. 313 V (vs. Ag/AgCl), respectively. The Mb immobilized in the modified electrode displays an excellent electrocatalytic activity towards HP in the 0. 6 to 78. 0 μM concentration range. The limit of detection is 50 nM (S/N = 3), and then the Michaelis-Menten constant is 71. 8 μM. We believe that such a composite film has potential to further investigate other redox proteins and in the fabrication of third-generation biosensors. (author)

  14. Orgasmic Dysfunction after Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Paolo Capogrosso

    2017-04-01

    Full Text Available In addition to urinary incontinence and erectile dysfunction, several other impairments of sexual function potentially occurring after radical prostatectomy (RP have been described; as a whole, these less frequently assessed disorders are referred to as neglected side effects. In particular, orgasmic dysfunctions (ODs have been reported in a non-negligible number of cases, with detrimental impacts on patients’ overall sexual life. This review aimed to comprehensively discuss the prevalence and physiopathology of post-RP ODs, as well as potential treatment options. Orgasm-associated incontinence (climacturia has been reported to occur in between 20% and 93% of patients after RP. Similarly, up to 19% of patients complain of postoperative orgasm-associated pain, mainly referred pain at the level of the penis. Moreover, impairment in the sensation of orgasm or even complete anorgasmia has been reported in 33% to 77% of patients after surgery. Clinical and surgical factors including age, the use of a nerve-sparing technique, and robotic surgery have been variably associated with the risk of ODs after RP, although robust and reliable data allowing for a proper estimation of the risk of postoperative orgasmic function impairment are still lacking. Likewise, little evidence regarding the management of postoperative ODs is currently available. In general, physicians should be aware of the prevalence of ODs after RP, in order to properly counsel all patients both preoperatively and immediately post-RP about the potential occurrence of bothersome and distressful changes in their overall sexual function.

  15. Orgasmic Dysfunction after Radical Prostatectomy

    Science.gov (United States)

    Ventimiglia, Eugenio; Cazzaniga, Walter; Montorsi, Francesco; Salonia, Andrea

    2017-01-01

    In addition to urinary incontinence and erectile dysfunction, several other impairments of sexual function potentially occurring after radical prostatectomy (RP) have been described; as a whole, these less frequently assessed disorders are referred to as neglected side effects. In particular, orgasmic dysfunctions (ODs) have been reported in a non-negligible number of cases, with detrimental impacts on patients' overall sexual life. This review aimed to comprehensively discuss the prevalence and physiopathology of post-RP ODs, as well as potential treatment options. Orgasm-associated incontinence (climacturia) has been reported to occur in between 20% and 93% of patients after RP. Similarly, up to 19% of patients complain of postoperative orgasm-associated pain, mainly referred pain at the level of the penis. Moreover, impairment in the sensation of orgasm or even complete anorgasmia has been reported in 33% to 77% of patients after surgery. Clinical and surgical factors including age, the use of a nerve-sparing technique, and robotic surgery have been variably associated with the risk of ODs after RP, although robust and reliable data allowing for a proper estimation of the risk of postoperative orgasmic function impairment are still lacking. Likewise, little evidence regarding the management of postoperative ODs is currently available. In general, physicians should be aware of the prevalence of ODs after RP, in order to properly counsel all patients both preoperatively and immediately post-RP about the potential occurrence of bothersome and distressful changes in their overall sexual function. PMID:28459142

  16. ORGASMIC FUNCTION AFTER RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    D. Yu. Pushkar

    2014-07-01

    Full Text Available Objective: to study orgasmic function (OF in patients undergoing radical prostatectomy (RPE.Subjects and methods. Seventy-nine patients who had undergone RPE for locally advanced prostate cancer without hormone and radiation therapies were examined. The patients’ mean age was 59.3 years. The mean EF-IIEF domain score was 24.4. OF was estimated by IIEF question 10 and the authors’ questionnaire. The Spearman rank correction coefficient and Mann-Whitney U-Wilcoxon tests were used.Results. After RPE, there was a reduction in the mean IIEF question 10 score from 3.9 (confidence interval 3.7–4.1 to 3.3 (3–3.5 (p = 0.000. The following changes were found in orgasm intensity: no changes in 43 %, mild worsening in 42 %, severe worsening in 8 %, and enhancement in 4 %; orgasm could not be achieved in 4 % of the patients. Pain usually of low intensity was reported by 8.8 %. The poor factors for preserving OF were its low baseline level, elderly age, or severe post-RPE erectile dysfunction.Conclusion. There were significant OF changes after RPE, which should be kept in mind while treating this category of patients.

  17. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    -assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very......One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper...

  18. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper......-assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very...

  19. Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

    Science.gov (United States)

    Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

    2015-04-01

    Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

  20. Some reactions of oxidizing radicals with enzymes in aqueous solution

    International Nuclear Information System (INIS)

    Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

    1979-01-01

    A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

  1. Radical pancreaticoduodenectomy for benign disease.

    LENUS (Irish Health Repository)

    Kavanagh, D O

    2008-01-01

    Whipple\\'s procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple\\'s procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple\\'s procedure during a 15-year period (1987-2002) were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%). One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30-75). The major presenting features included jaundice (five), pain (two), gastric outlet obstruction (one), and recurrent gastrointestinal haemorrhage (one). Investigations included ultrasound (eight), computerised tomography (eight), endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology), and endoscopic ultrasound (two). The pathological diagnosis included benign biliary stricture (two), chronic pancreatitis (two), choledochal cyst (one), inflammatory pseudotumour (one), cystic duodenal wall dysplasia (one), duodenal angiodysplasia (one), and granular cell neoplasm (one). There was no operative mortality. Morbidity included intra-abdominal collection (one), anastomotic leak (one), liver abscess (one), and myocardial infarction (one). All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple\\'s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound-guided fine needle aspirate (EUS-FNA) may reduce the need for Whipple\\'s operation

  2. Radical Pancreaticoduodenectomy for Benign Disease

    Directory of Open Access Journals (Sweden)

    D. O. Kavanagh

    2008-01-01

    Full Text Available Whipple's procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple's procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple's procedure during a 15-year period (1987–2002 were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%. One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30–75. The major presenting features included jaundice (five, pain (two, gastric outlet obstruction (one, and recurrent gastrointestinal haemorrhage (one. Investigations included ultrasound (eight, computerised tomography (eight, endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology, and endoscopic ultrasound (two. The pathological diagnosis included benign biliary stricture (two, chronic pancreatitis (two, choledochal cyst (one, inflammatory pseudotumour (one, cystic duodenal wall dysplasia (one, duodenal angiodysplasia (one, and granular cell neoplasm (one. There was no operative mortality. Morbidity included intra-abdominal collection (one, anastomotic leak (one, liver abscess (one, and myocardial infarction (one. All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple'’s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound–guided fine needle aspirate (EUS-FNA may reduce the need for Whipple's operation in

  3. Photodynamically generated bovine serum albumin radicals

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    Porphyrin-sensitized photoxidation of bovine serum albumin (BSA) results in oxidation of the protein at (at least) two different, specific sites: the Cys-34 residue giving rise to a thiyl radical (RS.); and one or both of the tryptophan residues (Trp-134 and Trp-214) resulting in the formation...... of tertiary carbon-centred radicals and disruption of the tryptophan ring system. In the case of porphyrins such as hematoporphyrin, which bind at specific sites on BSA, these species appear to arise via long-range transfer of damage within the protein structure, as the binding site is some distance from...... the ultimate site of radical formation. This transfer of damage is shown to depend on a number of factors including the conformation of the protein, the presence of blocking groups and pH. Alteration of the protein conformation results in radical formation at additional (or alternative) sites, as does blocking...

  4. Radical production in the radiolysis of benzene

    International Nuclear Information System (INIS)

    LaVerne, J.A.; Araos, M.S.

    1998-01-01

    Complete text of publication follows. Benzene is the prototypical aromatic compound and yet the radiation chemistry of the radicals formed in its radiolysis is not well understood. Temporal information on the yield of phenyl radical, the major radical produced in the radiolysis, is important for understanding the radiation chemistry of many other types of aromatic compounds including some polymers. The effects of track structure on the production of phenyl radicals have been examined using iodine-scavenging techniques. The variation of the yields of iodobenzene and the other major molecular products such as biphenyl as a function of iodine concentration gives a good indication of the competition kinetics occurring in particle tracks. Experimental results of the scavenger experiments will be shown and their implications in the radiolysis of condensed hydrocarbons will be discussed

  5. Radical Sustainable Innovation of office buildings

    DEFF Research Database (Denmark)

    Koch, Christian; Berker, Thomas; Koch-Ørvad, Nina

    2017-01-01

    by high degrees of newness in the entire life cycle. RSI should offer significant enhancements of known benefits, entirely new benefits, or substantial cost reductions, leading to the transformation of existing markets, the creation of sustainable growth, and global sustainability. Thus, if buildings were....../could be radically new. How to evaluate radicality is a major challenge. It is tentatively proposed, to use standards for sustainable office buildings. Standards are developed to accelerate the sustainable development but has to some extent come to constrain possibilities of radical innovation. As the criteria...... of newness is incorporated in standards, going beyond them, could be viewed as radical. Empirically a selection of international cases of office buildings with very high scores of BREEAM, LEED and DGNB are examined. Six selected cases were analysed more in detail, one of them, Geelens...

  6. Interactions between simple radicals and water

    International Nuclear Information System (INIS)

    Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Suardiaz, Reynier; Montero, Luis A.; Sander, Wolfram

    2008-01-01

    The interactions of the simple radicals CH 3 , NH 2 , OH, and F with water have been studied by DFT (UB3LYP/6-311++G(2d,2p)) and ab initio (RHF-UCCSD(T)/6-311++G(2d,2p)) methods. In this order the number of lone pairs (from zero to three), the electronegativity, and the strength of the X-H bonds increase (X = C, N, and O). The various minima of the radical-water complexes were located using the multiple minima hypersurface (MMH) approach which had previously been proven to be useful for closed-shell molecules. The role of the unpaired electron in hydrogen bonding was investigated using the natural bond orbital (NBO) analysis. A considerable contribution of the unpaired electron to the complex stabilization was only found for the methyl radical and the fluorine atom, whereas in the aminyl and the hydroxyl radical the role of the unpaired electron is negligible

  7. Psychopathology according to behaviorism: a radical restatement.

    Science.gov (United States)

    Pérez-Alvarez, Marino

    2004-11-01

    This article is a radical restatement of the predominant psychopathology, which is characterized by nosological systems and by its approach towards a neurobiological conception of the so-called mental disorders. The "radical" sense of this restatement is that of radical behaviorism itself. As readers will recall, "radical" applied to behaviorism means total (not ignoring anything that interests psychology), pragmatic (referring to the practical sense of knowledge), and it also derives from the Latin word for "root" (and thus implies change beginning at a system's roots or getting to the root of things, in this case, of psychological disorders). Based on this, I introduce the Aristotelian distinction of material and form, which, besides being behaviorist avant la lettre, is used here as a critical instrument to unmask the hoax of psychopathology as it is presented. The implications of this restatement are discussed, some of them already prepared for clinical practice.

  8. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...

  9. Prison Radicalization: The New Extremist Training Grounds?

    National Research Council Canada - National Science Library

    Coffin, Jr., McKinley D

    2007-01-01

    As a nation with the largest prison population in the world, the United States has all the ingredients for criminals, extremists, and religious radicals to collaborate in producing a new breed of homegrown terrorist...

  10. Neo-liberal Governing of 'Radicals'

    DEFF Research Database (Denmark)

    Lindekilde, Lasse

    2012-01-01

    The Danish government’s counter-radicalization Action Plan of 2009 had intended and unintended effects. Primarily targeting Danish Muslims, it employs neoliberal governmentality approaches of governance through individual support and response, information and knowledge, empowerment, surveillance...

  11. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Neumark, D.M. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

  12. Analysis of radicals of irradiated garlic

    International Nuclear Information System (INIS)

    Kameya, Hiromi; Kaimori, Yoshihiko; Ukai, Mitsuko

    2010-01-01

    The detection method of gamma ray irradiated garlic using Electron Spin Resonance(ESR)spectroscopy was studied. The ESR spectrum was consisted of one singlet signal at g=2.00. This signal is due to an organic free radical. Upon irradiation, the intensity of the signal was increased. Also two signals due to cellulose radical were detected nearby the singlet. The intensity of the singlet signal was increased as depend on the increase of the irradiation dose level. (author)

  13. Western radicalization: rethinking the psychology of terrorism

    OpenAIRE

    Pierson, Vern

    2017-01-01

    Approved for public release; distribution is unlimited The U.S. strategy to counter violent extremism relies heavily on the expert consensus that terrorists are engaging in political group speak and are by nature psychologically normal. Thus, anyone is susceptible to radicalization. To counter radicalization, finding answers is like finding a needle in a haystack. However, in the psychologically similar phenomenon of arson by firefighter—when a firefighter deliberately sets and then exting...

  14. Free radicals trapped in polyethylene matrix

    International Nuclear Information System (INIS)

    Shimada, S.; Maeda, M.; Hori, Y.; Kashiwabara, H.

    1977-01-01

    Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. It can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. (author)

  15. Radical and Not So Radical Transgressions: Invading Backstage Domains

    Directory of Open Access Journals (Sweden)

    Lada Čale Feldman

    2012-06-01

    Full Text Available Featuring as one of the privileged metaphors in humanities and social sciences, theatre provides primarily an image of a circumscribed space whose spatial syntax and modes of human engagement take place within and with respect to the larger space of the city, the world, and, as in Calderon’s Gran teatro del mundo, the universe. It is precisely as a special organization of spatiality that theatre reached the status of Foucault’s radical hetero-topos, flexible as it proved to be as a model for not only counter-representing all the human dealings in the external space, but also of conceptualizing, as in Freud’s psychoanalysis, man’s inner world, his psychic topography. But theatre is above all a concrete place, a built form with its own spatial history, its changing social and ideological functions, and its ways of bestowing to the bodies that enter into it actual or phantasm identities, thoughts, sensations, feelings and memories.My intervention will deal with one of the ruling borders/dichotomies/barriers of theatrical space, the one dividing “front stage” from “backstage” regions. In his detailed analysis of the latter in an individual and concrete theatre building, Andrew Filmer relies among others on Edward Soja’s “trialectics of being”, and thus also on Lefebvre’s categories of perceptual, conceptual and lived aspects of spatiality which Soja evokes, which will here be of particular interest. In contrast to the repercussions of such an analytical triad for the ethnographic study of concrete theatrical sites, I will ask how it pertains to potential manipulations of the aforementioned division of front-stage and backstage within contemporary performance practice. The temporal aspect of this manipulation should also be emphasized, having in mind the historical provenance of a whole backstage mythology – evidenced in numerous novels, plays and films situated in the backstage world - in the elaborated architectural

  16. Development of a new free radical absorption capacity assay method for antioxidants: aroxyl radical absorption capacity (ARAC).

    Science.gov (United States)

    Nagaoka, Shin-ichi; Nagai, Kanae; Fujii, Yuko; Ouchi, Aya; Mukai, Kazuo

    2013-10-23

    A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

  17. Myoglobin-biomimetic electroactive materials made by surface molecular imprinting on silica beads and their use as ionophores in polymeric membranes for potentiometric transduction.

    Science.gov (United States)

    Moreira, Felismina T C; Dutra, Rosa A F; Noronha, Joao P C; Sales, M Goreti F

    2011-08-15

    Myoglobin (Mb) is among the cardiac biomarkers playing a major role in urgent diagnosis of cardiovascular diseases. Its monitoring in point-of-care is therefore fundamental. Pursuing this goal, a novel biomimetic ionophore for the potentiometric transduction of Mb is presented. It was synthesized by surface molecular imprinting (SMI) with the purpose of developing highly efficient sensor layers for near-stereochemical recognition of Mb. The template (Mb) was imprinted on a silane surface that was covalently attached to silica beads by means of self-assembled monolayers. First the silica was modified with an external layer of aldehyde groups. Then, Mb was attached by reaction with its amine groups (on the external surface) and subsequent formation of imine bonds. The vacant places surrounding Mb were filled by polymerization of the silane monomers 3-aminopropyltrimethoxysilane (APTMS) and propyltrimethoxysilane (PTMS). Finally, the template was removed by imine cleavage after treatment with oxalic acid. The results materials were finely dispersed in plasticized PVC selective membranes and used as ionophores in potentiometric transduction. The best analytical features were found in HEPES buffer of pH 4. Under this condition, the limits of detection were of 1.3 × 10(-6)mol/L for a linear response after 8.0 × 10(-7) mol/L with an anionic slope of -65.9 mV/decade. The imprinting effect was tested by preparing non-imprinted (NI) particles and employing these materials as ionophores. The resulting membranes showed no ability to detect Mb. Good selectivity was observed towards creatinine, sacarose, fructose, galactose, sodium glutamate, and alanine. The analytical application was conducted successfully and showed accurate and precise results. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Cardiac biomarkers in neonatology: BNP/NTproBNP, troponin I/T, CK-MB and myoglobin – a systematic review

    Directory of Open Access Journals (Sweden)

    Rita P. Teixeira

    2017-06-01

    Full Text Available Cardiac biomarkers play a central role in myocardial injury and heart failure in adult patients, but their clinical relevance in neonatology has not been clearly stablished. The aim of this systematic review was to evaluate the recent literature on B-type natriuretic peptide (BNP/N-terminal-pro-BNP (NTproBNP, troponin I/T, Creatine Kinase-MB (CK-MB and myoglobin and their relationship with different pathologies of the newborn. A total of 67 articles were included to undergo data extraction, after a first text and abstract analysis and a second full-text analysis, using the PubMed database.Evidence shows that cardiac biomarkers are a useful and fast diagnostic tool with great potential for becoming as important as clinical and echocardiographic findings in pathologies of the heart. BNP/NTproBNP and troponin I/T demonstrated to be the ones with greater value. BNP/NTproBNP is of particular significance in the diagnosis and management of patent ductus arteriosus, as it has a good correlation with diagnosis, treatment and prognosis. Troponin T may be a beneficial additional marker for this disease, correlating with ductal significance and treatment response. Moreover, BNP/NTproBNP can be used, with other clinical and laboratory findings, in the diagnosis and as a guide for treatment in pulmonary hypertension and in the diagnosis and management of cardiac sequela in bronchopulmonary dysplasia. Troponin I/T finds its clinical importance in perinatal asphyxia as a marker of myocardial injury and a reliable indicator of severity and mortality. Further studies with larger cohort populations are needed for stablishing the cutoff values specific for each neonatal pathology allowing its early and proper management.

  19. A Multi-Region Magnetoimpedance-Based Bio-Analytical System for Ultrasensitive Simultaneous Determination of Cardiac Biomarkers Myoglobin and C-Reactive Protein.

    Science.gov (United States)

    Yang, Zhen; Wang, Huanhuan; Guo, Pengfei; Ding, Yuanyuan; Lei, Chong; Luo, Yongsong

    2018-06-01

    Cardiac biomarkers (CBs) are substances that appear in the blood when the heart is damaged or stressed. Measurements of the level of CBs can be used in course of diagnostics or monitoring the state of the health of group risk persons. A multi-region bio-analytical system (MRBAS) based on magnetoimpedance (MI) changes was proposed for ultrasensitive simultaneous detection of CBs myoglobin (Mb) and C-reactive protein (CRP). The microfluidic device was designed and developed using standard microfabrication techniques for their usage in different regions, which were pre-modified with specific antibody for specified detection. Mb and CRP antigens labels attached to commercial Dynabeads with selected concentrations were trapped in different detection regions. The MI response of the triple sensitive element was carefully evaluated in initial state and in the presence of biomarkers. The results showed that the MI-based bio-sensing system had high selectivity and sensitivity for detection of CBs. Compared with the control region, ultrasensitive detections of CRP and Mb were accomplished with the detection limits of 1.0 pg/mL and 0.1 pg/mL, respectively. The linear detection range contained low concentration detection area and high concentration detection area, which were 1 pg/mL⁻10 ng/mL, 10⁻100 ng/mL for CRP, and 0.1 pg/mL⁻1 ng/mL, 1 n/mL⁻80 ng/mL for Mb. The measurement technique presented here provides a new methodology for multi-target biomolecules rapid testing.

  20. The usefulness of myoglobin radioimmunoassays to diagnose and monitor hereditary forms of muscular dystrophy linked to the X-chromosome and to identify its carriers

    International Nuclear Information System (INIS)

    Heim, L.

    1985-01-01

    A total of 376 children suffering from malignant muscular dystrophy (DMD), which is transmitted by recessive genes, were subjected to 478 radioimmunological tests for the presence of myoglobin (Mb) in the serum and found to be positive in 98% of the cases. There was a correlation between the Mb values and certain enzymes produced in the muscles, in particular CK and LDH, whereas no such link could be established regarding the age of the patients. The increases in the Mb values and related parameters seen in benign forms of muscular dystrophy failed to attain statistical significance, nor did the Mb values determined within the individual age groups permit any statistically relevant conclusions to be drawn as to the therapeutic success. Out of 58 proven carriers 73% were positive on the Mb tests, as compared to no more than 10% of the suspected carriers (the CK values remaining within normal limits). Among suspected juvenile carriers (sisters of DMD patients), increased Mb values were more frequent (25%) than increased CK values (12%). Within the group of suspected carriers there was a significant correlation between the increases in Mb and CK, which was absent in the proven carriers. One asset of radioimmunological tests to detect Mb in the serum is their superior sensitivity. They may yield valuable information in addition to that provided by muscle enzyme measurements, in particular in specific situations like those occurring during follow-up observations, in the assessment of drugs acting on muscular permeability and in the identification of carriers of either type of disease. (TRV) [de

  1. Free radicals in wood induced by γ-radiation

    International Nuclear Information System (INIS)

    Xu Honglin; Zhang Wenhui

    1994-01-01

    The free radicals in wood induced by γ-radiation were studied by electron spin resonance. The fine structure of the ESR signal from sawdust samples irradiated could be resolved into various radicals. These free radicals have a very long lifetime. The major spectrum for the free radicals will exponentially increased along with the radiation dose according to Y 1-Exp(-α a D). The intensity of radiation radicals is dependent on tree species. The stronger the intensity of mechanic free radicals is, the stronger the intensity of radiation free radicals

  2. HPLC-ESR techniques for detection of complex trapped radicals

    International Nuclear Information System (INIS)

    Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

    1992-01-01

    High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

  3. Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

    DEFF Research Database (Denmark)

    Souto, Manuel; Bendixen, Dan; Jensen, Morten

    2016-01-01

    During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF...

  4. How to counter radical narratives: Dutch deradicalization policy in the case of Moluccan and Islamic radicals

    NARCIS (Netherlands)

    Demant, F.; de Graaf, B.

    2010-01-01

    This article deals with the role of government in encouraging the decline of radical movements. The question posed is: "Which story can the government tell to encourage the decline of radical groups and the disengagement of their members?" The article makes use of the survey of factors promoting

  5. Radical Transversal Lightlike Submanifolds of Indefinite Para-Sasakian Manifolds

    OpenAIRE

    Shukla S.S.; Yadav Akhilesh

    2014-01-01

    In this paper, we study radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds giving some non-trivial examples of these submanifolds. Integrability conditions of distributions D and RadTM on radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds, have been obtained. We also study totally contact umbilical radical transvers...

  6. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded in the l......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...... radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem...

  7. Radical-pair based avian magnetoreception

    Science.gov (United States)

    Procopio, Maria; Ritz, Thorsten

    2014-03-01

    Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

  8. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    Science.gov (United States)

    Mehta, Deepali N.; Kidwell, Nathanael M.; Zwier, Timothy S.

    2011-06-01

    Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules in planetary atmospheres. Given the nitrogen-rich atmosphere of Titan, and the prevalence of nitriles there, it is likely that nitrile and isonitrile RSRs could be especially important in pathways leading to the formation of more complex nitrogen-containing compounds and the aerosols ("tholins") that are ultimately produced. In this talk, the results of a gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (C_6H_5.{C}HCN), the nitrogen-containing analog of the 1-phenylpropargyl radical, will be presented. A resonant two color photon ionization spectrum over the range 21,350-22,200 Cm-1 (450.0-468.0 nm) has been recorded, and the D_0-D_1 origin band has been tentatively identified at 21,400 Cm-1. Studies identifying the ionization threshold, and characterizing the vibronic structure will also be presented. An analogous study of the phenylisocyanomethyl radical, C_6H_5.{C}HNC, is currently being pursued for comparison with that of phenylcyanomethyl radical.

  9. Introducing Stable Radicals into Molecular Machines.

    Science.gov (United States)

    Wang, Yuping; Frasconi, Marco; Stoddart, J Fraser

    2017-09-27

    Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1'-dialkyl-4,4'-bipyridinium (BIPY •+ ) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY •+ -based molecular machines with useful functions.

  10. Analysis of radicals induced in irradiated foods

    International Nuclear Information System (INIS)

    Kishida, Keigo; Kaimori, Yoshihiko; Kawamura, Shoei; Sakamoto, Yuhki; Nakamura, Hideo; Ukai, Mitsuko; Kikuchi, Masahiro; Shimoyama, Yuhei; Kobayashi, Yasuhiko

    2012-01-01

    By electron spin resonance (ESR) spectroscopy, we revealed free radicals in γ-ray irradiated foods; black pepper, green coffee bean and ginseng. We also analyzed the decay behavior of radiation induced free radicals during storage of irradiated foods. The ESR spectrum of experimental irradiated foods consists of a sextet signal centered at g=2.0 and a singlet signal at the same g-value position and a singlet signal at g=4.0. The singlet signal at g=2.0 is originated from organic free radicals and its peak intensity showed the dependence of γ-ray irradiation dose levels. The signal intensity was decreased during storage. Only after 3 hours of radiation treatment the peak intensity was decreased fast and after that the intensity was decreased slowly. The relaxation times, T 1 and T 2 , of radiation induced free radicals showed the variations before and after irradiation. During long time storage period it was shown that T 1 was increased and T 2 was decreased. By analysis of decay process using the simulation methods based on the theory of reaction speed, it is considered that at least two kinds of radicals were induced in irradiated foods during long time storage. (author)

  11. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  12. Fragmentation characteristics of the unstable [CH3 CO][radical sign] radicals generated by neutralization of [CH3CO]+ cations

    Science.gov (United States)

    Hop, C. E. C. A.; Holmes, J. L.

    1991-03-01

    The stability and fragmentation characteristics of [CH3 CO][radical sign] radicals, generated by vertical charge exchange between acetyl cations and permanent gases or metal vapours (He, Xe, NO, Cd, Na and K), were examined mass spectrometrically. Two dissociation reactions were observed, the losses of CH[radical sign]3 and H[radical sign]. The H[radical sign] loss reaction, the higher energy dissociation, became of greater importance as the exothermicity of the charge exchange was increased. Based on the analysis of the kinetic energy releases it was concluded that these decompositions arose from the population of two excited states of the [CH3 CO][radical sign] radical.

  13. Time resolved resonance Raman spectra of anilino radical and aniline radical cation

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.; Schuler, R.H.

    1987-01-01

    We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

  14. Resveratrol products resulting by free radical attack

    Energy Technology Data Exchange (ETDEWEB)

    Bader, Yvonne; Quint, R.M. [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria)], E-mail: nikola.getoff@univie.ac.at

    2008-06-15

    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.

  15. Optimal pain management for radical prostatectomy surgery

    DEFF Research Database (Denmark)

    Joshi, Grish P; Jaschinski, Thomas; Bonnet, Francis

    2015-01-01

    BACKGROUND: Increase in the diagnosis of prostate cancer has increased the incidence of radical prostatectomy. However, the literature assessing pain therapy for this procedure has not been systematically evaluated. Thus, optimal pain therapy for patients undergoing radical prostatectomy remains...... controversial. METHODS: Medline, Embase, and Cochrane Central Register of Controlled Trials were searched for studies assessing the effects of analgesic and anesthetic interventions on pain after radical prostatectomy. All searches were conducted in October 2012 and updated in June 2015. RESULTS: Most...... treatments studied improved pain relief and/or reduced opioid requirements. However, there were significant differences in the study designs and the variables evaluated, precluding quantitative analysis and consensus recommendations. CONCLUSIONS: This systematic review reveals that there is a lack...

  16. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

      Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer...... involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy services and may play a decisive role. In doing this they most likely take on all the three user involvement...... roles defined in the literature of New Service and New Product Development. Also a number of conditions are found to be necessary in order for this collaboration to succeed. The conclusion is that another understanding and handling of the customer/supplier relation is needed along with a need...

  17. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  18. Formation of stable radicals during perfluoroalkane radiolysis

    International Nuclear Information System (INIS)

    Allayarov, S.R.; Demidov, S.V.; Kiryukhin, D.P.; Mikhajlov, A.I.; Barkalov, I.M.

    1984-01-01

    Accumulation and stabilization kinetics of perfluoroalkyls during α-radiolysis ( 60 Co) of perfluoralkanes (PFA) in a wide temperature range for different PFA fractions differing in the average molecular weight, is investigated. It is noted that low temperature (PFA) radiolysis (77 K) is of a linear nature of accumulation of stabilized radicals up to doses of approximately 700 KGy. In the case of PFA radiolysis at 300 K radiation yields of stable radicals are somewhat lower than at 47 K and at doses of 200-300 KGy, their accumulation ceases. It is shown that kinetics of formation and accumulation of stable radicals does not depend on molecular mass and PFA fraction viscosity. Perfluoroalkyl stability is explained by intra molecular conformation spheric insulation of the free valency. Perfluoroalkyl stability in different PFA fractions in a wide time range in different media is investigated

  19. Hearing Status after Radical Mastoidectomy without Tympanoplasty.

    Science.gov (United States)

    Khan, Shamaila Nawaz; Udaipurwala, Iqbal Hussain; Mehmood, Talat; Rahat, Zahid Mehmood

    2017-12-01

    To find out the impairment of hearing associated with radical mastoidectomy by measuring the quantitative difference in the functional hearing level before and after radical mastoidectomy operation without tympanoplasty. Cross-sectional comparative study. Department of Otorhinolaryngology and Head Neck Surgery, Bahawal Victoria Hospital, Bahawalpur and PNS Shifa Hospital, Karachi, from November 2009 to January 2013. Eighty-five patients, diagnosed clinically as chronic suppurative otitis media with extensive cholesteatoma having history of ear discharge and hearing impairment for more than 6 weeks duration and requiring radical mastoidectomy for treatment, were included in this study. Pure tone audiogram was done before and after radical mastoidectomy. Hearing impairment was compared in each patient before and after the operation. Among the 85 patients, 54 (63.5%) were males and 31 (36.5%) were females, with the age ranged between 18 to 63 years, mean age being 42.31 4.8 years. The mean increase in hearing loss after radical mastoidectomy in air conduction was 7.19 dB, bone conduction was 4.16 dB, and air-bone gap was 3.75 dB (0.001). The ear became dry and safe in 82 patients (96.5%) out of a total of 85, and only 3 patients required revision surgery at a second stage. Radical mastoidectomy has a least negligible effect on hearing status and one should not limit this technique due to the concern of aggravated hearing in patients with extensive cholesteatoma at the cost of dry and safe ears, which should be of prime importance.

  20. Exploring how lead users develop radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher; Gemuenden, Hans Georg; Hienerth, C.

    2008-01-01

    in order to transform their radically new solutions into functional prototypes and then to convince established manufacturers of the technological and market potential of their innovations. Using a comparative case study design in the high-tech field of medical equipment technology, we find that individual...... the supply of diversified knowledge, the development and coordination of a network for further development of the innovation, and initial tests of technical or market feasibility. Our findings have implications for manufacturing firms that wish to design radical innovation projects with (individual) lead...

  1. Preparation and study of dialkyl nitroxide radicals

    International Nuclear Information System (INIS)

    Chenavas, P.

    1969-01-01

    These radicals are obtained by oxidation of N-hydroxy-imides with lead tetracetate or p-nitro-perbenzoic acid. These imides are prepared by heating dicarboxylic acids anhydrides with benzyloxy-amine followed by catalytic hydrogenation of N-benzyloxy-imides so obtained. Two series of radicals have mainly been studied, the first concerning five-membered cyclic imides, the second six-membered cyclic imides, these molecules having methyls substituents or no on the carbon ring. N. M. R. spectra of some O-benzyl-imides have been analysed. These different results have made it possible to study the conformation and stereochemistry of these imides. (author) [fr

  2. RADICAL. Radiation information centre with analysing logic

    International Nuclear Information System (INIS)

    Rantanen, H.

    1998-01-01

    in an emergency, the production of data is overwhelming and the need of accurate and up-to-date information is essential. In Finland a new system (RADICAL) has been developed in order to automatically collect and maintain an overall view of the radiation situation and to facilitate the analysis of the consequences of any radiation incident. The project was started in the beginning of 1992 and the system was operational in summer 1994. The main objectives of the development process and how they are being fulfilled with the RADICAL system are discussed. (author)

  3. Dibromine radical anion reactions with heme enzymes

    International Nuclear Information System (INIS)

    Gebicka, L.; Gebicki, J.L.

    1996-01-01

    Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs

  4. Radical Islamism and Migrant Integration in Denmark

    DEFF Research Database (Denmark)

    Goli, Marco; Rezaei, Shahamak

    2011-01-01

    It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate for – or c......It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate...

  5. Resonance ionization detection of combustion radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cool, T.A. [Cornell Univ., Ithaca, NY (United States)

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

  6. Competing with the radical right: Distances between the European radical right and other parties on typical radical right issues

    NARCIS (Netherlands)

    Immerzeel, T.; Lubbers, M.; Coffé, H.

    2016-01-01

    The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs' and other parties' stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

  7. Competing with the radical right. Distances between the European radical right and other parties on typical radical right issues

    NARCIS (Netherlands)

    Immerzeel, T.; Lubbers, M.; Coffe, H.R.

    2015-01-01

    The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs’ and other parties’ stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

  8. Serum Hydroxyl Radical Scavenging Capacity as Quantified with Iron-Free Hydroxyl Radical Source

    Science.gov (United States)

    Endo, Nobuyuki; Oowada, Shigeru; Sueishi, Yoshimi; Shimmei, Masashi; Makino, Keisuke; Fujii, Hirotada; Kotake, Yashige

    2009-01-01

    We have developed a simple ESR spin trapping based method for hydroxyl (OH) radical scavenging-capacity determination, using iron-free OH radical source. Instead of the widely used Fenton reaction, a short (typically 5 seconds) in situ UV-photolysis of a dilute hydrogen peroxide aqueous solution was employed to generate reproducible amounts of OH radicals. ESR spin trapping was applied to quantify OH radicals; the decrease in the OH radical level due to the specimen’s scavenging activity was converted into the OH radical scavenging capacity (rate). The validity of the method was confirmed in pure antioxidants, and the agreement with the previous data was satisfactory. In the second half of this work, the new method was applied to the sera of chronic renal failure (CRF) patients. We show for the first time that after hemodialysis, OH radical scavenging capacity of the CRF serum was restored to the level of healthy control. This method is simple and rapid, and the low concentration hydrogen peroxide is the only chemical added to the system, that could eliminate the complexity of iron-involved Fenton reactions or the use of the pulse-radiolysis system. PMID:19794928

  9. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  10. Radical scavenging activity of crude polysaccharides from Camellia sinensis

    Directory of Open Access Journals (Sweden)

    Yang Fan

    2011-01-01

    Full Text Available A preparation of crude polysaccharides (TPS was isolated from Camellia sinensis by precipitation and ultrafiltration. TPS1, TPS2, and TPS3 had molecular weights of 240, 21.4, and 2.46 kDa, respectively. The radical scavenging activities of TPS were evaluated by DPPH free radical, hydroxyl radical and superoxide radical scavenging. These results revealed that TPS exhibited strong radical scavenging activity in a concentration-dependent manner. TPS3 with lowest molecular weight showed a higher radical scavenging activity.

  11. Understanding political radicalization: The two-pyramids model.

    Science.gov (United States)

    McCauley, Clark; Moskalenko, Sophia

    2017-04-01

    This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  12. Can the United States Defeat Radical Islam

    Science.gov (United States)

    2008-05-22

    It strongly disapproves of idolatry, the popular cult of saints and tomb visitation. 11...twentieth century, Sayyid Qutb (1906-1966), an Egyptian Islamic radical, referencing al-Wahhab, developed a modified concept of jahiliyya. In Qutb’s...It strongly disapproves of idolatry, the popular cult of saints and tomb visitation. When ibn Taymiyya was asked if the murderous. Mongols, who

  13. Identity and Islamic Radicalization in Western Europe

    NARCIS (Netherlands)

    S.M. Murshed (Syed); S. Pavan (Sara)

    2009-01-01

    textabstractThis paper argues that both socio-economic disadvantage and political factors, such as the West’s foreign policy with regard to the Muslim world, along with historical grievances, play a part in the development of Islamic radicalized collective action in Western Europe. We emphasise the

  14. Lipophilic fluorescent products of free radicals

    Czech Academy of Sciences Publication Activity Database

    Ivica, Josko; Wilhelm, Jiří

    2014-01-01

    Roč. 158, č. 3 (2014), s. 365-372 ISSN 1213-8118 R&D Projects: GA ČR(CZ) GAP303/11/0298 Institutional support: RVO:67985823 Keywords : lipofuscin-like pigments * lipid peroxidation * free radical s * fluorescence Subject RIV: CE - Biochemistry Impact factor: 1.200, year: 2014

  15. Radical Negativity: Music Education for Social Justice

    Science.gov (United States)

    McLaren, Peter

    2011-01-01

    According to Hedges (2010), the real enemies of the liberal class are radical thinkers such as Noam Chomsky and Ralph Nader, iconoclastic intellectuals who possess the moral autonomy to defy the power elite. While this author agrees with Hedges, he would take this argument even further. In this article, the author argues that the real enemy of…

  16. Unimolecular reaction dynamics of free radicals

    International Nuclear Information System (INIS)

    Terry A. Miller

    2006-01-01

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

  17. Neglected Side Effects After Radical Prostatectomy

    DEFF Research Database (Denmark)

    Frey, Anders Ullmann; Sønksen, Jens; Fode, Mikkel

    2014-01-01

    INTRODUCTION: A series of previously neglected sexually related side effects to radical prostatectomy (RP) has been identified over the recent years. These include orgasm-associated incontinence (OAI), urinary incontinence in relation to sexual stimulation (UISS), altered perception of orgasm, or...

  18. Letter: OCCO*+, NNCO*+ and NNNN*+ radical cations.

    Science.gov (United States)

    Flammang, R; Srinivas, R; Nguyen, M T; Gerbaux, P

    2007-01-01

    Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

  19. Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic ...

    African Journals Online (AJOL)

    Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic Profile of Methanol Extracts of Wild Plants of Southern Sonora, Mexico. EF Moran-Palacio, LA Zamora-Álvarez, NA Stephens-Camacho, GA Yáñez- Farías, A Virgen-Ortiz, O Martínez-Cruz, JA Rosas-Rodríguez ...

  20. Quantification of Radicals Generated in a Sonicator

    Directory of Open Access Journals (Sweden)

    Kassim Badmus

    2016-06-01

    Full Text Available The hydroxyl radical (OH• is a powerful oxidant produced as a consequence of cavitation in water. It can react nonspecifically in breaking down persistent organic pollutants in water into their mineral form. It can also recombine to form hydrogen peroxide which is very useful in water treatment. In this study, terephthalic acid (TA and potassium iodide dosimetry were used to quantify and investigate the behaviour of the generated OH radical in a laboratory scale sonicator. The 2-hydroxyl terephthalic acid (HTA formed during terephthalic acid dosimetry was determined by optical fibre spectrometer. The production rate of HTA served as a means of evaluating and characterizing the OH• generated over given time in a sonicator. The influence of sonicator power intensity, solution pH and irradiation time upon OH• generation were investigated. Approximately 2.2 ´ 10-9 M s-1 of OH radical was generated during the sonication process. The rate of generation of the OH radicals was established to be independent of the concentration of the initial reactant. Thus, the rate of generation of OH• can be predicted by zero order kinetics in a sonicator.

  1. Parents’ Perspectives on Radicalization: A Qualitative Study

    NARCIS (Netherlands)

    E. Sikkens (Elga); M.R.P.J.R.S. van San (Marion); S. Sieckelinck (Stijn); M. de Winter (Micha)

    2018-01-01

    textabstractAbstract: Radicalization of young people might be influenced by the way parents react towards the development of political or religious ideals. However, these reactions have hardly been explored. This study aimed to discover how parents reacted to the development of extreme ideals, and

  2. Radical Feminism and the Subject of Writing.

    Science.gov (United States)

    Rhodes, Jacqueline

    The radical feminists of the late 1960s and early 1970s, as well as their online counterparts today, offer provocative examples of networked textuality, a discourse dependent on the constant and visible contextualization of self and writing within the discourses of hegemony. Given its potential use for liberatory writing pedagogies, it seems…

  3. Formation of radical cations of diaryloxadiazoles

    International Nuclear Information System (INIS)

    Helmstreit, W.

    1988-01-01

    The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

  4. Albert Einstein: Radical Pacifist and Democrat

    Science.gov (United States)

    Jayaraman, T.

    We draw attention here to the radical political grounding of Einstein's pacifism. We also drescribe some less commonly known aspects of his commitment to civil liberties, particularly in the context of the anti-l hysteria and anti-racism current in the United States of the late 1940s and 1950s. We also examine briefly his views on socialism.

  5. Phytochemical screening, free radical scavenging and antibacterial ...

    African Journals Online (AJOL)

    Cassia sieberiana is a tropical plant, widely distributed throughout Sudan and Guinea savannah. It is used in traditional medicine for the treatment of malarial, cancer and stomach ache. The study was conducted to screen for phytochemicals, free radical scavenging and antibacterial potentials of the root bark.

  6. Radicals derived from acetaldehyde and vinyl alcohol.

    Science.gov (United States)

    Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

    2017-10-18

    Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol -1 . The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol -1 . Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (1441 cm -1 ), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm -1 frequency in the acetyl radical to ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our

  7. Pertinent issues related to laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Sidney C. Abreu

    2003-12-01

    Full Text Available PURPOSE: We describe the critical steps of the laparoscopic radical prostatectomy (LRP technique and discuss how they impact upon the pertinent issues regarding prostate cancer surgery: blood loss, potency and continence. RESULTS: A major advantage of LRP is the reduced operative blood loss. The precise placement of the dorsal vein complex stitch associated with the tamponading effect of the CO2 pneumoperitoneum significantly decrease venous bleeding, which is the main source of blood loss during radical prostatectomy. At the Cleveland Clinic, the average blood loss of our first 100 patients was 322.5 ml, resulting in low transfusion rates. The continuous venous bleeding narrowed pelvic surgical field and poor visibility can adversely impact on nerve preservation during open radical prostatectomy. Laparoscopy, with its enhanced and magnified vision in a relatively bloodless field allows for excellent identification and handling of the neurovascular bundles. During open retropubic radical prostatectomy, the pubic bone may impair visibility and access to the urethral stump, and the surgeon must tie the knots relying on tactile sensation alone. Consequently, open prostatectomy is associated with a prolonged catheterization period of 2 - 3 weeks. Comparatively, during laparoscopic radical prostatectomy all sutures are meticulously placed and each is tied under complete visual control, resulting in a precise mucosa-to-mucosa approximation. CONCLUSION: The laparoscopic approach may represent a reliable less invasive alternative to the conventional open approach. Despite the encouraging preliminary anatomical and functional outcomes, prospective randomized comparative trials are required to critically evaluate the role of laparoscopy for this sophisticated and delicate operation.

  8. Multiple free-radical scavenging capacity in serum

    Science.gov (United States)

    Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

    2012-01-01

    We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

  9. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  10. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  11. Glutathione as a radical scavenger and the biological consequences of thiyl radical production

    International Nuclear Information System (INIS)

    Winterbourn, C.C.

    1996-01-01

    A large number of compounds that have toxic effects can be metabolised to free radicals and secondary reactive oxygen species. These may be directly damaging or affect cell function by altering regulatory mechanisms through changing redox status. Protection is provided by an integrated system of antioxidant defenses. This includes reduced glutathione (GSH), one of the functions of which is as a free radical scavenger. For GSH to be an effective radical scavenging antioxidant, therefore, it must act in concert with superoxide dismutase to remove the superoxide so generated. Superoxide is produced in a variety of metabolic processes. It is also a secondary product of radicals reacting with oxygen either directly or through GSH. The biological reactivity of superoxide has been the subject of much debate ever since the discovery of superoxide dismutase in 1968. It has more recently become apparent that its rapid reaction with nitric oxide to give peroxynitrite, and its ability to reversibly oxidise and inactivate iron sulphur enzymes, contribute to the toxicity of superoxide. Another mechanism that could be important involves addition reactions of superoxide with other radicals to give organic peroxides. This reaction, to form a tyrosine peroxide, has come to authors attention through the study of the scavenging of tyrosyl radicals by GSH. It is also shown that a tyrosine peroxide is a major product of the oxidation of tyrosine by neutrophils

  12. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    Energy Technology Data Exchange (ETDEWEB)

    Tinga, D.J.; Bouma, J.; Aalders, J.G. (Dept. of Obstetrics and Gynaecology, State Univ. Hospital, Groningen (Netherlands)); Hollema, H. (Dept. of Pathology, State Univ. Hospital, Groningen (Netherlands))

    1990-01-01

    Forty-nine patients aged {le} 45 years, with cervical carcinoma stage IB ({le} 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors).

  13. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    International Nuclear Information System (INIS)

    Tinga, D.J.; Bouma, J.; Aalders, J.G.; Hollema, H.

    1990-01-01

    Forty-nine patients aged ≤ 45 years, with cervical carcinoma stage IB (≤ 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors)

  14. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

    Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

  15. Isoflurane preconditions myocardium against infarction via release of free radicals

    NARCIS (Netherlands)

    Müllenheim, Jost; Ebel, Dirk; Frässdorf, Jan; Preckel, Benedikt; Thämer, Volker; Schlack, Wolfgang

    2002-01-01

    BACKGROUND: Isoflurane exerts cardioprotective effects that mimic the ischemic preconditioning phenomenon. Generation of free radicals is implicated in ischemic preconditioning. The authors investigated whether isoflurane-induced preconditioning may involve release of free radicals. METHODS:

  16. Mechanism of protection of adenosine from sulphate radical anion ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

  17. Free Radical Scavenging Properties of Annona squamosa

    Science.gov (United States)

    Vikas, Biba; Akhil B, S; P, Remani; Sujathan, K

    2017-10-26

    Annona squamosa has extensively been used in the traditional and folkloric medicine and found to possess many biological activities. Different solvents, petroleum ether, chloroform, ethyl acetate and methanol extracts of Annona squamosa seeds (ASPE, ASCH, ASEA, ASME) have been used to prepare plant extracts. The present investigations dealt with the free radical scavenging activity of four extracts using various techniques such as total reducing power estimation, total phenolic count, 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging effect, evaluation of ABTS cation decolorisation capacity, FRAP assay, hdroxyl radical scavenging assay, super oxide assay and Nitric oxide radical scavenging assay of the extracts. The results showed that the four extracts of Annona squamosa showed significant reducing power in four extracts. The total phenolic contents in petroleum ether, chloroform, ethyl acetate, methanol extracts and positive control were 0.64±0.17, 0.54±0.27, 0.49±0.24, 0.57±0.22 and 0.66±0.33. The antioxidant capacity by ABTS assay of ASPE, ASCH, ASEA, ASME and positive control, trolox showed 77.75±0.5,73.25±1.7,78.5± 1.2 , 80 ± 0.8 μg/ml and 94.2 ± 0.9 respectively. The (50 % scavenging activity) SA50 of ASPE and ASCH, ASEA and ASME was found to be 34.4 μg/ml, 43.8 μg/ml 34.7 μg/m and 28.8 μg/ml respectively by DPPH assay. The percentage of hydroxyl radical scavenging increased with the increasing concentration of the extracts. ASPE, ASCH, ASEA and ASME showed superoxide radical scavenging activity, as indicated by their values 66 ± 0.5, 68 ± 1 ,63 ± 1 and 70 ± 0.5 μg/ml respectively compared to gallic acid which was 97 ± 0.5 μg/ml. The values for scavenging of nitric oxide for ASPE, ASCH, ASEA and ASME were 91.0 ± 1.0, 66.75 ± 0.5, 71.75 ± 1.1 and 75.75 ± 1.15 μg/ml while value for standard ascorbic acid was 91.0 ± 1.0 μg/ml. The results revealed strong antioxidants in four extracts may lead to the development of potent

  18. Leadership Styles for the Five Stages of Radical Change

    Science.gov (United States)

    1998-04-01

    radical change. This article continues prior work on radical change with theory and research on leadership style. The result is a model of radical...every stage of that process. Leadership style and organiza- tional change theory and re- search have ex- isted for de- cades, but have rarely con...phase, inspire and en- ergize them to adopt the change after it Figure 3. Senior Manager Leadership Styles for the Five Phases of Radical Change Phase

  19. Superoxide radical (O2-) reactivity with respect to glutathione

    International Nuclear Information System (INIS)

    Sekaki, A.; Gardes-Albert, M.; Ferradini, C.

    1984-01-01

    Influence of superoxide radicals formed during gamma irradiation of glutathione in aerated aqueous solutions is examined. Solutions are buffered at pH7 and contain sodium formate for capture of H and OH radicals which are transformed in COO - radicals and then O 2 - radicals. G value of glutathione disparition vs glutathione concentration are given with and without enzyme or catalase. Reaction mechanism are interpreted [fr

  20. Riboflavin photosensitized oxidation of myoglobin

    DEFF Research Database (Denmark)

    Grippa, Juliana M.; de Zawadzki, Andressa; Grossi, Alberto Blak

    2014-01-01

    of MbFe(II)O by Rib is (3.0 ± 0.5) × 10 L·mol·s and (3.1 ± 0.4) × 10 L·mol·s for MbFe(III) in phosphate buffer of pH 7.4 at 25 C as determined by laser flash photolysis. The high rates are rationalized by ground state hydrophobic interactions as detected as static quenching of fluorescence from singlet...

  1. Hybrid radical energy storage device and method of making

    Science.gov (United States)

    Gennett, Thomas; Ginley, David S; Braunecker, Wade; Ban, Chunmei; Owczarczyk, Zbyslaw

    2015-01-27

    Hybrid radical energy storage devices, such as batteries or electrochemical devices, and methods of use and making are disclosed. Also described herein are electrodes and electrolytes useful in energy storage devices, for example, radical polymer cathode materials and electrolytes for use in organic radical batteries.

  2. Responsibility for radical change in addressing climate change

    NARCIS (Netherlands)

    Bouvrie, des N.; Karlsson-Vinkhuyzen, S.I.S.E.; Jollands, N.

    2015-01-01

    To radically address the problem of climate change, it is not enough to modify specific attitudes and behaviors while upholding the present paradigms. This article aims to show why modifications will never bring about radical carbon emission reductions. We discuss what it implies to desire radical

  3. Biochemistry and pathology of radical-mediated protein oxidation

    DEFF Research Database (Denmark)

    Dean, R T; Fu, S; Stocker, R

    1997-01-01

    Radical-mediated damage to proteins may be initiated by electron leakage, metal-ion-dependent reactions and autoxidation of lipids and sugars. The consequent protein oxidation is O2-dependent, and involves several propagating radicals, notably alkoxyl radicals. Its products include several catego...

  4. Enhancing production through optimisation of DPPH and radical ...

    African Journals Online (AJOL)

    ... of dry matter for DPPH radical scavenging activity. Methanol had the lowest value (78 mg g-1 dry matter) for polyphenol extracts and 80 mg g-1 for the DPPH radical scavenging activity. The main extract compounds were gallic acid, catechin and epicatechin. Key Words: High density lipids, polyphenol, radical scavenging ...

  5. Radical radiotherapy for T3 laryngeal cancers

    International Nuclear Information System (INIS)

    Uno, T.; Itami, J.; Kotaka, K.; Toriyama, M.

    1996-01-01

    From 1974 through 1992, 37 previously untreated patients with T3 laryngeal cancer (supraglottic 15, glottic 22) were treated with initial radical radiotherapy and surgery for salvage. Two-year local control rate with radiotherapy alone, ultimate voice preservation rate, and ultimate local control rate for T3 supraglottic cancer were 33%, 33%, and 60%, respectively. Corresponding figures for T3 glottic cancer were 32%, 23%, and 77%, respecitvely. Five-year cause-specific survival rate for T3 supraglottic cancer and glottic cancer were 47% and 77%, respectively. In T3 supraglottic cancer, none of the 4 patients with subglottic tumor extension attained local control by radiotherapy alone, and local-regional recurrence-free time were significantly shorter in patients with subglottic tumor extension or tracheostomy before radiotherapy. There were no serious late complications such as chondronecrosis, rupture of carotid artery attributed to radical radiotherapy, while 3 patients had severe laryngeal edema requiring total laryngectomy. (orig.) [de

  6. Editorial: RADICALISM AND POLITICS OF RELIGION

    Directory of Open Access Journals (Sweden)

    Editorial Al-Jami'ah: Journal of Islamic Studies

    2008-02-01

    Full Text Available Radical Islamism has become the “sexiest” issue in the international scholarship of religion since the September 11 tragedy in 2001. It has been associated with a number of terrorist attacks not only in the West but also in Muslim countries. Every single of radical Islamism has caught the interest of not only scholars and policy makers but also general public. Interestingly, the general assumption that religion is the source of peace has been seriously challenged, not by non-religious communities, but by the violent practices of particular religious groups, however small they are. Indeed, there are certain groups striving for Islam but by using acts which could give awful image on Islam itself and against humanity.

  7. Freedom Now! Radical Jazz and Social Movements

    Directory of Open Access Journals (Sweden)

    Przemysław Pluciński

    2014-01-01

    Full Text Available Music is obviously not only an aesthetic phenomenon. It is embeddedin a dense network of social relations. However, its social involvementis rather ambiguous, particularly since the second half of the twentiethcentury. On the one hand, music is one of the main elements of culturalcapitalism and a part of the system of domination. On the other hand,music provokes, (coproduces or possibly strengthens and coexists witha number of counterdiscourses and social projects of counterhegemoniccharacter.The main objective of the paper is to examine relationships between both, revolutionary jazz and revolutionary social movements, namely the civil rights movement, but above all radical movements, especially black power movement. The crucial questions I am interested in are problems of selforganization, performative social practices, as well as alternatives elaborated by radical-oriented jazz circles in various social dimensions, for instance economic or symbolic.

  8. Electronic spectrum of 9-methylanthracenium radical cation

    Energy Technology Data Exchange (ETDEWEB)

    O’Connor, Gerard D.; Schmidt, Timothy W., E-mail: timothy.schmidt@unsw.edu.au [School of Chemistry, UNSW Sydney, New South Wales 2052 (Australia); Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J. [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2016-04-21

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm{sup −1} to 44 500 cm{sup −1}. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D{sub 1}←D{sub 0} transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH{sub 2} or CH{sub 3}. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  9. Peace journalism and radical media ethics

    Directory of Open Access Journals (Sweden)

    Marta Natalia Lukacovic

    2016-10-01

    Full Text Available The radical characteristics of peace journalism position it as a model that expands the current understandings of normative media theory. Peace journalism echoes the most innovative calls of media ethicists, such as the proposition of radical media ethics. This idea asserts the necessity to expand media ethics to better fit the globalized and democratized media landscape, which is enabled by contemporary new media technologies. Essentially a global shift, among professionals as well as regular citizen-communicators, should advance towards conflict sensitivity in order to transcend the culturally violent elements of covering conflicts. Similar efforts will bring numerous challenges, however, these efforts are tremendously worthwhile with their potential to assist the creation of more peace-prone global societies.

  10. Radical pancreatectomy: postoperative evaluation by CT

    Energy Technology Data Exchange (ETDEWEB)

    Heiken, J.P.; Balfe, D.M.; Picus, D.; Scharp, D.W.

    1984-10-01

    Twenty-four patients who had undergone radical pancreatic resection were evaluated by CT one week to 11 years after surgery. Eighteen patients had had the Whipple procedure; six had had total pancreatectomy. The region between the aorta and superior mesenteric artery, previously occupied by the uncinate process of the pancreas, is an important area to evaluate for tumor recurrence because periampullary tumors tend to metastasize to the lymph nodes in this region. Tumor recurrence here is readily detectable by CT since radical pancreatectomy leaves this area area free of soft tissue attenuation material. CT demonstrated postoperative complications or tumor recurrence in 16 of the 24 patients and was 100% accurate in patients who had follow-up.

  11. International Radical Cystectomy Consortium: A way forward

    Directory of Open Access Journals (Sweden)

    Syed Johar Raza

    2014-01-01

    Full Text Available Robot-assisted radical cystectomy (RARC is an emerging operative alternative to open surgery for the management of invasive bladder cancer. Studies from single institutions provide limited data due to the small number of patients. In order to better understand the related outcomes, a world-wide consortium was established in 2006 of patients undergoing RARC, called the International Robotic Cystectomy Consortium (IRCC. Thus far, the IRCC has reported its findings on various areas of operative interest and continues to expand its capacity to include other operative modalities and transform it into the International Radical Cystectomy Consortium. This article summarizes the findings of the IRCC and highlights the future direction of the consortium.

  12. Coming to Grips with Radical Social Constructivisms

    Science.gov (United States)

    Phillips, D. C.

    This essay distinguishes two broad groups - psychological constructivists and social constructivists - but focusses upon the second of these, although it is stressed that there is great within group variation. More than half of the paper is devoted to general clearing of the ground, during which the reasons for the growing acrimony in the debates between social constructivists and their opponents are assessed, an important consequence of these debates for education is discussed, and an examination is carried out of the radical social constructivist tendency to make strong and exciting but untenable claims which are then backed away from (a tendency which is documented by a close reading of the early pages in Bloors classic book). The last portion of the essay focuses upon social constructivist accounts of the causes of belief in science - the more radical of which denegrate the role of warranting reasons, and which give an exalted place to quasi-anthropological or sociological studies of scientific communities.

  13. Radical pancreatectomy: postoperative evaluation by CT

    International Nuclear Information System (INIS)

    Heiken, J.P.; Balfe, D.M.; Picus, D.; Scharp, D.W.

    1984-01-01

    Twenty-four patients who had undergone radical pancreatic resection were evaluated by CT one week to 11 years after surgery. Eighteen patients had had the Whipple procedure; six had had total pancreatectomy. The region between the aorta and superior mesenteric artery, previously occupied by the uncinate process of the pancreas, is an important area to evaluate for tumor recurrence because periampullary tumors tend to metastasize to the lymph nodes in this region. Tumor recurrence here is readily detectable by CT since radical pancreatectomy leaves this area area free of soft tissue attenuation material. CT demonstrated postoperative complications or tumor recurrence in 16 of the 24 patients and was 100% accurate in patients who had follow-up

  14. EPR study of free radicals in bread

    Science.gov (United States)

    Yordanov, Nicola D.; Mladenova, Ralitsa

    2004-05-01

    The features of the recorded EPR spectra of paramagnetic species formed in bread and rusk are reported. The appearance of free radicals in them is only connected with their thermal treatment since the starting materials (flour and grains) exhibit very weak EPR signal. The obtained EPR spectra are complex and indicate that: (i) the relative number of paramagnetic species depends on the temperature and treating time of the raw product; (ii) the g-values are strongly temperature dependent with a tendency to coincide at t≥220 °C. Because of the relatively low (150-220 °C) temperature of thermal treatment, the studied free radicals can be assumed to appear in the course of the browning (Maillard) reaction and not to the carbonization of the material.

  15. EARLY POSTOPERATIVE COMPLICATIONS AFTER RADICAL CYSTECTOMY

    Directory of Open Access Journals (Sweden)

    V. O. Mager

    2014-08-01

    Full Text Available Radical cystectomy (RCE is associated with a considerable number of early postoperative complications as before. Based on 10 years’ experience, this paper demonstrates the frequency (33.9 % and types of early complications following RCE, as well as postoperative mortality (5.5 % and its resulting causes. Although postoperative mortality is relatively low today, the frequency of early postoperative complications remains high as before.

  16. Hydroxyl free radical production during torsional phacoemulsification.

    Science.gov (United States)

    Aust, Steven D; Hebdon, Thomas; Humbert, Jordan; Dimalanta, Ramon

    2010-12-01

    To quantitate free radical generation during phacoemulsification using an ultrasonic phacoemulsification device that includes a torsional mode and evaluate tip designs specific to the torsional mode. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. Experimental study. Experiments were performed using the Infiniti Vision System and OZil handpiece. Hydroxyl radical concentrations in the aspirated irrigation solution during torsional phacoemulsification were quantitated as nanomolar malondialdehyde (nM MDA) and determined spectrophotometrically using the deoxyribose assay. The mean free radical production during phacoemulsification with torsional modality at 100% amplitude was 30.1 nM MDA ± 5.1 (SD) using a 0.9 mm 45-degree Kelman tapered ABS tip. With other tip designs intended for use with the torsional modality, free radical production was further reduced when fitted with the 0.9 mm 45-degree Kelman mini-flared ABS tip (13.2 ± 5.6 nM MDA) or the 0.9 mm 45-degree OZil-12 mini-flared ABS tip (14.3 ± 6.7 nM MDA). Although the measurements resulting from the use of the latter 2 tips were not statistically significantly different (P ≈ .25), they were different from those of the tapered tip (P<.0001). The MDA concentration in the aspirated irrigation solution using the torsional modality was approximately one half that reported for the handpiece's longitudinal modality in a previous study using the same bent-tip design (Kelman tapered, P<.0001). The level of MDA was further reduced approximately one half with torsional-specific tips. Copyright © 2010 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

  17. How Hume's Philosophy Informed Radical Behaviorism.

    Science.gov (United States)

    Nuzzolilli, Andrew E; Diller, James W

    2015-05-01

    The present paper analyzes consistencies between the philosophical systems of David Hume and B. F. Skinner, focusing on their conceptualization of causality and attitudes about scientific behavior. The ideas that Hume initially advanced were further developed in Skinner's writings and shaped the behavior-analytic approach to scientific behavior. Tracing Skinner's logical antecedents allows for additional historical and philosophical clarity when examining the development of radical behaviorism.

  18. Western Radicalization: Rethinking the Psychology of Terrorism

    Science.gov (United States)

    2017-03-01

    to do so, they assert, locks both the researcher and the research subject into a “spiral of ignorance and suspicion.” Moreover, “social identity ...percentage of firefighters who commit this type of arson do so to establish an identity and sense of belonging. Similarly, disconnected Westerners...percentage of firefighters who commit this type of arson do so to establish an identity and sense of belonging. Similarly, disconnected Westerners radicalize

  19. Computed tomography after radical pancreaticoduodenectomy (Whipple's procedure)

    International Nuclear Information System (INIS)

    Smith, S.L.; Hampson, F.; Duxbury, M.; Rae, D.M.; Sinclair, M.T.

    2008-01-01

    Whipple's procedure (radical pancreaticoduodenectomy) is currently the only curative option for patients with periampullary malignancy. The surgery is highly complex and involves multiple anastomoses. Complications are common and can lead to significant postoperative morbidity. Early detection and treatment of complications is vital, and high-quality multidetector computed tomography (MDCT) is currently the best method of investigation. This review outlines the surgical technique and illustrates the range of normal postoperative appearances together with the common complications

  20. Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

    Directory of Open Access Journals (Sweden)

    Ken Reidy

    2018-03-01

    Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

  1. Free radicals induced archive paper by irradiation

    International Nuclear Information System (INIS)

    Cutrubinis, M.; Moise, I.V.; Negut, C.D.; Georgescu, R.; Suvaila, R.; Virgolici, M.; Manea, M.M.

    2011-01-01

    Complete text of publication follows. Irradiation of archive paper (document archives of institutions, companies etc. and library or museum collections of books and documents) can solve the problems related to the bio-deterioration and bio-contamination of paper and sometimes save valuable cultural heritage paper items. For valuable paper items care should be taken to the degradation induced instantly by the ionising radiation to the cellulosic support and also to the long term post-irradiation effects. The free radicals formed due to the irradiation treatment could contribute to instant degradation of paper. Part of them are also trapped for months and years after irradiation and they could be related to the post-irradiation effects in paper items. In this study, different sorts of cellulosic support samples (soft wood and hard wood cellulose, contemporary paper, paper from archives and from collections etc.) have been irradiated with dosis up to 100 kGy and the radiation induced free radicals have been measured by ESR spectrometry. The ESR signals have shown the type and quantity of radiation induced free radicals. Their study can be used for a realistic estimation of the degradative effect of the ionising radiation treatment of archive paper.

  2. Complications of Radical Cystectomy and Orthotopic Reconstruction

    Directory of Open Access Journals (Sweden)

    Wei Shen Tan

    2015-01-01

    Full Text Available Radical cystectomy and orthotopic reconstruction significant morbidity and mortality despite advances in minimal invasive and robotic technology. In this review, we will discuss early and late complications, as well as describe efforts to minimize morbidity and mortality, with a focus on ileal orthotopic bladder substitute (OBS. We summarise efforts to minimize morbidity and mortality including enhanced recovery as well as early and late complications seen after radical cystectomy and OBS. Centralisation of complex cancer services in the UK has led to a fall in mortality and high volume institutions have a significantly lower rate of 30-day mortality compared to low volume institutions. Enhanced recovery pathways have resulted in shorter length of hospital stay and potentially a reduction in morbidity. Early complications of radical cystectomy occur as a direct result of the surgery itself while late complications, which can occur even after 10 years after surgery, are due to urinary diversion. OBS represents the ideal urinary diversion for patients without contraindications. However, all patients with OBS should have regular long term follow-up for oncological surveillance and to identify complications should they arise.

  3. Radical Homemaking in Contemporary American Environmental Fiction

    Directory of Open Access Journals (Sweden)

    Kristin J. Jacobson

    2018-02-01

    Full Text Available Ursula K. Heise in ‘Ecocriticism and the Transnational Turn in American Studies’ critiques ‘the portrayal of multicultural and sometimes transnational nuclear families as the narrative solution to environmental and political problems’ (Heise, 2008: 383. This essay places Heise’s critique of the ‘ecological family romance’ in conversation with three other ecological domestic fictions: T. C. Boyle’s 'A Friend of the Earth' (2000, Jonathan Franzen’s 'Freedom' (2010, and Barbara Kingsolver’s 'Flight Behavior' (2012. Heise’s critique and Shannon Hayes’ 'Radical Homemakers' (2010 frame my close readings of the novels’ interconnected themes of radical homemaking, transnationalism, and environmentalism. My reading of the novels highlights their shared use of marginalized, racially-other characters to develop their entwined romantic and environmental plots (Lalitha in 'Freedom', several minor characters in 'A Friend of the Earth', and Ovid in 'Flight Behavior' and their use of sentimental deaths, especially of key female characters (Lalitha in Freedom, Sierra in A Friend of the Earth, and Dellarobia’s uncertain fate in Flight Behavior. By adopting the sentimental, domestic romance plot for ecological aims, the three novels highlight how environmental aims get stymied when cultural and ecological diversity are relegated to the margins. They also suggest that more is gained than lost through their use of ecological allegory. While the fictions do not offer solutions, they do push their readers to confront the Anthropocene’s ecological realities and their radical domestic-environmental politics.

  4. The Rise of Radicals in Bioinorganic Chemistry.

    Science.gov (United States)

    Gray, Harry B; Winkler, Jay R

    2016-10-01

    Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O 2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O 2 -reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O 2 is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O 2 reduction.

  5. Peroxy Radical Measurements via Laser Induced Fluorescence

    Science.gov (United States)

    Trawny, Katrin; Tatum Ernest, Cheryl; Novelli, Anna; Elste, Thomas; Plaß-Dülmer, Christian; Rudolf, Markus; Martinez, Monica; Harder, Hartwig; Lelieveld, Jos

    2013-04-01

    We present a newly built Laser Induced Fluorescence (LIF) system to measure the sum of all peroxy radicals (RO2) utilizing chemical conversion to OH. This instrument operates in two different modes: the ROx mode (sum of OH, HO2, and RO2) and the HOx mode (sum of OH and HO2). The HOx mode is used to derive the RO2 data from the ROx measurements. A model approach was used during instrumental development to identify the key parameters needed for the conversion process in front of the detection area and to optimize sensitivity. The instrument was then carefully characterized in various lab experiments, where it could be shown that the wall losses for HO2 are negligible and that nearly all HO2 is converted to OH in front of the detection zone. The pressure and temperature dependencies were also analyzed and assured that the instrument does not show any photolytical interference. As the instrument is calibrated with only one kind of peroxy radicals it was very important that the differences in sensitivity for different peroxy radicals are acceptable. Lab experiments as well as first results from the HOPE 2012 intensive field campaign, which took place in summer 2012 at the Global Atmosphere Watch (GAW) station of the German Weather Service, will be discussed.

  6. Laparoscopic radical prostatectomy in the canine model.

    Science.gov (United States)

    Price, D T; Chari, R S; Neighbors, J D; Eubanks, S; Schuessler, W W; Preminger, G M

    1996-12-01

    The purpose of this study was to determine the feasibility of performing laparoscopic radical prostatectomy in a canine model. Laparoscopic radical prostatectomy was performed on six adult male canines. A new endoscopic needle driver was used to construct a secure vesicourethral anastomosis. Average operative time required to complete the procedure was 304 min (range 270-345 min). Dissection of the prostate gland took an average of 67 min (range 35-90 min), and construction of the vesicourethral anastomosis took 154 min (rage 80-240 min). There were no intraoperative complications and only one postoperative complication (anastomotic leak). Five of the six animals recovered uneventfully from the procedure, and their foley catheters were removed 10-14 days postoperatively after a retrograde cystourethrogram demonstrated an intact vesicourethral anastomosis. Four (80%) of the surviving animals were clinically continent within 10 days after catheter removal. Post mortem examination confirmed that the vesicourethral anastomosis was intact with no evidence of urine extravasation. These data demonstrate the feasibility of laparoscopic radical prostatectomy in a canine model, and suggest that additional work with this technique should be continued to develop its potential clinical application.

  7. Radical inactivation of a biological sulphydryl molecule

    International Nuclear Information System (INIS)

    Lin, W.S.; Lal, M.; Gaucher, G.M.; Armstrong, D.A.

    1977-01-01

    Reactive species produced from the free radical-induced chain oxidation of low molecular weight sulphydryl-containing molecules in aerated solutions deactivate the sulphydryl-containing enzyme papain, forming both reparable mixed disulphides and non-reparable products. This inactivation is highly efficient for penicillamine and glutathione, but almost negligible with cysteine, which is a protector of papain for [cysteine] / [papain] >= 5 under all conditions used. In the case of glutathione, superoxide dismutase caused only a small reduction in the inactivation and peroxide yields were small, implying that the deactivating species are not .O 2 - but RSOO. radicals or products from them. For penicillamine, however, dimutase was highly effective and the peroxide yields were relatively large, demonstrating that .O 2 - or a radical with similar capabilities for forming H 2 O 2 and being deactivated by dismutase was involved. Although in the presence of dismutase penicillamine is a better protector of non-reparable papain inactivation than glutathione, it suffers from a deficiency in that the papain-penicillamine mixed disulphide, which is always formed, cannot be repaired by spontaneous reaction with RSH molecules. (author)

  8. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    Science.gov (United States)

    Yeung, Pui-sze; Ho, Connie Suk-han; Chan, David Wai-ock; Chung, Kevin Kien-hoa

    2016-01-01

    A 3-year longitudinal study among 239 Chinese students in Grades 2-4 was conducted to investigate the relationships between orthographic skills (including positional and functional knowledge of semantic radicals and phonetic radicals, and orthographic memory of radicals) and Chinese literacy skills (word reading, word spelling, reading…

  9. Generation and propagation of radical reactions on proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    2001-01-01

    The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...... be propagated and transferred within protein structures. The emphasis of this article is primarily on the deleterious actions of radicals generated on proteins, and their mechanisms of action, rather than on enzymatic systems where radicals are deliberately formed as transient intermediates. The final section...

  10. Formation and spectroscopy of {alpha}-muoniated radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

    2003-02-01

    Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

  11. Formation and spectroscopy of α-muoniated radicals

    International Nuclear Information System (INIS)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

    2003-01-01

    Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

  12. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Stasica, P.; Ulanski, P.; Rosiak, J.M.

    1998-01-01

    Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

  13. What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

    Science.gov (United States)

    Baum, William M

    2011-01-01

    B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

  14. Total free radical species and oxidation equivalent in polluted air.

    Science.gov (United States)

    Wang, Guoying; Jia, Shiming; Niu, Xiuli; Tian, Haoqi; Liu, Yanrong; Chen, Xuefu; Li, Lan; Zhang, Yuanhang; Shi, Gaofeng

    2017-12-31

    Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Electron spin resonance study of radicals in irradiated polyethylene

    International Nuclear Information System (INIS)

    Fujimura, Takashi

    1979-02-01

    In order to elucidate radiation effect in polyethylene, the nature and behavior of radicals produced in polyethylene and the model compound of polyethylene irradiated at 77 0 K were studied by using electron spin resonance. The structure of radical pairs, which are composed of two radicals produced very closely each other, was investigated in drawn polyethylene and the single crystal of n-eicosane. The radical pairs of intrachain type and interchain type were found in polyethylene and n-eicosane respectively. It was suggested that these two types of radical pairs are the precursors of double bonds and crosslinks respectively. The thermal decay reactions of radicals themselves produced in irradiated polyethylene were investigated. It was made clear that the short range distances between two radicals play an important role in the decay reaction of alkyl radicals at low temperatures. The trapping regions of radicals were studied and it was clarified that allyl radicals, which are produced by the reaction of alkyl radicals with double bonds, are trapped both in the crystalline and non-crystalline regions. (author)

  16. OH radical induced depolymerization of poly(methacrylic acid)

    Science.gov (United States)

    Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

    1999-05-01

    Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

  17. Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

    1992-01-01

    Reactions of carbonate (CO 3 - radical) and bicarbonate (HCO 3 radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10 6 -10 7 dm 3 mol -1 s -1 . From the time-resolved spectroscopy of the products formed after reaction of CO 3 - radical or HCO 3 radical, it is observed that CO 3 - radical or HCO 3 radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

  18. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  19. Even free radicals should follow some rules: a guide to free radical research terminology and methodology.

    Science.gov (United States)

    Forman, Henry Jay; Augusto, Ohara; Brigelius-Flohe, Regina; Dennery, Phyllis A; Kalyanaraman, Balaraman; Ischiropoulos, Harry; Mann, Giovanni E; Radi, Rafael; Roberts, L Jackson; Vina, Jose; Davies, Kelvin J A

    2015-01-01

    Free radicals and oxidants are now implicated in physiological responses and in several diseases. Given the wide range of expertise of free radical researchers, application of the greater understanding of chemistry has not been uniformly applied to biological studies. We suggest that some widely used methodologies and terminologies hamper progress and need to be addressed. We make the case for abandonment and judicious use of several methods and terms and suggest practical and viable alternatives. These changes are suggested in four areas: use of fluorescent dyes to identify and quantify reactive species, methods for measurement of lipid peroxidation in complex biological systems, claims of antioxidants as radical scavengers, and use of the terms for reactive species. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Lopes

    2003-01-01

    Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

  1. Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

    International Nuclear Information System (INIS)

    Mohr, C.; Schettler, D.; Bohndorf, W.

    1994-01-01

    A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

  2. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

  3. Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

    Directory of Open Access Journals (Sweden)

    I-Fan eSu

    2012-09-01

    Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

  4. Ultraviolet photodissociation dynamics of the benzyl radical.

    Science.gov (United States)

    Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

    2011-05-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

  5. Resonance Raman study of benzyl radical

    DEFF Research Database (Denmark)

    Langkilde, F.W.; Bajdor, K.; Wilbrandt, R.

    1992-01-01

    Time-resolved resonance Raman spectra are obtained of benzyl radicals created by laser flash photolysis of benzylchloride and diphenylacetone in solution. The spectra are obtained in resonance with the intense 2 2A2-1 B-2(2) transition of benzyl. The strong Raman bands are assigned to totally...... symmetric a1 modes. The remaining observed bands are tentatively assigned to fundamental modes of b1, a2, and b2 symmetry, and to overtones and combinations. The resonance Raman spectra are found to be quite different from previous fluorescence spectra of benzyl, and the origins of these differences...

  6. Dissociative Photoionization of the Elusive Vinoxy Radical.

    Science.gov (United States)

    Adams, Jonathan D; Scrape, Preston G; Lee, Shih-Huang; Butler, Laurie J

    2017-08-24

    These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser-molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH 3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic-energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH 3 + relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O( 3 P) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl + ) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO + calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH 3 + . We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH 3 + and HCO + .

  7. Processing of free radical damaged DNA bases

    International Nuclear Information System (INIS)

    Wallace, S.

    2003-01-01

    Free radicals produced during the radiolysis of water gives rise to a plethora of DNA damages including single strand breaks, sites of base loss and a wide variety of purine and pyrimidine base lesions. All these damages are processed in cells by base excision repair. The oxidative DNA glycosylases which catalyze the first step in the removal of a base damage during base excision repair evolved primarily to protect the cells from the deleterious mutagenic effects of single free radical-induced DNA lesions arising during oxidative metabolism. This is evidenced by the high spontaneous mutation rate in bacterial mutants lacking the oxidative DNA glycosylases. However, when a low LET photon transverses the DNA molecule, a burst of free radicals is produced during the radiolysis of water that leads to the formation of clustered damages in the DNA molecule, that are recognized by the oxidative DNA glycosylases. When substrates containing two closely opposed sugar damages or base and sugar damages are incubated with the oxidative DNA glycosylases in vitro, one strand is readily incised by the lyase activity of the DNA glycosylase. Whether or not the second strand is incised depends on the distance between the strand break resulting from the incised first strand and the remaining DNA lesion on the other strand. If the lesions are more than two or three base pairs apart, the second strand is readily cleaved by the DNA glycosylase, giving rise to a double strand break. Even if the entire base excision repair system is reconstituted in vitro, whether or not a double strand break ensues depends solely upon the ability of the DNA glycosylase to cleave the second strand. These data predicted that cells deficient in the oxidative DNA glycosylases would be radioresistant while those that overproduce an oxidative DNA glycosylase would be radiosensitive. This prediction was indeed borne in Escherichia coli that is, mutants lacking the oxidative DNA glycosylases are radioresistant

  8. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  9. Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

    Science.gov (United States)

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  10. NOx removal characteristics of corona radical shower with ammonia and methylamine radical injections

    Energy Technology Data Exchange (ETDEWEB)

    Urashima, K.; Ara, M.; Chang, J.S. [McMaster Univ., Hamilton, ON (Canada). Dept. of Engineering Physics; Uchida, Y. [Aichi Inst. of Technology, (Japan). Dept. of Engineering

    2010-07-01

    Air pollutants such as nitrogen oxides (NOx) and sulfur oxides (SOx) are the major cause of acid rain. There are different types of NOx and SOx conversion techniques such as wet scrubber, selective catalytic reactor, sorbent injection, and low NOx burner. Non-thermal plasma techniques have also been utilized in commercial plants, but the energy efficiency of the non-thermal plasma reactors have not yet been optimized. The direct plasma treatments of flue gases including, the electron beam, barrier discharge and pulsed corona reactors, may lose input energy to activate unwanted components of flue gases such as carbon dioxide (CO{sub 2}) and nitrogen (N{sub 2}). The corona discharge ammonia radical shower system has demonstrated significant NOx removal with higher energy efficiency for large bench scale and pilot plant tests for combustion exhausts. An experiment has also demonstrated that methane can replace ammonia as an injection gas with less NOx removal efficiency. This paper presented an experimental investigation that compared methylamine radical injection with traditional ammonia and methane radical injections. The paper discussed the bench scale test facilities and corona radical shower plasma reactor. It was concluded that the processes to form ammonium nitrate could be observed from trace white solid particles deposited on the reactor wall as observed by scanning electron microscopy pictures. 10 refs., 5 figs., 2 appendices.

  11. Encapsulation of Gibbsite platelets with free radical and controlled radical emulsion polymerization approaches, a small review

    NARCIS (Netherlands)

    Loiko, O.P.; Spoelstra, A.B.; van Herk, A.M.; Meuldijk, J.; Heuts, J.P.A.

    2016-01-01

    Water-borne anisotropic polymer-Gibbsite latex particles were prepared by a conventional and an atom transfer radical polymerisation (ATRP) based starved-feed emulsion polymerisation without any chemical modification of the platelet surface. Anionic co-oligomers, synthesised via ATRP, were used in

  12. Nitroxide-mediated controlled radical polymerisation: towards control of molar mass Controlled Radical Polymerisation

    NARCIS (Netherlands)

    Bon, S.A.F.; Bergman, F.A.C.; Es, van J.J.G.S.; Klumperman, B.; German, A.L.; Matyjaszewski, K.

    1998-01-01

    The mechanism of the TEMPO-mediated controlled radical polymerization of styrene in bulk is discussed. It is shown that the isotropic correlation time (tc) of a nitroxide can be used as a measure of the diffusive rate coefficient of trapping (ketD). A general empirical relationship for the density

  13. Electron spin resonance spectroscopy of organic radicals spectroscopy of organic radicals

    CERN Document Server

    Gerson, Fabian

    2006-01-01

    ""This book should serve as a comprehensive one-volume source for finding what is known about the splitting constants and g factors of virtually all types of organic radicals."" Journal of the American Chemistry Society, 2004, Vol. 126 No. 20

  14. Hydrogen Radicals, Nitrogen Radicals, and the Production of Ozone in the Middle and Upper Troposphere

    Science.gov (United States)

    Bui, T. P.

    1997-01-01

    The concentrations of hydrogen radicals, OH and HO2, in the middle and upper troposphere were measured simultaneously with those of NO, O3,CO, H20, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field.

  15. Radical constructivism and radical constructedness: Luhmann's sociology of semantics, organizations, and self-organization

    NARCIS (Netherlands)

    Leydesdorff, L.

    2012-01-01

    Context: Using radical constructivism, society can be considered from the perspective of asking the question, "Who conceives of society?" In Luhmann’s social systems theory, this question itself is considered as a construct of the communication among reflexive agents. Problem: Structuration of

  16. COST Action CM1201 "Biomimetic Radical Chemistry": free radical chemistry successfully meets many disciplines

    Czech Academy of Sciences Publication Activity Database

    Ferreri, C.; Golding, B. T.; Jahn, Ullrich; Ravanat, J. L.

    2016-01-01

    Roč. 50, Suppl 1 (2016), S112-S128 ISSN 1071-5762 Institutional support: RVO:61388963 Keywords : radical enzyme * membrane stress * phospholipid remodeling * DNA damage and repair * biomimetic models * bio-inspired synthetic methodologies Subject RIV: CC - Organic Chemistry Impact factor: 3.188, year: 2016 http://www.tandfonline.com/doi/full/10.1080/10715762.2016.1248961

  17. The mitochondrial free radical theory of aging.

    Science.gov (United States)

    Barja, Gustavo

    2014-01-01

    The mitochondrial free radical theory of aging is reviewed. Only two parameters currently correlate with species longevity in the right sense: the mitochondrial rate of reactive oxygen species (mitROS) production and the degree of fatty acid unsaturation of tissue membranes. Both are low in long-lived animals. In addition, the best-known manipulation that extends longevity, dietary restriction, also decreases the rate of mitROS production and oxidative damage to mtDNA. The same occurs during protein restriction as well as during methionine restriction. These two manipulations also increase maximum longevity in rodents. The decrease in mitROS generation and oxidative stress that takes place in caloric restriction seems to be due to restriction of a single dietary substance: methionine. The information available supports a mitochondrial free radical theory of aging focused on low generation of endogenous damage and low sensitivity of membranes to oxidation in long-lived animals. © 2014 Elsevier Inc. All rights reserved.

  18. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Cyr, Douglas Robert [Univ. of California, Berkeley, CA (United States)

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

  19. Radical reactions in vivo - an overview

    International Nuclear Information System (INIS)

    Saran, M.; Bors, W.

    1990-01-01

    Generation of radicals in vivo depends on metabolic activities. The reactions are usually influenced by (i) the presence and concentration of oxygen, (ii) the availability of transition metals (effects of binding and compartimentalization), (iii) the level of reductants and antioxidants (e.g. nutritional effects). The effects of radicals are thought to be due to (i) membrane damage (affecting passive or active transport through altered fluidity/function interrelationships, intercellular messenging through modifications in the synthesis of prostaglandins and leukotrienes); (ii) protein damage (e.g. affecting membrane transporters, channel proteins, receptor or regulatory proteins, immunomodulators); (iii) damage to DNA. Defense mechanisms consist of (i) prevention of the 'spreading' of primary damage by low molecular weight antioxidants (e.g. vitamin E, GSH, vitamin C, β-carotene, uric acid); (ii) prevention or limitation of 'secondary' damage by enzymes (e.g. GSH-peroxidase, catalase, superoxide dismutase, DT-diaphorase) and/or chelators; (iii) repair processes, e.g. lipid degradation/membrane repair enzymes (phospholipases, peroxidases, some transferases and reductases), protein disposal or repair enzymes (proteases, GSSG-reductase), DNA degradation or repair enzymes (exonucleases III, endonucleases III and IV, glycosylases, polymerases). Recent hypotheses on a messenging function of the superoxide anion O 2 - are discussed and possible implications of cross-reactions between O 2 - and nitric oxide (endothelium-derived relaxing factor EDRF) are shortly mentioned. (orig.)

  20. The Rovibronic Spectra of the Cyclopentadienyl Radical

    Science.gov (United States)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  1. Mechanisms of radical removal by SO2

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund; Glarborg, Peter; Marshall, Paul

    2007-01-01

    It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO2 acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO2 + H......(+M) reversible arrow HOSO(+M), HOSO + H/OH reversible arrow SO2 + H-2/H2O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO2 interactions. We find...... that the interaction of SO, with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO2 recombination and with SO + H2O, rather than SO2 + H-2, as major products of the HOSO + H...

  2. Free Radicals and Extrinsic Skin Aging

    Directory of Open Access Journals (Sweden)

    Borut Poljšak

    2012-01-01

    Full Text Available Human skin is constantly directly exposed to the air, solar radiation, environmental pollutants, or other mechanical and chemical insults, which are capable of inducing the generation of free radicals as well as reactive oxygen species (ROS of our own metabolism. Extrinsic skin damage develops due to several factors: ionizing radiation, severe physical and psychological stress, alcohol intake, poor nutrition, overeating, environmental pollution, and exposure to UV radiation (UVR. It is estimated that among all these environmental factors, UVR contributes up to 80%. UV-induced generation of ROS in the skin develops oxidative stress, when their formation exceeds the antioxidant defence ability of the target cell. The primary mechanism by which UVR initiates molecular responses in human skin is via photochemical generation of ROS mainly formation of superoxide anion (O2−•, hydrogen peroxide (H2O2, hydroxyl radical (OH•, and singlet oxygen (1O2. The only protection of our skin is in its endogenous protection (melanin and enzymatic antioxidants and antioxidants we consume from the food (vitamin A, C, E, etc.. The most important strategy to reduce the risk of sun UVR damage is to avoid the sun exposure and the use of sunscreens. The next step is the use of exogenous antioxidants orally or by topical application and interventions in preventing oxidative stress and in enhanced DNA repair.

  3. Nitrate radicals and biogenic volatile organic compounds ...

    Science.gov (United States)

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in

  4. Radical cystectomy: Analysis of postoperative course

    Directory of Open Access Journals (Sweden)

    Jeremić Dimitrije

    2010-01-01

    Full Text Available Background/Aim. Radical cystectomy is a method of choice in the therapy of infiltrative bladder cancer. The aim of this research was to analyze postoperative course after radical cystectomy (length of hospitalization, most frequent complications and utilization of antibiotics and transfusions. Methods. We analyzed the records of 82 patients operated on in the Department of Urology, Clinical Center of Vojvodina, in a three-year period. In order to aquire data World Health Organization (WHO has developed Anatomical Therapeutic Chemical/Defined Daily Dose (ATC/DDD methodology. Defined daily dose (DDD is the assumed average maintenance dose per day for a drug use for its main indication. Results. Continent urinary derivation was preformed in 23.15% cases. Postoperative complications occurred in 18.29% of patients. Average blood utilization was 2.19 units. Blood utilization for continent derivations (n = 48 was 4.6 units, and incontinent ones 3.36 units. Totally 159.33 DDD/100 bed days were used. Conclusion. When preforming continent derivation there is a significant increase in blood utilization. Frequency of postoperative complications correlates to those reported in the literature.

  5. Hydroxyl radical induced degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: erzsebet.illes@chem.u-szeged.hu [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Takács, Erzsébet [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Dombi, András [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Gajda-Schrantz, Krisztina [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged (Hungary); EMPA, Laboratory for High Performance Ceramics, Duebendorf (Switzerland); Rácz, Gergely; Gonter, Katalin; Wojnárovits, László [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary)

    2013-03-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm{sup −3}. For end product characterization {sup 60}Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of {sup ·}OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation.

  6. Fast beam studies of free radical photodissociation

    International Nuclear Information System (INIS)

    Cyr, D.R.; California Univ., Berkeley, CA

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward

  7. Ascorbyl radical disproportionation in reverse micellar systems

    Science.gov (United States)

    Gębicki, J. L.; Szymańska-Owczarek, M.; Pacholczyk-Sienicka, B.; Jankowski, S.

    2018-04-01

    Ascorbyl radical was generated by the pulse radiolysis method and observed with the fast kinetic spectrophotometry within reverse micelles stabilized by AOT in n-heptane or by Igepal CO-520 in cyclohexane at different water to surfactant molar ratio, w0. Rate constants for the disproportionation of the ascorbyl radicals were smaller than those for intermicellar exchange for both type of reverse micelles and slower than those in homogeneous aqueous solutions. However, they increased with increasing w0 for AOT/n-heptane system, while they decreased for Igepal CO-520 system. The absorption spectra of ascorbic acid AOT/n-heptane reverse micellar system showed that the "pH" sensed by this molecule is lower than that in respective homogeneous aqueous solutions. The obtained results were rationalized taking into account three main factors (i) preferential location of ascorbic acid molecules in the interfacial region of the both types of reverse micelles; (ii) postulate that the pH of the interface is lower than that of the water pool of reverse micelles and (iii) different structure of the interface of the reverse micelles made by AOT in n-heptane and those formed by Igepal CO-520 I cyclohexane. Some possible consequences of these findings are discussed.

  8. The Prospects of Radical Change Today

    Directory of Open Access Journals (Sweden)

    Slavoj Žižek

    2018-05-01

    Full Text Available In this contribution, Slavoj Žižek takes the occasion of Marx’s bicentenary for reflecting on the prospects of radical change today. First, it is shown that under Stalinism, Lenin’s works were quoted out of context in an arbitrary way in order to legitimise arbitrary political measures. Marxism thereby became an ideology that justified brutal subjective interventions. Second, this contribution poses the question of the revolutionary subject and democracy today. It stresses the role of both contingency and strategy in revolutions. In political assemblages taking place on public squares, the inert mass of ordinary people is transubstantiated into a politically engaged united force. The basic political problem today is how to best reconfigure democracy. Third, this contribution analyses the “interesting times” we live in. These are times that feature multiple crises, right-wing populism à la Donald Trump and Marine Le Pen, the lower classes’ opposition to immigration, and the refugee crisis. Questions about human rights and their violation and about radical change need to be asked in this context.

  9. Hegel’s Gesture Towards Radical Cosmopolitanism

    Directory of Open Access Journals (Sweden)

    Shannon Brincat

    2009-09-01

    Full Text Available This is a preliminary argument of a much larger research project inquiring into the relation betweenHegel’s philosophical system and the project of emancipation in Critical International Relations Theory. Specifically, the paper examines how Hegel’s theory of recognition gestures towards a form of radical cosmopolitanism in world politics to ensure the conditions of rational freedom for all humankind. Much of the paper is a ground-clearing exercise defining what is ‘living’ in Hegel’s thought for emancipatory approaches in world politics, to borrow from Croce’s now famous question. It focuses on Hegel’s unique concept of freedom which places recognition as central in the formation of self-consciousness and therefore as a key determinant in the conditions necessary forhuman freedom to emerge in political community. While further research is needed to ascertain the precise relationship between Hegel’s recognition theoretic, emancipation and cosmopolitanism, it is contended that the intersubjective basis of Hegel’s concept of freedom through recognition necessitates some form of radical cosmopolitanism that ensures successful processes of recognition between all peoples, the precise institutional form of which remains unspecified.

  10. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  11. Hydroxyl radical induced degradation of ibuprofen

    International Nuclear Information System (INIS)

    Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Rácz, Gergely; Gonter, Katalin; Wojnárovits, László

    2013-01-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm −3 . For end product characterization 60 Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of · OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation

  12. Radicals of DNA and DNA nucleotides generated by ionising radiation

    International Nuclear Information System (INIS)

    Przybytniak, G.

    2004-01-01

    A first stage of cell processes leading to DNA damage of initiated by radical reactions. In a model system such transformations were generated by ionising radiation which involves production of electron loss and electron gain centers of the substrate and radical formation. Using cryogenic ESR spectroscopy it was found that the DNA nucleotides, which convert to radical anions upon electron capture undergo the separation of unpaired spin and charge due to protonation. Circular and linear dichroism studies enabled to conclude that iron ions(III) induce strong changes in the DNA helical structure indicating their coordination with nitrogen bases. The repair of DNA radicals produced via radiolytic oxidation, i.e. the guanine radical cation and the allyl type radical of thymine, is possible at elevated temperatures due to the involvement of sulphydryl groups. The influence of the thiol charge is then limited

  13. Acyclic diastereoselection in prochiral radical addition to prochiral olefins.

    Science.gov (United States)

    Sibi, Mukund P; Rheault, Tara R; Chandramouli, Sithamalli V; Jasperse, Craig P

    2002-03-27

    The stereochemical preference (syn or anti) when prochiral radicals add to prochiral acceptors is of fundamental interest. The primary focus of this research was to determine which factors influence the relative stereochemistry between the beta and gamma chiral centers when these are formed concurrently. While moderate diastereoselectivity was found for addition of alkyl (6a-d) and alpha-alkoxy radicals (16a-c) (15:1 anti). Steric influence in alkyl radical additions was difficult to evaluate due to decreased reactivity when using bulky reaction partners; however, more reactive alpha-alkoxy radicals, it was found that increasing steric bulk leads to moderate increases in selectivity. In addition, higher selectivity was observed when employing lanthanide Lewis acids whose environment (reactivity) was modified using achiral additives, suggesting a potentially simple means for selectivity enhancements in radical reactions. Overall these results indicate that significant stereoelectronic effects are necessary to achieve high levels of selectivity in prochiral radical additions to prochiral acceptors.

  14. Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets

    Science.gov (United States)

    Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.

    2016-04-01

    Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

  15. [Radicalism and feminism: The case of Poulain de la Barre].

    Science.gov (United States)

    Pellegrin, Marie-Frédérique

    2015-12-01

    Early modern radicalism and its criteria are described and defined by Jonathan Israel in various works. Poulain de la Barre, one of the first modern feminist thinkers, first is used by Israel as an example of the so-called radical Enlightenment and finally is rejected as such. This case study exhibed the necessity of questionning the coherence of the required criteria for defining a « radical » thinker, especially when examinating carefully the last paragraph of Spinoza's Political Treatise.

  16. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Radical polarization in double switching of external magnetic field

    International Nuclear Information System (INIS)

    Lukzen, N.N.; Morozov, V.A.; Sagdeev, R.Z.

    1999-01-01

    Theoretical treatment of radical spin evolution under the action of double switching of external magnetic field is proposed. Account is taken of evolution of the radical spin state during laser pulse which generates paramagnetic particles. It is shown that the most effective beats in the nuclear magnetization of diamagnetic products of recombination occur upon the jump into zero magnetic field after laser pulse. The phase of observed beats bears information about the type of the initial radical polarization. The frequency of the beats is determined by radical hyperfine structure. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  18. The research progress of several kinds of free radical scavengers

    International Nuclear Information System (INIS)

    Qian Liren; Huang Yuecheng; Cai Jianming

    2009-01-01

    Ionization radiation can generate free radicals in biological system, which could induce lipid peroxi-dation, biomacromolecule and biomembrane damage, lost of cell function, cell cycle disturbance, genetic mutation and so on. The scavenging free radicals can protect organism from radiation damage. Many radio-protective agents, such as amylase, hydroxyl-benzene derivatives, hormone, vitamin, have great abilities to protect organism from radiation via scavenging free radicals. In this paper, we mainly review the free radical scavenging effects of several kinds of radio-protective agents. (authors)

  19. Progress on resonance ionization detection of combustion radicals

    International Nuclear Information System (INIS)

    Cool, T.A.

    1994-01-01

    Selective laser ionization techniques are used in our laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames. The progress made on the following three separate experiments during the past year is briefly described in this report. Flame Radical Concentration Measurements with VUV Spectroscopy; observation of hyperfine quantum beats in cyanogen; and the spectroscopy of the ClCO radical

  20. Incontinence and Erectile Dysfunction Following Radical Prostatectomy: A Review

    Directory of Open Access Journals (Sweden)

    Gerasimos Alivizatos

    2005-01-01

    Full Text Available Radical prostatectomy remains the treatment of choice for localized prostate cancer in age-appropriate and health-appropriate men. Although cancer control is the most important aspect of a radical prostatectomy, minimization of postoperative morbidity, especially urinary incontinence and erectile dysfunction, is becoming a greater concern. We reviewed recent data available on Medline regarding the incidence, pathophysiology, evaluation, and treatment of incontinence and sexual dysfunction after radical prostatectomy. Health-related quality of life issues have been specifically addressed. Although low incidences of incontinence and erectile dysfunction after radical prostatectomy have been reported in the hands of experienced surgeons, the literature review revealed a great variety, with incontinence rates ranging from 0.3–65.6% and potency rates ranging from 11–87%. Several factors contribute to this wide difference, the most important being the application of a meticulous surgical technique. General and cancer-specific health-related quality of life is not being affected after radical prostatectomy. The incidence of incontinence and erectile dysfunction is higher after radical prostatectomy when compared to the incidence observed when other therapies for localized prostate cancer are applied. However, the majority of the patients undergoing radical prostatectomy would vote for the operation again. Today, avoidance of major complications after radical prostatectomy depends mostly on a high-quality surgical technique. When incontinence or erectile dysfunction persists after radical prostatectomy, the majority of the treated patients can be managed effectively by various methods.

  1. Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

    International Nuclear Information System (INIS)

    Hayon, E.; Rao, P.S.

    1975-01-01

    The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

  2. CRITICAL THEORY OF THE RADICAL LOVE

    Directory of Open Access Journals (Sweden)

    Lena de Botton

    2009-11-01

    Full Text Available The understanding of the sexual-affective relationships has historically notbeen tackled by science, but placed in the context of instincts and irrationality. In thissense, the critical theory of the Radical Love provides a contribution to critical pedagogyallowing people to understand the mechanisms that direct their emotions and theprocess of election in the sexual-affective relationships. It is about understanding whodo we fall in love for, why and to which values is this desire linked being able to have agreat repercussion in our lives as it provides us with the tools to develop satisfactorysexual-affective relationships. It also offers us guidelines for a preventive educationregarding gender violence by enabling us to understand the attraction models in whichwe have been socialised and which are influencing our desire and elections.

  3. DEMOCRACIA RADICAL Y CIUDADANÍA

    Directory of Open Access Journals (Sweden)

    Pedro Pablo Serna

    2008-01-01

    Full Text Available En el presente texto se presentan dos miradas con respecto a la democracia y su relación con el pensamiento liberal, mostrando de manera específica las características principales de la democracia radical y la manera como ésta puede realizar un adecuado encuentro entre lo individual y lo social, sin afectar las garantías mínimas que se le deben dar a todos los individuos para la realización de su propia concepción de bien. Debe propiciar también unas condiciones adecuadas de participación y control sobre lo público. Para ello, mostraré las visiones de Hayek y Nozick, confrontadas con la mirada de autores como Mouffe, Fraser y otros, quienes proponen un sentido viable, más amplio e incluyente de democracia.

  4. Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nesbitt, David J. [Research/Professor

    2013-08-06

    Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

  5. Schoenberg and the Radical Economies of Harmonielehre

    Directory of Open Access Journals (Sweden)

    Murray Dineen

    2009-06-01

    Full Text Available This article examines Schoenberg’s Harmonielehre as a text shaped by the influence of Central European science and politics. In accord with a severely economical approach to his subject, Schoenberg’s critique of figured bass and chorale harmonization is compared with Ernst Mach’s writings on scientific method. In support of this comparison, the article addresses the role played in Schoenberg’s political development by the Leftist editor and organizer, David J. Bach, one of Schoenberg’s closest childhood friends and a student of Mach. The comparison between Schoenberg and Mach, then, is drawn not only in terms of scientific method but also in light of the radical politics of the Austrian Left at the time, a politics for which both Mach and Schoenberg held sympathies. It should not be overlooked that later, however, they ceased to acknowledge these sympathies explicitly, and Schoenberg would appear to have abandoned them entirely.

  6. CN radical in diffuse interstellar clouds

    International Nuclear Information System (INIS)

    Federman, S.R.; Danks, A.C.; Lambert, D.L.

    1984-01-01

    A survey of 15 lines of sight for the CN B 2 Σ + --X 2 Σ + interstellar absorption lines shows that the CN column density in diffuse interstellar clouds follows the relation log N(CN)proportionalm log N(H 2 ), where mroughly-equal3. This result is reproduced by a reaction network in which CN is produced primarily from C 2 by the neutral-neutral reaction C 2 +N → CN+C, and photodissociation is the main destruction pathway for the neutral molecules CH, C 2 , and CN. The CN radical is the first molecular species observed in diffuse clouds that requires a neutral-neutral reaction for its formation in the gas phase. The network also reproduces the observed ratio N(CN)/N(H 2 )

  7. ESR study of free radicals in mango

    Science.gov (United States)

    Kikuchi, Masahiro; Hussain, Mohammad S.; Morishita, Norio; Ukai, Mitsuko; Kobayashi, Yasuhiko; Shimoyama, Yuhei

    2010-01-01

    An electron spin resonance (ESR) spectroscopic study of radicals induced in irradiated fresh mangoes was performed. Mangoes in the fresh state were irradiated with γ-rays, lyophilized and then crushed into a powder. The ESR spectrum of the powder showed a strong main peak at g = 2.004 and a pair of peaks centered at the main peak. The main peak was detected from both flesh and skin specimens. This peak height gradually decreased during storage following irradiation. On the other hand, the side peaks showed a well-defined dose-response relationship even at 9 days post-irradiation. The side peaks therefore provide a useful means to define the irradiation of fresh mangoes.

  8. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

    Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

    2017-09-28

    High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

  9. Radical radiotherapy for T3 laryngeal cancers

    Energy Technology Data Exchange (ETDEWEB)

    Uno, T. [International Medical Center of Japan, Tokyo (Japan). Dept. of Radiation Therapy; Itami, J. [International Medical Center of Japan, Tokyo (Japan). Dept. of Radiation Therapy; Kotaka, K. [International Medical Center of Japan, Tokyo (Japan). Dept. of Radiation Therapy; Toriyama, M. [International Medical Center of Japan, Tokyo (Japan). Dept. of Otolaryngology

    1996-08-01

    From 1974 through 1992, 37 previously untreated patients with T3 laryngeal cancer (supraglottic 15, glottic 22) were treated with initial radical radiotherapy and surgery for salvage. Two-year local control rate with radiotherapy alone, ultimate voice preservation rate, and ultimate local control rate for T3 supraglottic cancer were 33%, 33%, and 60%, respectively. Corresponding figures for T3 glottic cancer were 32%, 23%, and 77%, respecitvely. Five-year cause-specific survival rate for T3 supraglottic cancer and glottic cancer were 47% and 77%, respectively. In T3 supraglottic cancer, none of the 4 patients with subglottic tumor extension attained local control by radiotherapy alone, and local-regional recurrence-free time were significantly shorter in patients with subglottic tumor extension or tracheostomy before radiotherapy. There were no serious late complications such as chondronecrosis, rupture of carotid artery attributed to radical radiotherapy, while 3 patients had severe laryngeal edema requiring total laryngectomy. (orig.) [Deutsch] Von 1974 bis 1992 wurden 37 zuvor nicht behandelte Patienten mit T3-Larynxkarzinomen (15 supraglottisch, 22 glottisch) primaer kurativ bestrahlt und, wenn erforderlich, einer Salvage-Operation unterzogen. Die Zwei-Jahres-Kontrollrate bei alleiniger Strahlentherapie, die Rate der Stimmerhaltung sowie die unter Einschluss der Operation erreichbare lokale Kontrollrate bei supraglottischen T3-Larynxkarzinomen betrugen 33%, 33% und 60%. Bei glottischen T3-Karzinomen wurden jeweils 32%, 23% und 77% erreicht. Die Fuenf-Jahres-Ueberlebensrate betrug 47% bei supraglottischen T3-Karzinomen und 77% bei den glottischen Karzinomen. Im Fall von supraglottischen Karzinomen erreichte keiner der vier Patienten mit subglottischer Tumorausdehnung eine lokale Kontrolle durch alleinige Strahlentherapie. Die lokoregionale rezidivfreie Zeit war bei den Patienten mit subglottischer Tumorausdehnung oder Tracheostomie vor Einleitung der

  10. Laccase catalyzed grafting of-N-OH type mediators to lignin via radical-radical coupling

    DEFF Research Database (Denmark)

    Munk, Line; Punt, A. M.; Kabel, M. A.

    2017-01-01

    Lignin is an underexploited resource in biomass refining. Laccases (EC 1.10.3.2) catalyze oxidation of phenolic hydroxyls using O2 as electron acceptor and may facilitate lignin modification in the presence of mediators. This study assessed the reactivity of four different synthetic mediators...... better than HBT (1-hydroxybenzotriazole). Three different mechanisms are suggested to explain the grafting of HPI and HBT, all involving radical-radical coupling to produce covalent bonding to lignin. Lignin from exhaustive cellulase treatment of wheat straw was more susceptible to grafting than beech...... organosolv lignin with the relative abundance of grafting being 35% vs. 11% for HPI and 5% vs. 1% for HBT on these lignin substrates. The data imply that lignin can be functionalized via laccase catalysis with-N-OH type mediators....

  11. Two-photon laser-induced fluorescence studies of HS radicals, DS radicals, and I atoms

    Energy Technology Data Exchange (ETDEWEB)

    Tiee, J J; Ferris, M J; Loge, G W; Wampler, F B

    1983-04-15

    A two-photon laser-induced excitation and fluorescence technique has been used to study the A /sup 2/..sigma../sup +/ - X/sup 2/PI transition of HS and DS radicals and various high-lying /sup 4/P/sup 0/, /sup 2/D/sup 0/, and /sup 4/D/sup 0/ states of the I atom. The two-photon excitation cross sections and detection sensitivity are discussed. 13 references, 5 figures.

  12. ESR study of the anion radicals of 5-nitropyrimidines: conversion to iminoxy radicals

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Clark, C.; Failor, R.

    1976-01-01

    The anion radicals of a number of 5-nitropyrimidines have been investigated by ESR spectroscopy. The anions are formed by electrolysis in dimethylformamide and by electron attachment in aqueous glasses, 12 M LiCl--D 2 O and 8 M NaOD. The electrolysis of 5-nitrouracil and 5-nitro-6-methyluracil results in relatively stable anion radicals. The results for 5-nitrouracil give evidence for two or perhaps three anions which differ only by the degree of ring nitrogen protonation. The results for 5-nitro-6-methyluracil suggest that the nitro group of the anion is twisted so that it is coupled only weakly to the ring π-electron system. The anions of 5-nitrouracil, 5-nitroorotic acid, 5-nitrobarbituric acid, and 5-nitro-6-methyluracil have been produced in the alkaline and neutral aqueous glasses. The anisotropic spectra found have been analyzed with the aid of computer simulations which assume axial symmetry. For example, the analysis of the spectrum of 5-nitrouracil anion in 12 M LiCl yields A/sub parallel//sup N/ = 33; A/sub perpendicular to//sup N/ = 5, a 6 /sup H/ = 5.5 G, g/sub parallel/ = 2.0016, and g/sub perpendicular to/ = 2.0059. A concentration dependence in the splittings is noted and discussed. Ultraviolet photolysis of the anions of 5-nitro-6-methyluracil and 5-nitrobarbituric acid results in the formation of iminoxy radicals. Mechanisms of formation of the iminoxy radicals are discussed and results found in this work are compared to results found in single crystals and aqueous solution

  13. Uma análise behaviorista radical dos sonhos A radical behaviorist analysis of the dreams

    Directory of Open Access Journals (Sweden)

    Francynete Melo e Silva

    2000-01-01

    Full Text Available Embora não haja um consenso acerca de questões sobre o que são os sonhos, porque sonhamos, etc., a maioria dos estudos sobre a natureza dos sonhos concorda que ela está relacionada a condições internas do organismo. Contrariamente, o behaviorismo radical analisa os sonhos como comportamentos privados, sendo produtos das histórias filogenética, ontogenética e cultural. Neste sentido, este trabalho tem como objetivo analisar os sonhos a partir da perspectiva behaviorista radical, considerando-os como comportamentos perceptuais encobertos, argumentando-se que são aprendidos. Afirma-se que a interpretação dos sonhos é impossível se não se conhecem as contingências de reforço com as quais a pessoa está interagindo.In spite of the fact that there is no consensus concerning questions about the nature and origin of dreams, the majority of the studies on the nature of the dreams agrees that they are related to internal conditions of the organism. As opposed to that notion, the radical behaviorism analyses the dreams as private behaviors and, thus, as products of philogenetical, ontogenetical, and cultural histories. In this sense, this paper aims to analyze the dreams from a radical behaviorism perspective, considering them as private events, perceptual behaviors, and arguing that they are learned processes. It is asserted that the dreams interpretation is impossible if the contingencies that control such activity are unknown.

  14. Radical versus Social Constructivism: Dilemma, Dialogue, and Defense

    Science.gov (United States)

    Belbase, Shashidhar

    2011-01-01

    This paper aims to discuss epistemological and philosophical foundation of meaningful learning and teaching mathematics and science from the perspective of radical and social constructivism. I have reflected on my experiences of radical and social constructivism through dilemma, dialogue, and defense of my personal epistemology of learning. I went…

  15. Radicals versus Moderates: A Critique of Gyekye's Moderate ...

    African Journals Online (AJOL)

    The communitarian conception of person is a widely accepted view in African thought. Kwame Gyekye thinks there is a distinction between what he calls radical communitarianism and his own version of moderate communitarianism. He is of the view that radical communitarianism is faced with insurmountable problems and ...

  16. Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

    Science.gov (United States)

    Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

    2018-04-26

    In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

  17. Free radicals generated by radiolysis of aqueous solutions

    International Nuclear Information System (INIS)

    Schwarz, H.A.

    1981-01-01

    The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

  18. Teaching Methods in Nutrition: Free Radicals, Antioxidants, and Human Disease.

    Science.gov (United States)

    Janowiak, John J.

    This article presents a teaching methodology for free radical theory and discusses the role of antioxidants in human health. Free radicals are a normal byproduct of respiration, which allows the body to use oxygen, liberate energy, and dispose of harmful substances. The body's antioxidants and nutritional antioxidants quench most of the free…

  19. IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

    Science.gov (United States)

    Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

    2013-01-01

    Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

  20. Free Radical Scavenging Activities of Methanol Extract and ...

    African Journals Online (AJOL)

    Michael Horsfall

    fractions were subjected to in vitro antioxidant evaluation using the DPPH free radical scavenging ... The crude extract has IC-50 value for radical scavenging activity of 5μg/mL which was .... effective concentration of the sample that is required.

  1. Tin-free enantioselective radical reactions using silanes.

    Science.gov (United States)

    Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

    2008-12-04

    Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

  2. Crotylations of alpha-carbonyl radicals with crotylstannane.

    Science.gov (United States)

    Sibi, Mukund P; Miyabe, Hideto

    2002-10-03

    Electrophilic radicals undergo crotylation with crotylstannane with moderate to good efficiency. The reaction provides the syn isomer as the major product. The present methodology is complementary to Claisen protocols for the synthesis of gamma,delta-unsaturated carboxylic acid derivatives. Details of the new radical methodology are presented. [reaction: see text

  3. Fast Resonance Raman Spectroscopy of Short-Lived Radicals

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin

    1976-01-01

    We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

  4. Saul Alinsky, community organizing and rules for Radicals

    OpenAIRE

    Seal, Mike

    2012-01-01

    Saul Alinsky's work is an important reference point for thinking about community organizing and community development. His books Reveille for Radicals (1946) and Rules for Radicals (1971) were both classic explorations of organizing and remain popular today. Mike Seal examines Alinsky's continuing relevance to the activities of informal educators, community organizers and animateurs.

  5. Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

    Directory of Open Access Journals (Sweden)

    Michael Gurry

    2014-09-01

    Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

  6. Mu (H) radical addition to flat and curved polyaromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Addison-Jones, B.; Brodovitch, J.C.; Ghandi, K.; Percival, P.W.; Schuth, J. [Simon Fraser Univ., Dept. of Chemistry, Burnaby, BC (Canada)

    1998-09-01

    A study was conducted in which muonium-substituted free radicals formed from fullerenes, pyrene and pyrenophane were examined to determine how curvature of an unsaturated carbon skeleton affects radical adduct formation. The question is of relevance to C{sub 70}. It was demonstrated that in order to mimic a fullerene it is necessary to introduce curvature to the pyrene system. 2 figs.

  7. Free radical detection by means of 212Pb mirrors

    International Nuclear Information System (INIS)

    Molera, M.J.; Gamboa, J. M.; Garcia Guijarro, E.

    1961-01-01

    Radicals have been detected at low temperatures (550-700 degree centigrade) in the thermal decomposition of dimethyl and methyl-ethyl-ketone by the Paneth method. the sensitivity of the method has been increased by the use of radioactive mirrors of PB 2 12. They have proved to detect one radical among 2.10 6 molecules. (Author) 18 refs

  8. Critical appraisal of outcomes following open radical prostatectomy.

    Science.gov (United States)

    Galvin, David J; Eastham, James A

    2009-05-01

    Radical prostatectomy has evolved enormously over the last 25 years. Improvements include the use of smaller incisions, reduced blood loss, shorter hospital stays, and surgical refinement to improve the recovery of continence and potency. In addition, new technologies and minimally invasive techniques with the potential to further improve patient outcomes have been introduced. This article focuses on outcomes with open radical prostatectomy and is not meant to compare open radical prostatectomy and minimally invasive approaches. Despite a lack of randomized controlled trials, strong observational cohort studies demonstrate lower rates of positive surgical margins, high 10-year and 15-year biochemical recurrence-free rates, excellent prostate cancer-specific mortality rates, and improved recovery of urinary incontinence and erectile function after open radical prostatectomy. We review publications from the past 24 months regarding oncologic outcome, continence, and erectile function, as well as some earlier manuscripts that emphasize key aspects of open radical prostatectomy. Today open radical prostatectomy is a less-invasive procedure with low morbidity providing excellent control of clinically localized prostate cancer. Although open radical prostatectomy now accounts for a minority of radical prostatectomies in the United States, the concepts that have improved oncologic and quality-of-life outcomes are equally applicable to minimally invasive procedures.

  9. Radical-induced oxidation of RAFT agents : a kinetic study

    NARCIS (Netherlands)

    Li, Changxi; He, Junpo; Zhou, Yanwu; Gu, Yuankai; Yang, Yuliang

    2011-01-01

    Radical-induced oxidn. of reversible addn.-fragmentation chain transfer (RAFT) agents is studied with respect to the effect of mol. structure on oxidn. rate. The radicals are generated by homolysis of either azobisisobutyronitrile or alkoxyamine and transformed in situ immediately into peroxy

  10. pi-Dimers of end-capped oligopyrrole cation radicals

    NARCIS (Netherlands)

    Haare, van J.A.E.H.; Groenendaal, L.; Havinga, E.E.; Janssen, R.A.J.; Meijer, E.W.

    1996-01-01

    In two consecutive one-electron oxidations, oligopyrroles substituted with phenyl capping groups (PhPynPh, n = 2–4) can be oxidized reversibly to give stable cation radicals and dications. Spectroelectrochemical studies give direct evidence that diamagnetic p-dimers of cation radicals are formed in

  11. Method for recovering or recirculating stable nitroxide radicals

    NARCIS (Netherlands)

    Heeres, Andre; Van Doren, Hendrik Arend; Bleeker, Ido Pieter; Gotlieb, Kornelis Fester.

    1996-01-01

    The invention relates fo a method for recovering stable nitroxide radicals, wherein at least a part of a reaction mixt. consisting of a soln. or suspension, or a filtrate or supernatant of a suspension, in which stable nitroxide radicals are present in non-solid form, is subjected to an azeotropic

  12. Identification of Radical Scavengers in Sweet Grass (Hierochloe odorata)

    NARCIS (Netherlands)

    Pukalskas, A.; Beek, van T.A.; Venskutonis, R.P.; Linssen, J.P.H.; Veldhuizen, van A.; Groot, de Æ.

    2002-01-01

    Extracts from aerial parts of sweet grass (Hierochloe odorata) were active DPPH free radical scavengers, The active compounds were detected in extract fractions using HPLC with on-line radical scavenging detection. After multistep fractionation of the extract, two new natural products possessing

  13. prepared via atom transfer radical polymerization, reverse atom

    Indian Academy of Sciences (India)

    Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

  14. Robot-assisted radical prostatectomy is a safe procedure

    DEFF Research Database (Denmark)

    Thomsen, Frederik Birkebæk; Berg, Kasper Drimer; Hvarness, Helle

    2013-01-01

    We present our departmental experience with robot-assisted radical prostatectomy and describe complications and early results for the first 239 consecutive patients.......We present our departmental experience with robot-assisted radical prostatectomy and describe complications and early results for the first 239 consecutive patients....

  15. Influence of Free Radicals on the Intrinsic MRI Relaxation Properties.

    Science.gov (United States)

    Tain, Rong-Wen; Scotti, Alessandro M; Li, Weiguo; Zhou, Xiaohong Joe; Cai, Kejia

    2017-01-01

    Free radicals are critical contributors in various conditions including normal aging, Alzheimer's disease, cancer, and diabetes. Currently there is no non-invasive approach to image tissue free radicals based on endogenous contrast due to their extremely short lifetimes and low in vivo concentrations. In this study we aim at characterizing the influence of free radicals on the MRI relaxation properties. Phantoms containing free radicals were created by treating egg white with various H 2 O 2 concentrations and scanned on a 9.4 T MRI scanner at room temperature. T 1 and T 2 relaxation maps were generated from data acquired with an inversion recovery sequence with varied inversion times and a multi-echo spin echo sequence with varied echo times (TEs), respectively. Results demonstrated that free radicals express a strong shortening effect on T 1 , which was proportional to the H 2 O 2 concentration, and a relatively small reduction in T 2 (free radicals was estimated to be in the pM range that is within the physiological range of in vivo free radical expression. In conclusion, the free radicals show a strong paramagnetic effect that may be utilized as an endogenous MRI contrast for its non-invasive in vivo imaging.

  16. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Dzeba, I.; Mihaljevic, B.

    2011-01-01

    Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

  17. Characterization and DPPH Radical Scavenging Activity of Gallic ...

    African Journals Online (AJOL)

    Characterization and DPPH Radical Scavenging Activity of Gallic Acid-Lecithin Complex. C Liu, C Chen, H Ma, E Yuan, Q Li. Abstract. Purpose: To investigate the physicochemical properties and DPPH radical scavenging activity of gallic acid–lecithin complex. Methods: The complex of gallic acid with lecithin was prepared ...

  18. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  19. Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

    Science.gov (United States)

    Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.; hide

    1998-01-01

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

  20. Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

    Science.gov (United States)

    Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

    2016-11-17

    The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

  1. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  2. Evidence of radicals created by plasma in bacteria in water

    International Nuclear Information System (INIS)

    Lee, Chae Bok; Na, Young Ho; Hong, Tae-Eun; Choi, Eun Ha; Uhm, Han S.; Baik, Ku Youn; Kwon, Gichung

    2014-01-01

    Heavy water (D 2 O) was introduced into a non-thermal plasma-jet (NTPJ) device to generate deuterium monoxide (OD) radicals at room temperature. Owing to the similar reactivity and low prevalence of deuterium in nature, OD radicals can be utilized to visualize the OH radical interactions with water and living cells. Escherichia coli in water were treated with OD radicals, and D atom incorporation into cells was visualized using time-of-flight SIMS and Nano-SIMS. The results show that D atoms from NTPJ reach the cytoplasm of E. coli in H 2 O, indicating the usefulness of this OD-tracking method for the study of radical interactions with living cells.

  3. Hydroxyl-radical induced dechlorination of pentachlorophenol in water

    International Nuclear Information System (INIS)

    He Yongke; Wu Jilan; Fang Xingwang; Sonntag, C. von

    1998-01-01

    The hydroxyl-radical induced dechlorination of pentachlorophenol (PCP) in water has been investigated pulse radiolytically. Hydroxyl radicals react with PCP by both electron transfer and addition. The former process results in pentachlorophenoxyl radicals (PCP-O), the latter process followed by rapid HCl elimination gives birth to deprotonated hydroxytetrachlorophenoxyl radicals ( - O-TCP-O). These phenoxyl radicals exhibit maximum absorption around 452 nm, which hinders the proper estimation of the ratio of the two processes. However, these two processes cause different changes in conductivity. In basic solution, the electron transfer causes a conductivity increase due to the formation of OH - whereas an addition followed by HCl elimination results in a conductivity decrease. The concurrence of these two processes reduces the relative variation in conductivity, from which about 53% electron transfer is deduced

  4. EPR assessment of the free radicals in irradiated foodstuffs

    International Nuclear Information System (INIS)

    Tencheva, S.; Katsareva, Ts.; Malinovski, A.; Kabasanov, K.

    1985-01-01

    In the hygienic assessment of radiation treated foodstuffs the study of free radicals formed during radiation exposure, their concentration and disintegration kinetics are of particular interest. In the work presented the concentration of the free radicals in irradiated prunes, nuts and corn is determined using EPR spectroscopy. The following doses are applied: 2, 10 and 20 kGy for prunes, 1, 10 and 20 kGy for nuts, and 0.75, 10 and 20 kGy for corn. EPR measurements are done immediately after the irradiation: 24 hours, and 3, 6, 9 and 15 days after the exposure. In the small radiation doses the formation of single radicals is observed. In doses of 10 kGy the spectra get complicated with the occurence of radicals R 1 , R 2 , R 3 and R 4 . The assessment of radicals proves to be a prospective method for the identification and determination of the preservation terms of foodstuffs

  5. Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin.

    Science.gov (United States)

    Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

    2016-01-14

    Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health.

  6. Reactions of inorganic free radicals with liver protecting drugs

    International Nuclear Information System (INIS)

    Gyoergy, I.; Foeldiak, G.; Blazovics, A.; Feher, J.

    1990-01-01

    Liver protecting drugs, silibinin, a flavonolignane, and the dihydroquinoline derivatives, CH 402 and MTDQ-DA, were shown to inhibit processes in which enzymatically or non-enzymatically generated free radicals were involved. Inorganic free radicals (N 3 , (SCN) 2 - , OH, Trp, CO 2 - , O 2 - ) produced by pulse radiolysis readily react with the compounds, which transform into exceptionally long-lived, unreactive transients. Time evolution of the UV and visible spectra indicate that oxidising radicals form a phenoxyl type radical from silibinin, while OH forms an adduct by attacking, simultaneously, at various sites of the molecule. Superoxide radicals reduce silibinin and oxidise CH 402 and MTDQ-DA. It is concluded that the drugs might exhibit antioxidant behavior in living systems. (author)

  7. Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen

    2009-01-01

    Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

  8. Long-lived gas-phase radicals from combustion

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  9. Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2011-09-30

    By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

  10. The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

    Science.gov (United States)

    Herrling, Thomas; Jung, Katinka; Fuchs, Jürgen

    2008-05-01

    Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.

  11. Detection of free radicals by radical trapping and 15N NMR spectroscopy in copolymerization of methyl acrylate and styrene

    NARCIS (Netherlands)

    Kelemen, P.; Klumperman, B.

    2003-01-01

    The macroradicals taking part in the copolymn. of Me acrylate and styrene were trapped by reaction with a 15N labeled stable nitroxyl radical at 70 DegC. The nitroxyl radical is formed in situ from a thermally instable alkoxyamine precursor. 15N NMR spectroscopy is applied to detect the trapping

  12. Application of ABTS radical cation for selective on-line detection of radical scavengers in HPLC eluates

    NARCIS (Netherlands)

    Koleva, [No Value; Niederlander, HAG; van Beek, TA

    2001-01-01

    The radical cation 2,2 ' -azinobis-(3 -ethylbenzothiazoline-6-sulfonate), (ABTS(.+)) was utilized in an on-line HPLC method for the detection of radical scavengers in complex matrixes. The HPLC-separated analytes react postcolumn with the preformed ABTS(.+), and the induced bleaching is detected as

  13. Structure and reactivity of the N-acetyl-cysteine radical cation and anion: does radical migration occur?

    NARCIS (Netherlands)

    Osburn, S.; Berden, G.; Oomens, J.; O'Hair, R.A.J.; Ryzhov, V.

    2011-01-01

    The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of

  14. Structure and Reactivity of the N-Acetyl-Cysteine Radical Cation and Anion: Does Radical Migration Occur?

    NARCIS (Netherlands)

    Osburn, S.; G. Berden,; Oomens, J.; O' Hair, R. A. J.; Ryzhov, V.

    2011-01-01

    The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of

  15. Radically Different Kinetics at Low Temperatures

    Science.gov (United States)

    Sims, Ian

    2014-06-01

    The use of the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or Reaction Kinetics in Uniform Supersonic Flow) technique coupled with pulsed laser photochemical kinetics methods has shown that reactions involving radicals can be very rapid at temperatures down to 10 K or below. The results have had a major impact in astrochemistry and planetology, as well as proving an exacting test for theory. The technique has also been applied to the formation of transient complexes of interest both in atmospheric chemistry and combustion. Until now, all of the chemical reactions studied in this way have taken place on attractive potential energy surfaces with no overall barrier to reaction. The F + H2 {→} HF + H reaction does possess a substantial energetic barrier ({\\cong} 800 K), and might therefore be expected to slow to a negligible rate at very low temperatures. In fact, this H-atom abstraction reaction does take place efficiently at low temperatures due entirely to tunneling. I will report direct experimental measurements of the rate of this reaction down to a temperature of 11 K, in remarkable agreement with state-of-the-art quantum reactive scattering calculations by François Lique (Université du Havre) and Millard Alexander (University of Maryland). It is thought that long chain cyanopolyyne molecules H(C2)nCN may play an important role in the formation of the orange haze layer in Titan's atmosphere. The longest carbon chain molecule observed in interstellar space, HC11N, is also a member of this series. I will present new results, obtained in collaboration with Jean-Claude Guillemin (Ecole de Chimie de Rennes) and Stephen Klippenstein (Argonne National Labs), on reactions of C2H, CN and C3N radicals (using a new LIF scheme by Hoshina and Endo which contribute to the low temperature formation of (cyano)polyynes. H. Sabbah, L. Biennier, I. R. Sims, Y. Georgievskii, S. J. Klippenstein, I. W. M. Smith, Science 317, 102 (2007). S. D. Le Picard, M

  16. Free radical scavenging injectable hydrogels for regenerative therapy

    International Nuclear Information System (INIS)

    Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

    2017-01-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  17. Free radical scavenging injectable hydrogels for regenerative therapy

    Energy Technology Data Exchange (ETDEWEB)

    Komeri, Remya [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India); Thankam, Finosh Gnanaprakasam [Dept. of Biomedical Sciences, Creighton University, 2500 California Plaza, Omaha NE68178 (United States); Muthu, Jayabalan, E-mail: mjayabalan52@gmail.com [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India)

    2017-02-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  18. Inhibition of radiation-induced DNA strand breaks by hoechst 33258: OH-radical scavenging and DNA radical quenching

    International Nuclear Information System (INIS)

    Adhikary, A.; Bothe, E.; Von Sonntag, C.; Adhikary, A.

    1997-01-01

    The minor-groove-binding dye Hoechst 33258 has been found to protect pBR322 DNA in aqueous solution against radiation-induced single-strand breaks (ssb). This protective effect has been assumed to be largely due to the scavenging of the strand-break-generating OH radicals by Hoechst. From D 37 values for ssb at different Hoechst concentrations the value of the OH radical scavenging constant of DNA-bound Hoechst has been estimated at k Ho/DNA = 2.7 * 10 11 dm 3 mol -1 . This unexpectedly high value has led us to study the reactions of OH radicals with Hoechst in the absence and in the presence of double-stranded calf thymus DNA (ds DNA) by pulse radiolysis, and the formation of radiation-induced ssb by low angle laser light scattering. The D 37 /D 37 0 values at different Hoechst concentrations agree with the values obtained by Martin and al. and demonstrate the protection. However, this protection cannot be explained on the basis of OH radical scavenging alone using the above rate constants. There must, in addition, be some quenching of DNA radicals. Hoechst radicals are formed in the later ms time range, i.e a long time after the disappearance of the OH radicals. This delayed Hoechst radical formation has been assigned to a a reaction of DNA radicals with Hoechst, thereby inhibiting strand breakage. In confirmation, pulse radiolysis of aqueous solution of nucleotides in the presence of Hoechst yields a similar delayed Hoechst radical formation. The data indicate that in DNA the cross-section of this quenching has a diameter of 3 to 4 base pairs per Hoechst molecule. (N.C.)

  19. Process Improvement in a Radically Changing Organization

    Science.gov (United States)

    Varga, Denise M.; Wilson, Barbara M.

    2007-01-01

    This presentation describes how the NASA Glenn Research Center planned and implemented a process improvement effort in response to a radically changing environment. As a result of a presidential decision to redefine the Agency's mission, many ongoing projects were canceled and future workload would be awarded based on relevance to the Exploration Initiative. NASA imposed a new Procedural Requirements standard on all future software development, and the Center needed to redesign its processes from CMM Level 2 objectives to meet the new standard and position itself for CMMI. The intended audience for this presentation is systems/software developers and managers in a large, research-oriented organization that may need to respond to imposed standards while also pursuing CMMI Maturity Level goals. A set of internally developed tools will be presented, including an overall Process Improvement Action Item database, a formal inspection/peer review tool, metrics collection spreadsheet, and other related technologies. The Center also found a need to charter Technical Working Groups (TWGs) to address particular Process Areas. In addition, a Marketing TWG was needed to communicate the process changes to the development community, including an innovative web site portal.

  20. Reactions of radicals with lecithin bilayers

    International Nuclear Information System (INIS)

    Barber, D.J.W.; Thomas, J.K.

    1978-01-01

    The kinetics of reaction of .OH and e/sub aq/ - with lecithin bilayers have been measured. The rate for .OH + lecithin is 5.1 +- 0.9 x 10 8 M -1 sec -1 while the e/sub aq/ - + lecithin rate is very slow. When a solute such as pyrene is solubilized in the bilayer, .OH and e/sub aq/ - may react with the solute; rates of 1.65 +- 0.12 x 10 9 M -1 sec -1 and 7 x 10 7 M -1 sec -1 have been measured for reaction of .OH and e/sub aq/ - , respectively, with pyrene in lecithin. These rates are lower than those observed for similar reactions in homogeneous systems. This is explained in terms of (a) the protective effect of the bilayer, this being especially true for e/sub aq/ - which does not readily leave the aqueous phase, and (b) in terms of the restricted diffusion imposed on the reactive species by the bilayer. The kinetics in these model systems are relevant to reactions of radicals with membranes. Long-term alteration in the model membrane following .OH attack is manifested in terms of damage to the head group, increasing water penetration of the bilayer, and of cross-linking with the membrane, thereby restricting motion in the interior of the bilayer. Increased rigidity and leakiness of membranes is an expected consequence of radiation damage