Sample records for entails initial hydroxylation

  1. Phenytoin-initiated hydroxyl radical formation: characterization by enhanced salicylate hydroxylation. (United States)

    Kim, P M; Wells, P G


    Bioactivation of phenytoin and related teratogens by peroxidases such as prostaglandin H synthase (PHS) may initiate hydroxyl radical (.OH) formation that is teratogenic. Salicylate is hydroxylated by .OH at the third and fifth carbon atoms, forming 2,3- and 2,5-dihydroxybenzoic acids (DHBA). In vivo salicylate metabolism produces only the 2,5-isomer, so 2,3-DHBA formation may reflect .OH production. In the present study, we validated the salicylate assay using the known .OH generator paraquat and evaluated .OH production by phenytoin. Female CD-1 mice were treated with paraquat (30 mg/kg, intraperitoneally) given 30 min after acetylsalicylic acid (ASA) (200 mg/kg, intraperitoneally). Blood was collected at 5, 15, and 30 min and 1 and 2 hr after paraquat, and plasma was analyzed for DHBA isomers and glucuronide conjugates by high performance liquid chromatography with electrochemical detection. Paraquat increased 2,3-DHBA formation 19.2-fold, with substantial inter-individual variability in the time of maximal formation (p = 0.0001). The 2,3-DHBA glucuronide conjugates in vivo and in hepatic microsomal studies amounted to approximately 11% and 0.43%, respectively, of total 2,3-DHBA equivalents. To investigate putative .OH production initiated via PHS-catalyzed phenytoin bioactivation, ASA was given 30 min before phenytoin (65 or 100 mg/kg, intraperitoneally), resulting in respective 7.6-fold (p = 0.02) and 14.2-fold (p = 0.003) increases in phenytoin-initiated maximal 2,3-DHBA formation. Maximal 2,3-DHBA formation was 2.1-fold higher when ASA was administered after rather than before the same dose (65 mg/kg) of phenytoin (p = 0.03), indicating ASA inhibition of PHS-catalyzed phenytoin bioactivation. Urinary analysis was much less sensitive, and the 2,5-isomer reflected enzymatic rather than .OH-mediated hydroxylation. The paraquat studies demonstrate the importance of timing in accurately quantifying 2,3-DHBA formation and suggest that glucuronidation does not

  2. What Justice Entails

    Directory of Open Access Journals (Sweden)

    Víctor M. Muñiz-Fraticelli


    Full Text Available In The Birthright Lottery, Ayelet Shachar subjects the institution of birthright citizenship to close scrutiny by applying to citizenship the historical and philosophical critique of hereditary ownership built up over four centuries of liberal and democratic theory, and proposing compelling alternatives drawn from the theory of private law to the usual modes of conveyance of membership. Nonetheless, there are some difficulties with this critique. First, the analogy between entailed property and birthright citizenship is not as illustrative as Shachar intends it to be; second, the mechanism of the birthright privilege levy is insufficient for addressing structural impediments to growth; and third, the principle of ius nexi, while an important corrective to currently dominant principles of nationality, will likely have effects both unnecessary and insufficient to correct the injustices that Shachar identifies. In the end, the most significant improvements in the lives of the neediest persons on the planet are more likely advanced through conventional arguments for the lowering of barriers to the circulation of goods, labor, and capital. This shift in attention from opening borders to extending citizenship risks being a distraction from more effective means of addressing the injustices associated with global inequality.Dans son livre The Birthright Lottery, Ayelet Shachar soumet l’institution de la citoyenneté par droit de naissance à un examen rigoureux, en appliquant à la citoyenneté la critique philosophique et historique de la propriété héritée construite pendant quatre siècles de théorie démocratique libérale, et en proposant aux modes habituels d’attribution de la citoyenneté une alternative séduisante tirée de la théorie du droit privé. Néanmoins, cette critique comporte certaines difficultés. Premièrement, l’analogie entre la transmission de la propriété par l’institution de la taille et la citoyenneté par

  3. Laboratory investigations of the hydroxyl radical-initiated oxidation of atmospheric volatile organic compounds (United States)

    Vimal, Deepali

    The hydroxyl radical (OH) is one of the most important oxidants in the atmosphere, because reaction with OH is the dominant atmospheric fate of most trace atmospheric species. OH is intimately involved in a complex non-linear photochemical pathway involving anthropogenic and biogenic emissions of volatile organic compounds (VOCs) and nitrogen oxides that are emitted from vehicular exhaust and industrial emissions. This chemistry generates secondary tropospheric ozone which is an important greenhouse gas as well as a component of photochemical smog. In addition, this chemistry leads to the formation of secondary organic aerosols in the atmosphere which have implications for public health and climate change. The focus of this dissertation is to improve our understanding of this complex chemistry by investigating the rate-limiting elementary reactions which are part of the OH-initiated oxidation of important VOCs. Experimental (discharge flow technique coupled with resonance fluorescence and laser induced fluorescence) and theoretical studies (Density Functional Theory computations) of the kinetics of three atmospheric VOCs, acetic acid, 1,3-butadiene and methyl ethyl ketone are discussed. The acetic acid and OH reaction has been thought to undergo a hydrogen-bonded complex mediated pathway instead of a direct one leading to faster rate constants at lower temperature. Our results for the experimental investigation between 263-373 K and pressures of 2-5 Torr for the gas phase reaction of acetic acid with OH confirm the complex mediated reaction mechanism and indicate that acetic acid can play an important role especially in the oxidative chemistry of upper troposphere. The 1,3-butadiene and OH reaction is thought to undergo electrophilicaddition by OH which could display a complex pressure dependence similar to isoprene and 232-butenol as noted earlier in this laboratory. However, our results for the kinetics of the reaction between 273-423 K and a pressure range of 1

  4. Generation mechanism of hydroxyl radical species and its lifetime prediction during the plasma-initiated ultraviolet (UV) photolysis (United States)

    Attri, Pankaj; Kim, Yong Hee; Park, Dae Hoon; Park, Ji Hoon; Hong, Young J.; Uhm, Han Sup; Kim, Kyoung-Nam; Fridman, Alexander; Choi, Eun Ha


    Through this work, we have elucidated the mechanism of hydroxyl radicals (OH•) generation and its life time measurements in biosolution. We observed that plasma-initiated ultraviolet (UV) photolysis were responsible for the continues generation of OH• species, that resulted in OH• to be major reactive species (RS) in the solution. The density and lifetime of OH• species acted inversely proportional to each other with increasing depth inside the solution. The cause of increased lifetime of OH• inside the solution is predicted using theoretical and semiempirical calculations. Further, to predict the mechanism of conversion of hydroxide ion (OH−) to OH• or H2O2 (hydrogen peroxide) and electron, we determined the current inside the solution of different pH. Additionally, we have investigated the critical criterion for OH• interaction on cancer cell inducing apoptosis under effective OH• exposure time. These studies are innovative in the field of plasma chemistry and medicine. PMID:25790968

  5. Mechanism of DNA cleavage by cationic manganese porphyrins: hydroxylations at the 1'-carbon and 5'-carbon atoms of deoxyriboses as initial damages. (United States)

    Pratviel, G; Pitié, M; Bernadou, J; Meunier, B


    Cationic manganese-porphyrin complexes, free or targetted with an intercalating agent, are able to cleave DNA using oxygen atom donors like potassium monopersulfate or magnesium monoperphthalate as coreactants. Detailed studies of the cleavage of calf thymus DNA, before and after a heating step, show that free bases and 5-methylene-2-furanone are the main reaction products, indicating that hydroxylation at the 1'-carbon atom is the main target of these chemical agents. These data confirm that metalloporphyrin derivatives interact with the minor groove of double-stranded DNA. Hydroxylation of one of the two C-H bonds at position-5' is another initial DNA damage, characterized by the formation of furfural as sugar degradation product. Besides these two main initial damage sites, a low contribution of a hydroxylation reaction at C4' can not be definitively discounted, while an hydroperoxidation route at C4' can be excluded.

  6. Chemical characterization of organosulfates from the hydroxyl radical-initiated oxidation and ozonolysis of cis-3-hexen-1-ol (United States)

    Barbosa, Thais S.; Riva, Matthieu; Chen, Yuzhi; da Silva, Cleyton M.; Ameida, Jose Claudino S.; Zhang, Zhenfa; Gold, Avram; Arbilla, Graciela; Bauerfeldt, Glauco F.; Surratt, Jason D.


    Cis-3-hexen-1-ol (cis-HXO) is a green leaf volatile emitted from plants under stress and belongs to an important class of biogenic volatile organic compounds. In this study, we have investigated the potential formation of organosulfates (OSs) from the hydroxyl radical (OH)-initiated oxidation and ozonolysis of cis-HXO using either non-acidified or acidified sulfate seed aerosols under different relative humidity (RH) conditions. For selected ozonolysis experiments, an OH scavenger was utilized. Ultra performance liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry with electrospray ionization (UPLC/ESI-HR-Q-TOFMS) was used to characterize cis-HXO-derived secondary organic aerosol (SOA) formation. Chemical characterization of cis-HXO-derived SOA products reveals that OSs were generated in significant quantity from multiphase chemistry of gas-phase oxidation products of cis-HXO. Ambient fine aerosol (PM2.5) samples collected from Rio de Janeiro, Brazil, were also analyzed. Seven cis-HXO-derived OSs identified in the lab study with molecular weights 154, 186, 170, 210, 212, 226 and 270 were also found in the PM2.5 samples collected in Brazil. This study provides direct evidence that the oxidation of cis-HXO by OH and O3 yields biogenic SOA through the formation of polar OSs.

  7. Cross-Lingual Textual Entailment and Applications


    Mehdad, Yashar


    Textual Entailment (TE) has been proposed as a generic framework for modeling language variability. The great potential of integrating (monolingual) TE recognition components into NLP architectures has been reported in several areas, such as question answering, information retrieval, information extraction and document summarization. Mainly due to the absence of cross-lingual TE (CLTE) recognition components, similar improvements have not yet been achieved in any corresponding cross-lingual a...

  8. Kinetic and Product Studies of the Hydroxyl Radical Initiated Oxidation of Dimethyl Sulfide in the Temperature Range 250 - 300 K


    Albu, Mihaela


    This work presents investigations on the gas-phase chemistry of dimethyl sulfide (DMS: CH3-S-CH3) with hydroxyl (OH) radicals performed in a 336 l quartz glass reactor in the laboratory of the Department of Physical Chemistry of the University of Wuppertal, Germany. In this work kinetic, product and mechanistic data for the reaction of OH radicals with DMS were obtained. The investigations were aimed at achieving a better understanding of the oxidation mechanism for DMS as a function of tempe...

  9. Recognizing textual entailment models and applications

    CERN Document Server

    Dagan, Ido; Sammons, Mark


    In the last few years, a number of NLP researchers have developed and participated in the task of Recognizing Textual Entailment (RTE). This task encapsulates Natural Language Understanding capabilities within a very simple interface: recognizing when the meaning of a text snippet is contained in the meaning of a second piece of text. This simple abstraction of an exceedingly complex problem has broad appeal partly because it can be conceived also as a component in other NLP applications, from Machine Translation to Semantic Search to Information Extraction. It also avoids commitment to any sp

  10. Recognizing Question Entailment for Medical Question Answering. (United States)

    Abacha, Asma Ben; Dina, Demner-Fushman


    With the increasing heterogeneity and specialization of medical texts, automated question answering is becoming more and more challenging. In this context, answering a given medical question by retrieving similar questions that are already answered by human experts seems to be a promising solution. In this paper, we propose a new approach for the detection of similar questions based on Recognizing Question Entailment (RQE). In particular, we consider Frequently Asked Question (FAQs) as a valuable and widespread source of information. Our final goal is to automatically provide an existing answer if FAQ similar to a consumer health question exists. We evaluate our approach using consumer health questions received by the National Library of Medicine and FAQs collected from NIH websites. Our first results are promising and suggest the feasibility of our approach as a valuable complement to classic question answering approaches.

  11. Biological constraints do not entail cognitive closure. (United States)

    Vlerick, Michael


    From the premise that our biology imposes cognitive constraints on our epistemic activities, a series of prominent authors--most notably Fodor, Chomsky and McGinn--have argued that we are cognitively closed to certain aspects and properties of the world. Cognitive constraints, they argue, entail cognitive closure. I argue that this is not the case. More precisely, I detect two unwarranted conflations at the core of arguments deriving closure from constraints. The first is a conflation of what I will refer to as 'representation' and 'object of representation'. The second confuses the cognitive scope of the assisted mind for that of the unassisted mind. Cognitive closure, I conclude, cannot be established from pointing out the (uncontroversial) existence of cognitive constraints. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. What does leadership in surgery entail? (United States)

    Patel, Vanash M; Warren, Oliver; Humphris, Penny; Ahmed, Kamran; Ashrafian, Hutan; Rao, Christopher; Athanasiou, Thanos; Darzi, Ara


    Leadership is not formally taught at any level in surgical training; there are no mandatory leadership courses or qualifications for trainees or specialists, and leadership performance is rarely evaluated within surgical appraisal or assessment programmes. Literature obtained from a MEDLINE search was reviewed to determine the characteristics of surgical leaders; outline an analytical framework through which these characteristics can be developed both in surgeons and surgical departments; and reflect on future challenges and recommendations for the central role of leadership in the field of surgery. Leadership in surgery entails professionalism, technical competence, motivation, innovation, teamwork, communication skills, decision-making, business acumen, emotional competence, resilience and effective teaching. Leadership skills can be developed through experience, observation, and education using a framework including mentoring, coaching, networking, stretch assignments, action learning and feedback. Modern surgery will need leaders with superior leadership skills that are well defined. It is vital that leadership programmes to develop leadership skills are put into practice in medical education curriculum and postgraduate surgical training. This will ensure maintenance and improvement in the quality of patient care. © 2010 The Authors. ANZ Journal of Surgery © 2010 Royal Australasian College of Surgeons.

  13. Preferential Entailments, Extensions and Reductions of The Vocabulary


    Moinard, Yves; Rolland, Raymond


    A preferential entailment is defined by a binary relation, or «preference relation», either among interpretations (or models) or among «states» which are «copies of interpretations». Firstly, we show how an extension of the vocabulary allows to express any preferential entailment as a preferent- ial entailment without state. Secondly, by reducing the vocabulary, we show how to express some preferential entailments in a smaller language. This second method works only for particular preferentia...

  14. Novel relationship between hydroxyl radical initiation and surface group of ceramic honeycomb supported metals for the catalytic ozonation of nitrobenzene in aqueous solution. (United States)

    Zhao, Lei; Sun, Zhizhong; Ma, Jun


    Comparative experiments have been performed to investigate the degradation efficiency of nitrobenzene and the removal efficiency of TOC in aqueous solution bythe processes of ceramic honeycomb supported different metals (Fe, Ni, and Zn) catalytic ozonation, indicating that the modification with metals can enhance the activity of ceramic honeycomb for the catalytic ozonation of nitrobenzene, and the loading percentage of metal and the metallicity respectively presents a positive influence on the degradation of nitrobenzene. The degradation efficiency of nitrobenzene is determined by the initiation of hydroxyl radical (*OH) according to a good linear correlation in all the processes of modified ceramic honeycomb catalytic ozonation at the different loading percentages of metals. The modification of ceramic honeycomb with metals results in the conversion of the pH at the point of zero charge (pHpzc) and the evolution of surface groups. Divergence from the conventional phenomenon, the enhancement mechanism of ozone decomposition on the modified ceramic honeycomb with metals is proposed due to the basic attractive forces of electrostatic forces or/and hydrogen bonding. Consequently, a novel relationship between the initiation of *OH and the surface-OH2+ group on the modified catalyst is established based on the synergetic effect between homogeneous and heterogeneous reaction systems.

  15. On the entailment problem for a logic of typicality

    CSIR Research Space (South Africa)

    Booth, R


    Full Text Available simultaneously. Closer inspection reveals that this result is best interpreted as an argument for advocating the development of more than one type of PTL entailment. In the spirit of this interpretation, we define two primary forms of entailment for PTL...

  16. Hydroxylation of multi-walled carbon nanotubes: Enhanced biocompatibility through reduction of oxidative stress initiated cell membrane damage, cell cycle arrestment and extrinsic apoptotic pathway. (United States)

    Liu, Zhenbao; Liu, Yanfei; Peng, Dongming


    Modification of CNTs with hydroxyl group promotes their applications in biomedical area. However, the impact of hydroxylation on their biocompatibility is far from being completely understood. In this study, we carried out a comprehensive evaluation of hydroxylated multi-walled carbon nanotubes (MWCNTs-OH) on the human normal liver L02 cell line, and compared it with that of pristine multi-walled carbon nanotubes (p-MWCNTs). Results demonstrated that compared with p-MWCNTs, MWCNTs-OH induced significantly lower oxidative stress as indicated by the level of intracellular antioxidant glutathione (GSH), subsequently lead to less cell membrane damage as demonstrated by lactate dehydrogenase (LDH) leakage assay, and showed slightly decreased arrestment of cell cycle distribution at G0/G1. More interestingly, MWCNTs-OH exhibited significantly lower tendency to activate caspase-8, a key molecule involved in the extrinsic apoptotic pathway. All these in vitro results demonstrated that hydroxylation of MWCNTs enhanced their biocompatibility compare with p-MWCNTs. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Mechanism of DNA cleavage by cationic manganese porphyrins: hydroxylations at the 1'-carbon and 5'-carbon atoms of deoxyriboses as initial damages.


    Pratviel, G; Pitié, M.; Bernadou, J.; Meunier, B


    Cationic manganese-porphyrin complexes, free or targetted with an intercalating agent, are able to cleave DNA using oxygen atom donors like potassium monopersulfate or magnesium monoperphthalate as coreactants. Detailed studies of the cleavage of calf thymus DNA, before and after a heating step, show that free bases and 5-methylene-2-furanone are the main reaction products, indicating that hydroxylation at the 1'-carbon atom is the main target of these chemical agents. These data confirm that...

  18. Aliphatic peptidyl hydroperoxides as a source of secondary oxidation in hydroxyl radical protein footprinting


    Saladino, Jessica; Liu, Mian; Live, David; Sharp, Joshua S.


    Hydroxyl radical footprinting is a technique for studying protein structure and binding that entails oxidizing a protein system of interest with diffusing hydroxyl radicals, and then measuring the amount of oxidation of each amino acid. One important issue in hydroxyl radical footprinting is limiting amino acid oxidation by secondary oxidants to prevent uncontrolled oxidation which can cause amino acids to appear more solvent accessible than they really are. Previous work suggested that hydro...

  19. Learning Hereditary and Reductive Prolog Programs from Entailment (United States)

    Hussain, Shahid; Rao, M. R. K. Krishna

    In this paper we study exact learning of Prolog programs from entailment and present an algorithm to learn two rich classes of Prolog programs namely hereditary and reductive Prolog programs. These classes contain standard Prolog programs with and without recursion like append, merge, split, delete, member, prefix, suffix, length, add, etc. Additionally our algorithm learns the hereditary Prolog programs in polynomial time.

  20. Natural Solution to FraCaS Entailment Problems

    NARCIS (Netherlands)

    Abzianidze, Lasha


    Reasoning over several premises is not a common feature of RTE systems as it usually requires deep semantic analysis. On the other hand, FraCaS is a collection of entailment problems consisting of multiple premises and covering semantically challenging phenomena. We employ the tableau theorem prover

  1. Logic of approximate entailment in quasimetric and in metric spaces. (United States)

    Vetterlein, Thomas


    It is known that a quasimetric space can be represented by means of a metric space; the points of the former space become closed subsets of the latter one, and the role of the quasimetric is assumed by the Hausdorff quasidistance. In this paper, we show that, in a slightly more special context, a sharpened version of this representation theorem holds. Namely, we assume a quasimetric to fulfil separability in the original sense due to Wilson. Then any quasimetric space can be represented by means of a metric space such that distinct points are assigned disjoint closed subsets. This result is tailored to the solution of an open problem from the area of approximate reasoning. Following the lines of E. Ruspini's work, the Logic of Approximate Entailment ([Formula: see text]) is based on a graded version of the classical entailment relation. We present a proof calculus for [Formula: see text] and show its completeness with regard to finite theories.

  2. Entailments, pragmatic assertion and mood in Spanish complements

    Directory of Open Access Journals (Sweden)

    Errapel Mejías-Bikandi


    Full Text Available This paper examines a frequently overlooked class of expressions in Spanish that license the subjunctive mood in a complement clause. This class contains expressions such as poco/a/s “few”, menos de “less than” and solo “only”. The goal of the paper is to offer an account of the use of mood with these expressions that incorporates the data under discussion into previous pragmatic accounts of mood based on notions of assertion and informative value. The paper first offers a semantic characterization of this class of expressions that is based on their monotonic properties (Ladusaw 1980, Ladusaw 1983. Next, it explores the pragmatic effects of their semantic properties. Following Stalnaker (1978, I assume that the effect of a pragmatic assertion is to reduce the set of possible worlds that represents the presuppositions held by a speaker and their audience (referred to as the context set. It is argued that propositions under the scope of an upward entailing expression are more informative, and they are thus more relevant and higher in a scale of assertability (Lunn 1989, in that they allow for inferences that further reduce the context set. Propositions under the scope of expressions that are not upward entailing lose some of their informative value, and thus they are lower in the scale of assertability, which correlates with the possibility of using subjunctive mood in a complement under their scope.

  3. New Directions: Watching over tropospheric hydroxyl (OH)

    NARCIS (Netherlands)

    Lelieveld, J.|info:eu-repo/dai/nl/411295810; Brenninkmeijer, C.A.M.; Joeckel, P.; Isaksen, I.S.A.; Krol, M.C.|info:eu-repo/dai/nl/078760410; Mak, J.E.; Dlugokencky, E.; Montzka, S.A.; Novelli, P.C.; Peters, W.; Tans, P.P.


    Mean tropospheric hydroxyl radical (OH) abundance is often used as a measure of the oxidation capacity (or “self-cleansing”) of the atmosphere. The primary mechanism by which atmospheric pollutant gases are removed from the atmosphere is initiated by the reaction with OH. As a result, large

  4. Relationship between acceleration of hydroxyl radical initiation and increase of multiple-ultrasonic field amount in the process of ultrasound catalytic ozonation for degradation of nitrobenzene in aqueous solution. (United States)

    Zhao, Lei; Ma, Weichao; Ma, Jun; Wen, Gang; Liu, Qianliang


    The synergetic effect between ozone and ultrasound can enhance the degradation of nitrobenzene and removal efficiency of TOC in aqueous solution, and the degradation of nitrobenzene follows the mechanism of hydroxyl radical (OH) oxidation. Under the same total ultrasonic power input condition, the degradation rate of nitrobenzene (kNB), the volumetric mass transfer coefficient of ozone (kLa), and the initiation rate of OH (kOH) increases with introduction of additional ultrasonic field (1-4) in the process of ozone/ultrasound. The increasing amount of ultrasonic fields accelerates the decomposition of ozone, leading to the rapid appearance of the maximum equilibrium value and the decrease in the accumulation concentration of ozone in aqueous solution with the increasing reaction time. The increase in mass transfer of gaseous ozone dissolved into aqueous solution and the acceleration in the decomposition of ozone in aqueous solution synchronously contribute to the increase of kLa. The investigation of mechanism confirms that the increasing amount of ultrasonic fields yields the increase in cavitation activity that improves the mass transfer and decomposition of ozone, resulting in acceleration of OH initiation, which determines the degradation of nitrobenzene in aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Syntheses of 11-hydroxylated guaianolides

    DEFF Research Database (Denmark)

    Lauridsen, A.; Cornett, Claus; Vulpius, T.


    Two epimeric guaianolides, both prepared from alpha-santonin, were 11-hydroxylated using 2-phenylsulfonyl-3-phenyloxaziridine as a reagent. Extensive use of protecting groups enabled selective acylation of the 3- and 10-hydroxy groups....

  6. Beyond Reductionism Twice: No Laws Entail Biosphere Evolution, Formal Cause Laws Beyond Efficient Cause Laws


    Kauffman, Stuart


    Newton set the stage for our view of how science should be done. We remain in what I will call the `Newtonian Paradigm' in all of physics, including Newton, Einstein, and Schrodinger. As I will show shortly, Newton invented and bequeathed to us `efficient cause entailing laws' for the entire becoming of the universe. With Laplace this became the foundation of contemporary reductionism in which all that can happen in the world is due to efficient cause entailing laws. More this framework stand...

  7. Enforcement of entailment constraints in distributed service-based business processes. (United States)

    Hummer, Waldemar; Gaubatz, Patrick; Strembeck, Mark; Zdun, Uwe; Dustdar, Schahram


    A distributed business process is executed in a distributed computing environment. The service-oriented architecture (SOA) paradigm is a popular option for the integration of software services and execution of distributed business processes. Entailment constraints, such as mutual exclusion and binding constraints, are important means to control process execution. Mutually exclusive tasks result from the division of powerful rights and responsibilities to prevent fraud and abuse. In contrast, binding constraints define that a subject who performed one task must also perform the corresponding bound task(s). We aim to provide a model-driven approach for the specification and enforcement of task-based entailment constraints in distributed service-based business processes. Based on a generic metamodel, we define a domain-specific language (DSL) that maps the different modeling-level artifacts to the implementation-level. The DSL integrates elements from role-based access control (RBAC) with the tasks that are performed in a business process. Process definitions are annotated using the DSL, and our software platform uses automated model transformations to produce executable WS-BPEL specifications which enforce the entailment constraints. We evaluate the impact of constraint enforcement on runtime performance for five selected service-based processes from existing literature. Our evaluation demonstrates that the approach correctly enforces task-based entailment constraints at runtime. The performance experiments illustrate that the runtime enforcement operates with an overhead that scales well up to the order of several ten thousand logged invocations. Using our DSL annotations, the user-defined process definition remains declarative and clean of security enforcement code. Our approach decouples the concerns of (non-technical) domain experts from technical details of entailment constraint enforcement. The developed framework integrates seamlessly with WS-BPEL and the Web

  8. Beyond Reductionism Twice: No Laws Entail Biosphere Evolution, Formal Cause Laws Beyond Efficient Cause Laws

    CERN Document Server

    Kauffman, Stuart


    Newton set the stage for our view of how science should be done. We remain in what I will call the `Newtonian Paradigm' in all of physics, including Newton, Einstein, and Schrodinger. As I will show shortly, Newton invented and bequeathed to us `efficient cause entailing laws' for the entire becoming of the universe. With Laplace this became the foundation of contemporary reductionism in which all that can happen in the world is due to efficient cause entailing laws. More this framework stands as our dominant way to do science. The Newtonian Paradigm has done enormous work in science, and helped lead to the Industrial Revolution, and even our entry into Modernity. In this paper I propose to challenge the adequacy of the Newtonian Paradigm on two ground: 1) For the evolution of the biosphere beyond the watershed of life, we can formulate no efficient cause entailing laws that allow us to deduce the evolution of the biosphere. A fortiori, the same holds for the evolution of the economy, legal systems, social sy...

  9. Prolyl hydroxylation in elastin is not random. (United States)

    Schmelzer, Christian E H; Nagel, Marcus B M; Dziomba, Szymon; Merkher, Yulia; Sivan, Sarit S; Heinz, Andrea


    This study aimed to investigate the prolyl and lysine hydroxylation in elastin from different species and tissues. Enzymatic digests of elastin samples from human, cattle, pig and chicken were analyzed using mass spectrometry and bioinformatics tools. It was confirmed at the protein level that elastin does not contain hydroxylated lysine residues regardless of the species. In contrast, prolyl hydroxylation sites were identified in all elastin samples. Moreover, the analysis of the residues adjacent to prolines allowed the determination of the substrate site preferences of prolyl 4-hydroxylase. It was found that elastins from all analyzed species contain hydroxyproline and that at least 20%-24% of all proline residues were partially hydroxylated. Determination of the hydroxylation degrees of specific proline residues revealed that prolyl hydroxylation depends on both the species and the tissue, however, is independent of age. The fact that the highest hydroxylation degrees of proline residues were found for elastin from the intervertebral disc and knowledge of elastin arrangement in this tissue suggest that hydroxylation plays a biomechanical role. Interestingly, a proline-rich domain of tropoelastin (domain 24), which contains several repeats of bioactive motifs, does not show any hydroxyproline residues in the mammals studied. The results show that prolyl hydroxylation is not a coincidental feature and may contribute to the adaptation of the properties of elastin to meet the functional requirements of different tissues. The study for the first time shows that prolyl hydroxylation is highly regulated in elastin. Copyright © 2016 Elsevier B.V. All rights reserved.


    Directory of Open Access Journals (Sweden)

    Máximo Andrés Rodríguez Pérez


    Full Text Available Entailment theories linking University enterprise state, give us guidelines for what knowledge societies must do to obtain a sustainable development, experiences accumulated in different countries of the world bring us the way that countries and universities that do not have developed this theme should follow. The core activities of any higher education institution are teaching, research and extension. To accomplish these activities with the greatest success it must be done in association with the above institutions and society as a whole

  11. Functionalization of hydroxyl terminated polybutadiene with ...

    Indian Academy of Sciences (India)

    ... hydroxyl value and microstructure of the parent HTPB. The formation of hydrogen bonding between the terminal hydroxyl groups and the nitrogen atoms of triazine moiety is the driving force for the terminal attachment chemistry. The functionalized HTPB (HTPB–CBDT) shows a strong fluorescence emission at 385 nm.

  12. Prolyl hydroxylation in elastin is not random

    DEFF Research Database (Denmark)

    Schmelzer, Christian E H; Nagel, Marcus B M; Dziomba, Szymon


    at the protein level that elastin does not contain hydroxylated lysine residues regardless of the species. In contrast, prolyl hydroxylation sites were identified in all elastin samples. Moreover, the analysis of the residues adjacent to prolines allowed the determination of the substrate site preferences...

  13. [Industrial sound spectrum entailing noise-induced occupational hearing loss in Iasi industry]. (United States)

    Carp, Cristina Maria; Costinescu, V N


    In European Union every day millions of employees are exposed to noise at work and the risk this can entail. this study presents the sound spectrum in Iasi heavy industry: metal foundries industry, punching and embossing of metal sheets, cold and hot metal processing. it was used a type 2 Sound Level Meter (SLM) and the considered value was the average value over 10 test values in 10 consecutive days for each octave band in common audible frequency range. It is obviously that the large values of sound intensities in the most of frequency octave band exceed maximum admissible and legal values. The study reveals the necessity of hardware, medical and managerial measures in order to reduce the occupational noise and to prevent the hearing acuity damage of the workers.

  14. Hydroxyl Tagging Velocimetry for Rocket Plumes Project (United States)

    National Aeronautics and Space Administration — A non-intrusive method for measuring velocities in a rocket exhaust is proposed in a joint effort by MetroLaser and Vanderbilt University. Hydroxyl Tagging...

  15. An ab initio study of hydroxylated graphane (United States)

    Buonocore, Francesco; Capasso, Andrea; Lisi, Nicola


    Graphene-based derivatives with covalent functionalization and well-defined stoichiometry are highly desirable in view of their application as functional surfaces. Here, we have evaluated by ab initio calculations the energy of formation and the phase diagram of hydroxylated graphane structures, i.e., fully functionalized graphene derivatives coordinated with -H and -OH groups. We compared these structures to different hydrogenated and non-hydrogenated graphene oxide derivatives, with high level of epoxide and hydroxyl groups functionalization. Based on our calculations, stable phases of hydroxylated graphane with low and high contents of hydrogen are demonstrated for high oxygen and hydrogen partial pressure, respectively. Stable phases of graphene oxide with a mixed carbon hybridization are also found. Notably, the synthesis of hydroxylated graphane has been recently reported in the literature.

  16. The reflection of life functional entailment and imminence in relational biology

    CERN Document Server

    Louie, A H


    A. H. Louie’s The Reflection of Life: Functional Entailment and Imminence in Relational Biology is a continuation of the exploratory journey in relational biology which began with his 2009 monograph More Than Life Itself: A Synthetic Continuation in Relational Biology. The theme of his first book was ‘What is life?’; the theme of this sequel is “How do two life forms interact?” Biology is a subject concerned with organization of relations. Relational biology is the approach that advocates ‘function dictates structure”, rather than ‘structure implies function’. It is mathematics decoded into biological realizations. The book demonstrates some of the powers of the approach of relational biology, and illustrates how pertinent problems in biology can be better addressed this way. In the first volume the theory was developed by using partially ordered sets, lattices, simulations, models, Aristotle’s four causes, graphs, categories, simple and complex systems, anticipatory systems, and metabolis...

  17. Evolution of Drosophila resistance against different pathogens and infection routes entails no detectable maintenance costs. (United States)

    Faria, Vítor G; Martins, Nelson E; Paulo, Tânia; Teixeira, Luís; Sucena, Élio; Magalhães, Sara


    Pathogens exert a strong selective pressure on hosts, entailing host adaptation to infection. This adaptation often affects negatively other fitness-related traits. Such trade-offs may underlie the maintenance of genetic diversity for pathogen resistance. Trade-offs can be tested with experimental evolution of host populations adapting to parasites, using two approaches: (1) measuring changes in immunocompetence in relaxed-selection lines and (2) comparing life-history traits of evolved and control lines in pathogen-free environments. Here, we used both approaches to examine trade-offs in Drosophila melanogaster populations evolving for over 30 generations under infection with Drosophila C Virus or the bacterium Pseudomonas entomophila, the latter through different routes. We find that resistance is maintained after up to 30 generations of relaxed selection. Moreover, no differences in several classical life-history traits between control and evolved populations were found in pathogen-free environments, even under stresses such as desiccation, nutrient limitation, and high densities. Hence, we did not detect any maintenance costs associated with resistance to pathogens. We hypothesize that extremely high selection pressures commonly used lead to the disproportionate expression of costs relative to their actual occurrence in natural systems. Still, the maintenance of genetic variation for pathogen resistance calls for an explanation. © 2015 The Author(s). Evolution © 2015 The Society for the Study of Evolution.

  18. [Mental illnesses in childhood and adolescence: A bioethical view of the stigma they entail]. (United States)

    Bella, Mónica E; Vilarrodona, Hugo


    Literature suggests that general beliefs towards mental illnesses are strongly correlated to the social behavior towards people who suffer them. to explore beliefs and attitudes towards mental illnesses in children and adolescents and associate them to bioethics. exploratory, prospective and quantitative study. A questionnaire was administered to parents-tutors of children-adolescents with mental disorders, and to healthcare professionals of the Hospital de Niños de la Santísima Trinidad Córdoba (Argentina). Data processing was performed by means of frequency analysis. 68.5% of parents-tutors and 51.8% of healthcare professionals answered that mental illnesses are never considered like any other illness. Diagnose and treatment is perceived as a stigma by 25.9% of healthcare professionals. For 88.1% of parents-tutors and 9.8% of healthcare professionals, children and adolescents with mental illnesses are never dangerous. 77.1% of parents and 18.4% of professionals stated that people are never afraid of children-adolescents with MI. 42.8% of children-adolescents were excluded from school and 28.5% from family activities. mental illness during childhood entails a stigma that compromises development, equal opportunity and human rights.

  19. Hydroxyl-dependent Evolution of Oxygen Vacancies Enables the Regeneration of BiOCl photocatalyst

    KAUST Repository

    Wu, Sujuan


    Photoinduced oxygen vacancies (OVs) are widely investigated as a vital point defect in wide-band-gap semiconductors. Still, the formation mechanism of OVs remains unclear in various materials. To elucidate the formation mechanism of photoinduced OVs in bismuth oxychloride (BiOCl), we synthesized two surface hydroxyl discrete samples in light of the discovery of the significant variance of hydroxyl groups before and after UV light exposure. It is noted that OVs can be obtained easily after UV light irradiation in the sample with surface hydroxyl groups, while variable changes were observed in samples without surface hydroxyls. Density functional theory (DFT) calculations reveal that the binding energy of Bi-O is drastically influenced by surficial hydroxyl groups, which is intensely correlated to the formation of photoinduced OVs. Moreover, DFT calculations reveal that the adsorbed water molecules are energetically favored to dissociate into separate hydroxyl groups at the OV sites via proton transfer to a neighboring bridging oxygen atom, forming two bridging hydroxyl groups per initial oxygen vacancy. This result is consistent with the experimental observation that the disappearance of photoinduced OVs and the recovery of hydroxyl groups on the surface of BiOCl after exposed to a H2O(g)-rich atmosphere, and finally enables the regeneration of BiOCl photocatalyst. Here, we introduce new insights that the evolution of photoinduced OVs is dependent on surface hydroxyl groups, which will lead to the regeneration of active sites in semiconductors. This work is useful for controllable designs of defective semiconductors for applications in photocatalysis and photovoltaics.

  20. Using the concept of hubots to understand the work entailed in using digital technologies in healthcare. (United States)

    Pope, Catherine; Turnbull, Joanne


    Purpose The purpose of this paper is to explore the human work entailed in the deployment of digital health care technology. It draws on imagined configurations of computers and machines in fiction and social science to think about the relationship between technology and people, and why this makes implementation of digital technology so difficult. The term hubots is employed as a metaphorical device to examine how machines and humans come together to do the work of healthcare. Design/methodology/approach This paper uses the fictional depiction of hubots to reconceptualise the deployment of a particular technology - a computer decision support system (CDSS) used in emergency and urgent care services. Data from two ethnographic studies are reanalysed to explore the deployment of digital technologies in health services. These studies used comparative mixed-methods case study approaches to examine the use of the CDSS in eight different English NHS settings. The data include approximately 900 hours of observation, with 64 semi-structured interviews, 47 focus groups, and surveys of some 700 staff in call centres and urgent care centres. The paper reanalyses these data, deductively, using the metaphor of the hubot as an analytical device. Findings This paper focuses on the interconnected but paradoxical features of both the fictional hubots and the CDSS. Health care call handling using a CDSS has created a new occupation, and enabled the substitution of some clinical labour. However, at the same time, the introduction of the technology has created additional work. There are more tasks, both physical and emotional, and more training activity is required. Thus, the labour has been intensified. Practical implications This paper implies that if we want to realise the promise of digital health care technologies, we need to understand that these technologies substitute for and intensify labour. Originality/value This is a novel analysis using a metaphor drawn from fiction. This

  1. Mechanism of N-hydroxylation catalyzed by flavin-dependent monooxygenases. (United States)

    Badieyan, Somayesadat; Bach, Robert D; Sobrado, Pablo


    Aspergillus fumigatus siderophore (SidA), a member of class B flavin-dependent monooxygenases, was selected as a model system to investigate the hydroxylation mechanism of heteroatom-containing molecules by this group of enzymes. SidA selectively hydroxylates ornithine to produce N(5)-hydroxyornithine. However, SidA is also able to hydroxylate lysine with lower efficiency. In this study, the hydroxylation mechanism and substrate selectivity of SidA were systematically studied using DFT calculations. The data show that the hydroxylation reaction is initiated by homolytic cleavage of the O-O bond in the C(4a)-hydroperoxyflavin intermediate, resulting in the formation of an internal hydrogen-bonded hydroxyl radical (HO(•)). As the HO(•) moves to the ornithine N(5) atom, it rotates and donates a hydrogen atom to form the C(4a)-hydroxyflavin. Oxygen atom transfer yields an aminoxide, which is subsequently converted to hydroxylamine via water-mediated proton shuttling, with the water molecule originating from dehydration of the C(4a)-hydroxyflavin. The selectivity of SidA for ornithine is predicted to be the result of the lower energy barrier for oxidation of ornithine relative to that of lysine (16 vs 24 kcal/mol, respectively), which is due to the weaker stabilizing hydrogen bond between the incipient HO(•) and O3' of the ribose ring of NADP(+) in the transition state for lysine.

  2. Electron-induced processes in hydroxyl cations (United States)

    Cristian Stroe, Marius; Fifirig, Magda


    Competing processes (namely, dissociative recombination, vibrational excitation and vibrational de-excitation) taking place in the collisions between slow electrons and hydroxyl cations have been investigated for electron energies below 1 eV in the framework of the multichannel quantum defect theory. Rydberg states converging to the lowest excited ionic core have been included in some computations reported here.

  3. Hydroxyl radical formation in human gastric juice. (United States)

    Nalini, S; Ramakrishna, B S; Mohanty, A; Balasubramanian, K A


    The hydroxyl radical is the most potent free radical derived from oxygen, and has been implicated in damage caused to the gastroduodenal mucosa. The ability of human gastric juice to generate hydroxyl radicals has been investigated in 54 adults with endoscopically normal gastroduodenal mucosa and in 39 patients with chronic duodenal ulcer. Hydroxyl radical production was measured by the formation of formaldehyde from dimethylsulfoxide. Unlike other body fluids, this reaction could proceed without the extraneous addition of catalysts such as hydrogen peroxide (H2O2), ascorbate and iron. Measurement of H2O2, iron and ascorbate showed that these catalysts are already present in the gastric juice. There was no significant difference in the concentration of these components in gastric juice between normal subjects and patients with duodenal ulcer, except that H2O2 levels were slightly higher in duodenal ulcer patients. Although generation of free radicals has been investigated in other body fluids, this is the first reported case regarding the production of these active species in normal human gastric juice. Since hydroxyl production is not significantly enhanced in duodenal ulcer, we suggest that attention may be turned to mucosal antioxidant defences in this disease.

  4. Bacterial formation of hydroxylated aromatic compounds

    NARCIS (Netherlands)

    Tweel, van den W.J.J.


    As stated in the introduction of this thesis, hydroxylated aromatic compounds in general are of great importance for various industries as for instance pharmaceutical, agrochemical and petrochemical industries. Since these compounds can not be isolated in sufficient amounts from natural

  5. Light-driven cytochrome P450 hydroxylations

    DEFF Research Database (Denmark)

    Jensen, Kenneth; Jensen, Poul Erik; Møller, Birger Lindberg


    Plants are light-driven "green" factories able to synthesize more than 200,000 different bioactive natural products, many of which are high-value products used as drugs (e.g., artemisinin, taxol, and thapsigargin). In the formation of natural products, cytochrome P450 (P450) monooxygenases play...... a key role in catalyzing regio- and stereospecific hydroxylations that are often difficult to achieve using the approaches of chemical synthesis. P450-catalyzed monooxygenations are dependent on electron donation typically from NADPH catalyzed by NADPH-cytochrome P450 oxidoreductase (CPR......). The consumption of the costly cofactor NADPH constitutes an economical obstacle for biotechnological in vitro applications of P450s. This bottleneck has been overcome by the design of an in vitro system able to carry out light-driven P450 hydroxylations using photosystem I (PSI) for light harvesting...

  6. Hydroxyl radical induced degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: [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)


    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.

  7. Simon's fundamental rich-gets-richer model entails a dominant first-mover advantage

    CERN Document Server

    Dodds, Peter Sheridan; Hazlehurst, Fletcher F; Van Oort, Colin M; Mitchell, Lewis; Reagan, Andrew J; Williams, Jake Ryland; Danforth, Christopher M


    Herbert Simon's classic rich-gets-richer model is one of the simplest empirically supported mechanisms capable of generating heavy-tail size distributions for complex systems. Simon argued analytically that a population of flavored elements growing by either adding a novel element or randomly replicating an existing one would afford a distribution of group sizes with a power-law tail. Here, we show that, in fact, Simon's model does not produce a simple power law size distribution as the initial element has a dominant first-mover advantage, and will be overrepresented by a factor proportional to the inverse of the innovation probability. The first group's size discrepancy cannot be explained away as a transient of the model, and may therefore be many orders of magnitude greater than expected. We demonstrate how Simon's analysis was correct but incomplete, and expand our alternate analysis to quantify the variability of long term rankings for all groups. We find that the expected time for a first replication is...

  8. Simon's fundamental rich-get-richer model entails a dominant first-mover advantage (United States)

    Dodds, Peter Sheridan; Dewhurst, David Rushing; Hazlehurst, Fletcher F.; Van Oort, Colin M.; Mitchell, Lewis; Reagan, Andrew J.; Williams, Jake Ryland; Danforth, Christopher M.


    Herbert Simon's classic rich-get-richer model is one of the simplest empirically supported mechanisms capable of generating heavy-tail size distributions for complex systems. Simon argued analytically that a population of flavored elements growing by either adding a novel element or randomly replicating an existing one would afford a distribution of group sizes with a power-law tail. Here, we show that, in fact, Simon's model does not produce a simple power-law size distribution as the initial element has a dominant first-mover advantage, and will be overrepresented by a factor proportional to the inverse of the innovation probability. The first group's size discrepancy cannot be explained away as a transient of the model, and may therefore be many orders of magnitude greater than expected. We demonstrate how Simon's analysis was correct but incomplete, and expand our alternate analysis to quantify the variability of long term rankings for all groups. We find that the expected time for a first replication is infinite, and show how an incipient group must break the mechanism to improve their odds of success. We present an example of citation counts for a specific field that demonstrates a first-mover advantage consistent with our revised view of the rich-get-richer mechanism. Our findings call for a reexamination of preceding work invoking Simon's model and provide an expanded understanding going forward.

  9. Global tropospheric hydroxyl distribution, budget and reactivity (United States)

    Lelieveld, Jos; Gromov, Sergey; Pozzer, Andrea; Taraborrelli, Domenico


    The self-cleaning or oxidation capacity of the atmosphere is principally controlled by hydroxyl (OH) radicals in the troposphere. Hydroxyl has primary (P) and secondary (S) sources, the former mainly through the photodissociation of ozone, the latter through OH recycling in radical reaction chains. We used the recent Mainz Organics Mechanism (MOM) to advance volatile organic carbon (VOC) chemistry in the general circulation model EMAC (ECHAM/MESSy Atmospheric Chemistry) and show that S is larger than previously assumed. By including emissions of a large number of primary VOC, and accounting for their complete breakdown and intermediate products, MOM is mass-conserving and calculates substantially higher OH reactivity from VOC oxidation compared to predecessor models. Whereas previously P and S were found to be of similar magnitude, the present work indicates that S may be twice as large, mostly due to OH recycling in the free troposphere. Further, we find that nighttime OH formation may be significant in the polluted subtropical boundary layer in summer. With a mean OH recycling probability of about 67 %, global OH is buffered and not sensitive to perturbations by natural or anthropogenic emission changes. Complementary primary and secondary OH formation mechanisms in pristine and polluted environments in the continental and marine troposphere, connected through long-range transport of O3, can maintain stable global OH levels.

  10. Hidden correlations entailed by q-non additivity render the q-monoatomic gas highly non trivial (United States)

    Plastino, A.; Rocca, M. C.


    It ts known that Tsallis' q-non-additivity entails hidden correlations. It has also been shown that even for a monoatomic gas, both the q-partition function Z and the mean energy 〈 U 〉 diverge and, in particular, exhibit poles for certain values of the Tsallis non additivity parameter q. This happens because Z and 〈 U 〉 both depend on a Γ-function. This Γ, in turn, depends upon the spatial dimension ν. We encounter three different regimes according to the argument A of the Γ-function. (1) A > 0, (2) A 0 outside the poles. (3) A displays poles and the physics is obtained via dimensional regularization. In cases (2) and (3) one discovers gravitational effects and quartets of particles. Moreover, bound states and gravitational effects emerge as a consequence of the hidden q-correlations.

  11. Hydrogen peroxide and hydroxyl radical formation by methylene blue in the presence of ascorbic acid

    Energy Technology Data Exchange (ETDEWEB)

    Buettner, G.R.; Doherty, T.P.; Bannister, T.D.


    Using ESR we have demonstrated the formation of the ascorbate free radical from sodium ascorbate, methylene blue and light. In oxygen uptake experiments we have observed the production of hydrogen peroxide while spin trapping experiments have revealed the iron catalyzed production of the hydroxyl free radical in this system. The presence of this highly reactive radical suggests that it could be the radical that initiates free radical damage in this photodynamic system. 39 refs.

  12. Footprinting protein-DNA complexes using the hydroxyl radical. (United States)

    Jain, Swapan S; Tullius, Thomas D


    Hydroxyl radical footprinting has been widely used for studying the structure of DNA and DNA-protein complexes. The high reactivity and lack of base specificity of the hydroxyl radical makes it an excellent probe for high-resolution footprinting of DNA-protein complexes; this technique can provide structural detail that is not achievable using DNase I footprinting. Hydroxyl radical footprinting experiments can be carried out using readily available and inexpensive reagents and lab equipment. This method involves using the hydroxyl radical to cleave a nucleic acid molecule that is bound to a protein, followed by separating the cleavage products on a denaturing electrophoresis gel to identify the protein-binding sites on the nucleic acid molecule. We describe a protocol for hydroxyl radical footprinting of DNA-protein complexes, along with a troubleshooting guide, that allows researchers to obtain efficient cleavage of DNA in the presence and absence of proteins. This protocol can be completed in 2 d.

  13. Searching for a One-Step Bioprocess for the Production of Hydroxyl Fatty Acids and Hydroxyl Oils from Soybean Oil (United States)

    Soybean oil is produced domestically in large supply, averaging over 20 billion pounds per year with an annual carryover of more than one billion pounds. It is important to find new uses for this surplus soybean oil. Hydroxyl fatty acids and hydroxyl oils are platform materials for specialty chemi...

  14. Postural instability of extremely obese individuals improves after a body weight reduction program entailing specific balance training. (United States)

    Maffiuletti, N A; Agosti, F; Proietti, M; Riva, D; Resnik, M; Lafortuna, C L; Sartorio, A


    The purposes of this study were to compare postural stability between obese and lean subjects and to investigate the effect of a 3-week body weight reduction (BWR) program entailing specific balance training on postural stability of extremely obese patients. Time of balance maintenance and mean error on the medial-lateral direction at the trunk and lower limb level were assessed during a single limb stance on a movable platform in 19 non-obese and in 20 extremely obese individuals (age range: 20-40 yr). Time of balance maintenance was shorter (obese: 21.1+/-7.7 vs lean: 27.3+/-3.1 sec) and medial-lateral sway of the trunk was larger in obese (5.4+/-3.2 degrees) than in lean (3.2+/-1.1 degrees) subjects (pprogram (energy-restricted diet, moderate physical exercise, nutritional education and psychological counselling) combined with or without 6 sessions of specific balance training on a movable platform. BWR plus specific balance training enhanced time of balance maintenance (pre: 23.8+/-7.2 vs post: 30.0+/-0.0 sec) and reduced the trunk sway (5.2+/-2.8 degrees vs 2.6+/-0.9 degrees ) more than BWR alone (pprogram. It was concluded that balance improvement is an important goal of rehabilitation, that would probably reduce the propensity of overweight individuals to fall while performing everyday activities.

  15. Radioprotective activity of some. beta. -hydroxylated indole-alkylamines

    Energy Technology Data Exchange (ETDEWEB)

    Deanovic, Z.; Trescec, A.; Kveder, S.; Iskric, S.; Supek, Z.


    Chain ..beta..-hydroxylated derivatives of tryptamine, 5-methoxytryptamine and 5-hydroxytryptamine (serotonin), respectively, were tested as radioprotectors in X-ray-irradiated mice. At midlethal dose of irradiation (725 cGy), tryptamine and serotonin protected all the animals, ..beta..-hydroxylated tryptamine was only slightly less effective (survival 85%). On the contrary, when mice were irradiated with absolutely lethal dose (900 cGy), only ..beta..-hydroxylated derivative of serotonin gave complete (100%) protection to the animals; 5-hydroxytryptamine and 5-methoxytryptamine protected about 90% of the animals. ..beta..-hydroxy-5-methosytryptamine 35%, tryptamine 29%, whereas ..beta..-hydroxytryptamine did not give any protection.

  16. Regioselective alkane hydroxylation with a mutant AlkB enzyme (United States)

    Koch, Daniel J.; Arnold, Frances H.


    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  17. Hydroxyl free radical production during torsional phacoemulsification. (United States)

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


    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.

  18. Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution (United States)

    Saksono, Nelson; Febiyanti, Irine Ayu; Utami, Nissa; Ibrahim


    Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H2O2 amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

  19. Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

    Energy Technology Data Exchange (ETDEWEB)

    Saksono, Nelson; Febiyanti, Irine Ayu, E-mail:; Utami, Nissa; Ibrahim [Department of Chemical Engineering, Universitas Indonesia, Depok 16424, Indonesia Phone: +62217863516, Fax: +62217863515 (Indonesia)


    Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H{sub 2}O{sub 2} amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

  20. Effect of curcumin against oxidation of biomolecules by hydroxyl radicals. (United States)

    Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little


    Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.

  1. Hydroxyl radical footprinting of protein-DNA complexes. (United States)

    Jagannathan, Indu; Hayes, Jeffrey J


    This unit details the use of hydroxyl radicals to characterize protein-DNA interactions. This method may be used to assess the exact location of contacts between a protein and its cognate DNA and details of the complex structure. We describe several methods to prepare DNA templates for footprinting and ways to avoid many of the pitfalls associated with the use of hydroxyl radical footprinting. In addition, we describe in detail one example of the application of this technique.

  2. Monolayer arrangement of fatty hydroxystearic acids on graphite: Influence of hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Medina, S. [Laboratorio de Rayos-X, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Benítez, J.J.; Castro, M.A. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Cerrillos, C. [Servicio de Microscopía, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Millán, C. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Alba, M.D., E-mail: [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain)


    Previous studies have indicated that long-chain linear carboxylic acids form commensurate packed crystalline monolayers on graphite even at temperatures above their melting point. This study examines the effect on the monolayer formation and structure of adding one or more secondary hydroxyl, functional groups to the stearic acid skeleton (namely, 12-hydroxystearic and 9,10-dihydroxystearic acid). Moreover, a comparative study of the monolayer formation on recompressed and monocrystalline graphite has been performed through X-ray diffraction (XRD) and Scanning Tunneling Microscopy (STM), respectively. The Differential Scanning Calorimetry (DSC) and XRD data were used to confirm the formation of solid monolayers and XRD data have provided a detailed structural analysis of the monolayers in good correspondence with obtained STM images. DSC and XRD have demonstrated that, in stearic acid and 12-hydroxystearic acid adsorbed onto graphite, the monolayer melted at a higher temperature than the bulk form of the carboxylic acid. However, no difference was observed between the melting point of the monolayer and the bulk form for 9,10-dihydroxystearic acid adsorbed onto graphite. STM results indicated that all acids on the surface have a rectangular p2 monolayer structure, whose lattice parameters were uniaxially commensurate on the a-axis. This structure does not correlate with the initial structure of the pure compounds after dissolving, but it is conditioned to favor a) hydrogen bond formation between the carboxylic groups and b) formation of hydrogen bonds between secondary hydroxyl groups, if spatially permissible. Therefore, the presence of hydroxyl functional groups affects the secondary structure and behavior of stearic acid in the monolayer. - Highlights: • Hydroxyl functional groups affect structure and behavior of acids in the monolayer. • Acids on the surface have a rectangular p2 monolayer structure. • Lattice parameters of acids are uniaxially

  3. Histopathology of fathead minnow (Pimephales promelas) exposed to hydroxylated fullerenes. (United States)

    Jovanović, Boris; Whitley, Elizabeth M; Palić, Dušan


    Hydroxylated fullerenes are reported to be very strong antioxidants, acting to quench reactive oxygen species, thus having strong potential for important and widespread applications in innovative therapies for a variety of disease processes. However, their potential for toxicological side effects is still largely controversial and unknown. Effects of hydroxylated fullerenes C60(OH)24 on the fathead minnow (Pimephales promelas) were investigated microscopically after a 72-hour (acute) exposure by intraperitoneal injection of 20 ppm of hydroxylated fullerenes per gram of body mass. Cumulative, semi-quantitative histopathologic evaluation of brain, liver, anterior kidney, posterior kidney, skin, coelom, gills and the vestibuloauditory system revealed significant differences between control and hydroxylated fullerene-treated fish. Fullerene-treated fish had much higher cumulative histopathology scores. Histopathologic changes included loss of cellularity in the interstitium of the kidney, a primary site of haematopoiesis in fish, and loss of intracytoplasmic glycogen in liver. In the coelom, variable numbers of leukocytes, including many macrophages and fewer heterophils and rodlet cells, were admixed with the nanomaterial. These findings raise concern about in vivo administration of hydroxylated fullerenes in experimental drugs and procedures in human medicine, and should be investigated in more detail.

  4. How hydroxylation affects hydrogen adsorption and formation on nanosilicates (United States)

    Kerkeni, Boutheïna; Bacchus-Montabonel, Marie-Christine; Bromley, Stefan T.


    Silicate dust constitutes one of the primary solid components of the Universe and is thought to be an essential enabler for complex chemistry in a number of astronomical environments. Hydroxylated silicate nanoclusters (MgO)x(SiO2)y(H2O)z, where strongly absorbed water molecules are dissociated on the silicate surface, are likely to be persistent in diffuse clouds. Such precursor species are thus also primary candidates as seeds for the formation and growth of icy dust grains in dense molecular clouds. Using density functional calculations we investigate the reactivity of hydroxylated pyroxene nanoclusters (Mg4Si4O12)(H2O)N (N = 1-4) towards hydrogen physisorption, chemisorption and H2 formation. Our results show that increased hydroxylation leads to a significant reduction in the energy range for the physisorption and chemisorption of single H atoms, when compared to bare silicate grains and bare bulk silicate surfaces. Subsequent chemisorption of a second H atom is, however, little affected by hydroxylation. The H2 reaction barrier for the recombination of two chemisorbed H atoms tends to follow a linear correlation with respect to the 2Hchem binding energy, suggestive of a general Brønsted-Evans-Polanyi relation for H2 formation on silicate grains, independent of dust grain size, composition and degree of hydroxylation.

  5. Ab initio dynamics of the cytochrome P450 hydroxylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Elenewski, Justin E.; Hackett, John C, E-mail: [Department of Physiology and Biophysics and The Massey Cancer Center, School of Medicine, Virginia Commonwealth University, 401 College Street, Richmond, Virginia 23219-1540 (United States)


    The iron(IV)-oxo porphyrin π-cation radical known as Compound I is the primary oxidant within the cytochromes P450, allowing these enzymes to affect the substrate hydroxylation. In the course of this reaction, a hydrogen atom is abstracted from the substrate to generate hydroxyiron(IV) porphyrin and a substrate-centered radical. The hydroxy radical then rebounds from the iron to the substrate, yielding the hydroxylated product. While Compound I has succumbed to theoretical and spectroscopic characterization, the associated hydroxyiron species is elusive as a consequence of its very short lifetime, for which there are no quantitative estimates. To ascertain the physical mechanism underlying substrate hydroxylation and probe this timescale, ab initio molecular dynamics simulations and free energy calculations are performed for a model of Compound I catalysis. Semiclassical estimates based on these calculations reveal the hydrogen atom abstraction step to be extremely fast, kinetically comparable to enzymes such as carbonic anhydrase. Using an ensemble of ab initio simulations, the resultant hydroxyiron species is found to have a similarly short lifetime, ranging between 300 fs and 3600 fs, putatively depending on the enzyme active site architecture. The addition of tunneling corrections to these rates suggests a strong contribution from nuclear quantum effects, which should accelerate every step of substrate hydroxylation by an order of magnitude. These observations have strong implications for the detection of individual hydroxylation intermediates during P450 catalysis.

  6. Histopathology of fathead minnow (Pimephales promelas) exposed to hydroxylated fullerenes (United States)

    Whitley, Elizabeth M.; Palić, Dušan


    Hydroxylated fullerenes are reported to be very strong antioxidants, acting to quench reactive oxygen species, thus having strong potential for important and widespread applications in innovative therapies for a variety of disease processes. However, their potential for toxicological side effects is still largely controversial and unknown. Effects of hydroxylated fullerenes C60(OH)24 on the fathead minnow (Pimephales promelas) were investigated microscopically after a 72-hour (acute) exposure by intraperitoneal injection of 20 ppm of hydroxylated fullerenes per gram of body mass. Cumulative, semi-quantitative histopathologic evaluation of brain, liver, anterior kidney, posterior kidney, skin, coelom, gills and the vestibuloauditory system revealed significant differences between control and hydroxylated fullerene-treated fish. Fullerene-treated fish had much higher cumulative histopathology scores. Histopathologic changes included loss of cellularity in the interstitium of the kidney, a primary site of haematopoiesis in fish, and loss of intracytoplasmic glycogen in liver. In the coelom, variable numbers of leukocytes, including many macrophages and fewer heterophils and rodlet cells, were admixed with the nanomaterial. These findings raise concern about in vivo administration of hydroxylated fullerenes in experimental drugs and procedures in human medicine, and should be investigated in more detail. PMID:23883179

  7. Hydroxyl Radical-Mediated Novel Modification of Peptides: N-Terminal Cyclization through the Formation of α-Ketoamide. (United States)

    Lee, Seon Hwa; Kyung, Hyunsook; Yokota, Ryo; Goto, Takaaki; Oe, Tomoyuki


    The hydroxyl radical-mediated oxidation of peptides and proteins constitutes a large group of post-translational modifications that can result in structural and functional changes. These oxidations can lead to hydroxylation, sulfoxidation, or carbonylation of certain amino acid residues and cleavage of peptide bonds. In addition, hydroxyl radicals can convert the N-terminus of peptides to an α-ketoamide via abstraction of the N-terminal α-hydrogen and hydrolysis of the ketimine intermediate. In the present study, we identified N-terminal cyclization as a novel modification mediated by a hydroxyl radical. The reaction of angiotensin (Ang) II (DRVYIHPF) and the hydroxyl radical generated by the Cu(II)/ascorbic acid (AA) system or UV/hydrogen peroxide system produced N-terminal cyclized-Ang II (Ang C) and pyruvamide-Ang II (Ang P, CH3COCONH-RVYIHPF). The structure of Ang C was confirmed by mass spectrometry and comparison to an authentic standard. The subsequent incubation of isolated Ang P in the presence of Cu(II)/AA revealed that Ang P was the direct precursor of Ang C. The proposed mechanism involves the formation of a nitrogen-centered (aminyl) radical, which cyclizes to form a five-membered ring containing the alkoxy radical. The subsequent β-scission reaction of the alkoxyl radical results in the cleavage of the terminal CH3CO group. The initial aminyl radical can be stabilized by chelation to the Cu(II) ions. The affinity of Ang C toward the Ang II type 1 receptor was significantly lower than that of Ang II or Ang P. Ang C was not further metabolized by aminopeptidase A, which converts Ang II to Ang III. Hydroxyl radical-mediated N-terminal cyclization was also observed in other Ang peptides containing N-terminal alanine, arginine, valine, and amyloid β 1-11 (DAEFRHDSGYE).

  8. Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface (United States)

    Zhang, Xinxing; Barraza, Kevin M.; Upton, Kathleen T.; Beauchamp, J. L.


    The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols.

  9. Electrocatalytic Properties of BDD Anodes: Its Loosely Adsorbed Hydroxyl Radicals

    Directory of Open Access Journals (Sweden)

    Nicolaos Vatistas


    Full Text Available The high oxidative action of boron doped diamond (BDD anodes on the biorefractory organic compounds has been attributed to the low adsorption of the generated hydroxyl radicals on the BDD surface in respect to other anodic materials. In a previous paper, the effect of low adsorption of BBD has been studied by proposing a continuum approach to represent the adsorption layer. The oxidative action of the hydroxyl radicals is attributed to the values of their diffusivity into the adsorption and adjacent reactive layer as well as to the value of kinetic constant in both layers. In this paper, more details on both layers are reported in order to justify the proposed continuum approach as well as the assumptions concerning diffusivity and kinetic constant in both adsorption and reactive layers, where the oxidative action of hydroxyl radicals occurs.

  10. Balloon borne LIDAR measurements of stratospheric hydroxyl radical (United States)

    Heaps, W. S.; Mcgee, T. J.


    A balloon-borne laser radar (LIDAR) system for determining the stratospheric hydroxyl radical concentration constructed and flown by the Goddard Space Flight Center is discussed. The system measured hydroxyl in the altitude range of 34-37 km during an afternoon and early evening, producing the first post-sunset hydroxyl determination ever obtained. Daytime values (approximately 5 x 10 to the 6th/cu cm) are somewhat lower than previous measurements using in situ resonance fluorescence. Nighttime values (approximately 7 x 10 to the 5th/cu cm at 2100 CDT) are found to be higher than predicted by current one-dimensional models. Possible sources of these discrepancies, together with improvements possible in future systems, are outlined.

  11. Progress in stratospheric hydroxyl measurement by balloon-borne lidar (United States)

    Heaps, W. S.; Mcgee, T. J.


    Knowledge of the concentration of hydroxyl radical is crucial to understanding the chemistry of the stratosphere. Hydroxyl participates in several catalytic cycles which destroy ozone and strongly influences the cycles of chlorine and nitrogen oxides by its reactions which form or destroy reservoirs for chlorine and odd-nitrogen compounds. Measurements have been conducted of the concentration of hydroxyl radical between the altitudes of 32.5 and 38.5 km using the technique of laser-induced fluorescence. The results ranging from 4 to 9 x 10 to the 6th per cu cm (with an accuracy of + or - 50 percent) are about 2-3 times lower than predicted by current one-dimensional models, although the uncertainties in the determination and in the models are sufficiently large to explain the differences. A number of potential improvements to the instrument are discussed.

  12. Characterization of the Ornithine Hydroxylation Step in Albachelin Biosynthesis

    Directory of Open Access Journals (Sweden)

    Kendra Bufkin


    Full Text Available N-Hydroxylating monooxygenases (NMOs are involved in siderophore biosynthesis. Siderophores are high affinity iron chelators composed of catechol and hydroxamate functional groups that are synthesized and secreted by microorganisms and plants. Recently, a new siderophore named albachelin was isolated from a culture of Amycolatopsis alba growing under iron-limiting conditions. This work focuses on the expression, purification, and characterization of the NMO, abachelin monooxygenase (AMO from A. alba. This enzyme was purified and characterized in its holo (FAD-bound and apo (FAD-free forms. The apo-AMO could be reconstituted by addition of free FAD. The two forms of AMO hydroxylate ornithine, while lysine increases oxidase activity but is not hydroxylated and display low affinity for NADPH.

  13. Hydroxyl Radical Dosimetry for High Flux Hydroxyl Radical Protein Footprinting Applications Using a Simple Optical Detection Method (United States)

    Xie, Boer; Sharp, Joshua S.


    Hydroxyl radical protein footprinting (HRPF) by Fast Photochemical Oxidation of Proteins (FPOP) is a powerful benchtop tool used to probe protein structure, interactions, and conformational changes in solution. However, the reproducibility of all HRPF techniques is limited by the ability to deliver a defined concentration of hydroxyl radicals to the protein. This ability is impacted by both the amount of radical generated and the presence of radical scavengers in solution. In order to compare HRPF data from sample to sample, a hydroxyl radical dosimeter is needed that can measure the effective concentration of radical that is delivered to the protein, after accounting for both differences in hydroxyl radical generation and non-analyte radical consumption. Here, we test three radical dosimeters (Alexa Fluor 488, terepthalic acid, and adenine) for their ability to quantitatively measure the effective radical dose under the high radical concentration conditions of FPOP. Adenine has a quantitative relationship between UV spectrophotometric response, effective hydroxyl radical dose delivered, and peptide and protein oxidation levels over the range of radical concentrations typically encountered in FPOP. The simplicity of an adenine-based dosimeter allows for convenient and flexible incorporation into FPOP applications, and the ability to accurately measure the delivered radical dose will enable reproducible and reliable FPOP across a variety of platforms and applications. PMID:26455423

  14. Hashish. Importance of the phenolic hydroxyl group in tetrahydrocannabinols. (United States)

    Uliss, D B; Dalzell, H C; Handrick, G R; Howes, J F; Razdan, R K


    Optically active delta-3- and delta-8-tetrahydrocannabinols (THC's), cannabidiol and racemic delta-9-cis-THC, and their corresponding analogs (1b yields 4b) in which the positions of the phenolic hydroxyl group and the n-C5 side chain have been interchanged are compared in selected pharmacological tests in mice. the results indicate that the phenolic hydroxyl group in the 1 position in THC's is very important for eliciting activity and that cannabidiol and delta-9-cis-THC possess weak CNS depressant properties.

  15. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution (United States)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László


    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV-vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved.

  16. Radiocarbon tracer measurements of atmospheric hydroxyl radical concentrations (United States)

    Campbell, M. J.; Farmer, J. C.; Fitzner, C. A.; Henry, M. N.; Sheppard, J. C.


    The usefulness of the C-14 tracer in measurements of atmospheric hydroxyl radical concentration is discussed. The apparatus and the experimental conditions of three variations of a radiochemical method of atmosphere analysis are described and analyzed: the Teflon bag static reactor, the flow reactor (used in the Wallops Island tests), and the aircraft OH titration reactor. The procedure for reduction of the aircraft reactor instrument data is outlined. The problems connected with the measurement of hydroxyl radicals are discussed. It is suggested that the gas-phase radioisotope methods have considerable potential in measuring tropospheric impurities present in very low concentrations.

  17. Stimulation of tolbutamide hydroxylation by acetone and acetonitrile in human liver microsomes and in a cytochrome P-450 2C9-reconstituted system. (United States)

    Palamanda, J; Feng, W W; Lin, C C; Nomeir, A A


    Organic solvents are often used to solubilize lipophilic new chemical entities before their addition to in vitro test systems such as microsomal stability or cytochrome P-450 (CYP) inhibition. However, the effect of these organic solvents on the test systems is not usually characterized. This study was initiated to evaluate the effect of acetonitrile and acetone, in addition to other organic solvents, on the tolbutamide hydroxylation activity of CYP2C9 in both human liver microsomes and a CYP2C9-reconstituted system. Both acetonitrile and acetone significantly stimulated the NADPH-dependent tolbutamide hydroxylation by nearly 2- to 3-fold in human liver microsomes and CYP2C9-reconstituted system when incubated at 2 and 4% final solvent concentrations. When cumene hydroperoxide was used instead of NADPH, both acetone and acetonitrile significantly inhibited tolbutamide hydroxylation. This NADPH-dependent stimulatory effect was further evaluated by examining the effect of a series of other organic solvents with different carbon chain lengths and various functional groups, including hydroxyl, ketone, and aldehyde. Unlike acetone, two other ketone-containing solvents, methyl ethyl ketone (2-butanone) and diethyl ketone (3-pentanone) failed to significantly enhance tolbutamide hydroxylation. Other solvents tested, including methanol, ethanol, propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, acetaldehyde, and dimethyl sulfoxide significantly inhibited NADPH-dependent tolbutamide hydroxylation. Overall, the stimulatory effect of both acetonitrile and acetone on tolbutamide hydroxylation was found to be primarily due to a consistent increase in V(max), whereas K(m) was unchanged in both human liver microsomes and the reconstituted CYP2C9 system. These data suggest that acetone and acetonitrile stimulate NADPH-mediated tolbutamide hydroxylation via the CYP reductase and not by modifying the affinity of tolbutamide for the CYP2C9 enzyme.

  18. Hydroxyl radical reactivity at the air-ice interface

    Directory of Open Access Journals (Sweden)

    T. F. Kahan


    Full Text Available Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at air-ice interfaces, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH anthracene at air-water interfaces, but no loss was observed at air-ice interfaces. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL that exists at air-ice interfaces.

  19. Observational evidence for interhemispheric hydroxyl-radical parity

    NARCIS (Netherlands)

    Patra, P.K.; Krol, M.C.; Montzka, S.A.; Arnold, T.; Atlas, E.L.; Lintner, B.R.; Stephens, B.B.; Xiang, B.


    The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere1, 2, 3. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species

  20. Shrinkage of vitreous body caused by hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Park, Myoung Joo; Shimada, Takashi; Matuo, Yoichirou; Akiyama, Yoko; Izumi, Yoshinobu; Nishijima, Shigehiro [Osaka University, Osaka (Japan)


    In the study, we examined the effect of hydroxyl radical generated by {gamma}-ray and UV irradiation on shrinkage of vitreous body. Change in gel ratio of vitreous body and change in the properties of its components (collagen, sodium hyaluronate) were analyzed. By comparing these results, the amount of hydroxyl radical, which induces the considerable shrinkage of vitreous body, was evaluated from theoretical calculation based on experimental condition and some reported kinetic parameters. It was concluded that the integrated amount of hydroxyl radical required to liquefy half of the vitreous body (vitreous body gel ratio = 50%) was estimated as 140 {mu}molg{sup -1} from {gamma}-ray irradiation experiment. Also, from UV irradiation experiment result, it was confirmed that the effect of hydroxyl radical is larger than that of other reactive species. The causes of shrinkage of vitreous body are supposed as follows, 1) decrease in viscosity by cleavage of glycoside bond in sodium hyaluronate, 2) leaching of collagen from vitreous body and 3) leaching of crosslinked products and scission products of collagen.

  1. Enantioselective Hydroxylation of 4-Alkylphenols by Vanillyl Alcohol Oxidase

    NARCIS (Netherlands)

    Drijfhout, Falko P.; Fraaije, Marco W.; Jongejan, Hugo; Berkel, Willem J.H. van; Franssen, Maurice C.R.


    Vanillyl alcohol oxidase (VAO) from Penicillium simplicissimum catalyzes the enantioselective hydroxylation of 4-ethylphenol, 4-propylphenol, and 2-methoxy-4-propylphenol into 1-(4'-hydroxyphenyl)ethanol, 1-(4'-hydroxyphenyl)propanol, and 1-(4'-hydroxy-3'-methoxyphenyl)propanol, respectively, with

  2. Hydroxyl radical scavenging activity of peptide from sea cucumber ...

    African Journals Online (AJOL)

    enzyme complex, sea cucumber protein hydrolysis was carried out to obtain hydrolysates that have hydroxyl-radical-scavenging activity (HRSA). The hydrolytic process was monitored by HRSA and conditions for this process were optimized as follows: pH 6.5, temperature 35°C, 12 mg enzyme complex in a reaction solution ...

  3. Decomposition of water into highly combustible hydroxyl gas used in ...

    African Journals Online (AJOL)

    The method proposed involves the decomposition of water into highly combustible hydroxyl gas via electrolysis, which is used in internal combustion engines of electrical generators for electricity generation. The by-product obtained from combustion of this gas is water vapour and oxygen to replenish the atmosphere.

  4. Dioxygen reactivity of meso-hydroxylated hemes: intermediates in ...

    Indian Academy of Sciences (India)

    Keywords. Heme oxygenase; heme degradation; coupled oxidation; variable temperature paramagnetic NMR. Abstract. Heme oxygenase (HO) is the only enzyme in mammals known to catalyse the physiological degradation of unwanted heme into biliverdin, Fe ion and CO. The process involves introduction of the hydroxyl ...

  5. Hydroxyl migration disorders the surface structure of hydroxyapatite nanoparticles (United States)

    Cheng, Xiajie; Wu, Hong; Zhang, Li; Ma, Xingtao; Zhang, Xingdong; Yang, Mingli


    The surface structure of nano-hydroxyapatite (HAP) was investigated using a combined simulated annealing and molecular dynamics method. The stationary structures of nano-HAP with 4-7 nm in diameter and annealed under different temperatures were analyzed in terms of pair distribution function, structural factor, mean square displacement and atomic coordination number. The particles possess different structures from bulk crystal. A clear radial change in their atomic arrangements was noted. From core to surface the structures change from ordered to disordered. A three-shell model was proposed to describe the structure evolution of nano-HAP. Atoms in the core zone keep their arrangements as in crystal, while atoms in the surface shell are in short-range order and long-range disorder, adopting a typically amorphous structure. Atoms in the middle shell have small displacements and/or deflections but basically retain their original locations as in crystal. The disordered shell is about 1 nm in thickness, in agreement with experimental observations. The disordering mainly stems from hydroxyl migration during which hydroxyls move to the surface and bond with the exposed Ca ions, and their left vacancies bring about a rearrangement of nearby atoms. The disordering is to some extent different for particles unannealed under different temperatures, resulting from fewer number of migrated hydroxyls at lower temperatures. Particles with different sizes have similar surface structures, and their surface energy decreases with increasing size. Moreover, the surface energy is reduced by hydroxyl migration because the exposed Ca ions on the surface are ionically bonded with the migrated hydroxyls. Our calculations proposed a new structure model for nano-HAP, which indicates a surface structure with activities different from those without surface reorganization. This is particularly interesting because most bioactivities of biomaterials are dominated by their surface activity.

  6. Differential effects of collagen prolyl 3-hydroxylation on skeletal tissues.

    Directory of Open Access Journals (Sweden)

    Erica P Homan


    Full Text Available Mutations in the genes encoding cartilage associated protein (CRTAP and prolyl 3-hydroxylase 1 (P3H1 encoded by LEPRE1 were the first identified causes of recessive Osteogenesis Imperfecta (OI. These proteins, together with cyclophilin B (encoded by PPIB, form a complex that 3-hydroxylates a single proline residue on the α1(I chain (Pro986 and has cis/trans isomerase (PPIase activity essential for proper collagen folding. Recent data suggest that prolyl 3-hydroxylation of Pro986 is not required for the structural stability of collagen; however, the absence of this post-translational modification may disrupt protein-protein interactions integral for proper collagen folding and lead to collagen over-modification. P3H1 and CRTAP stabilize each other and absence of one results in degradation of the other. Hence, hypomorphic or loss of function mutations of either gene cause loss of the whole complex and its associated functions. The relative contribution of losing this complex's 3-hydroxylation versus PPIase and collagen chaperone activities to the phenotype of recessive OI is unknown. To distinguish between these functions, we generated knock-in mice carrying a single amino acid substitution in the catalytic site of P3h1 (Lepre1(H662A . This substitution abolished P3h1 activity but retained ability to form a complex with Crtap and thus the collagen chaperone function. Knock-in mice showed absence of prolyl 3-hydroxylation at Pro986 of the α1(I and α1(II collagen chains but no significant over-modification at other collagen residues. They were normal in appearance, had no growth defects and normal cartilage growth plate histology but showed decreased trabecular bone mass. This new mouse model recapitulates elements of the bone phenotype of OI but not the cartilage and growth phenotypes caused by loss of the prolyl 3-hydroxylation complex. Our observations suggest differential tissue consequences due to selective inactivation of P3H1 hydroxylase

  7. A regioselective alkylation at the C-6 hydroxyl group of erythromycin A-oxime derivatives




    Erythromycin A contains five hydroxyl groups. The regioselective alkylation at the C-6 hydroxyl group was achieved to an extent ofmore than 97% when a 9-O-substituted erythromycin A-9-oxime was employed as the substrate.

  8. Hydroxyl accessibility in wood by deuterium exchange and ATR-FTIR spectroscopy

    DEFF Research Database (Denmark)

    Tarmian, Asghar; Burgert, Ingo; Thybring, Emil Engelund


    The accessibility of wood hydroxyls to water is commonly studied by infrared spectroscopy after deuteration where water-interacting hydroxyls have their H exchanged for D. In this study, the hydroxyl accessibility is determined with ATR-FTIR spectroscopy after deuteration of specimens with liquid D...

  9. Third-generation FAGE instrument for tropospheric hydroxyl radical measurement (United States)

    Chan, C. Y.; Hard, T. M.; Mehrabzadeh, A. A.; George, L. A.; O'Brien, R. J.


    A single-stage, frequency-doubled, copper vapor laser-pumped dye laser has been constructed to be used in the measurement of atmospheric hydroxyl radical concentrations. A new photon counting instrument is used for HO fluorescence detection. Theoretical and experimental studies of instrument performance show better sensitivities and reduced photolytic interferences than have been possible with previous systems based upon Nd:YAG pumping.

  10. The Haber Process Made Efficient by Hydroxylated Graphene


    Chaban, Vitaly; Prezhdo, Oleg


    The Haber-Bosch process is the main industrial method for producing ammonia from diatomic nitrogen and hydrogen. Very demanding energetically, it uses an iron catalyst, and requires high temperature and pressure. Any improvement of the Haber process will have an extreme scientific and economic impact. We report a significant increase of ammonia production using hydroxylated graphene. Exploiting the polarity difference between N2/H2 and NH3, as well as the universal proton acceptor behavior of...

  11. Chemistry of azopyrimidines. Part IV¦. Aromatic hydroxylation in ...

    Indian Academy of Sciences (India)

    A single Pd-Cl stretch at 360 cm-1 supports the composition of phenolato complex. Unlike Pd(aapm)Cl2 the hydroxylated product, Pd(aapmO)Cl, has a structured intense absorption in the visible region near 670 nm. The Pd-Cl bond in Pd(aapmO)Cl is highly sensitive to nucleophilic substitution and slowly hydrolyses in ...

  12. Polydopamine Generates Hydroxyl Free Radicals under Ultraviolet-Light Illumination. (United States)

    Wang, Zehuan; Tang, Feng; Fan, Hailong; Wang, Le; Jin, Zhaoxia


    Polydopamine (PDA) generally demonstrates as an efficient free-radical scavenger. However, its free-radical chemistry under illumination is unclear, which becomes important in view of growing studies of polydopamine applications in photoprotector and photothermal therapy. In this study, for the first time, we reported an experimental investigation of the generation of hydroxyl free radicals from ultraviolet (UV)-illuminated polydopamine in an aqueous environment. By using terephthalic acid as fluorescent probe, we measured hydroxyl radicals generated from UV-illuminated polydopamine with different shapes and sizes. The morphology of PDA shows significant influence on its productions of hydroxyl free radicals. Through characterizations of UV-vis absorption spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectrometry, mass spectrometry, and thermogravimetric analysis, we demonstrated the change of PDA nanomaterials brought by UV-light illumination in composition and thermal stability. We proposed a tentative mechanism for interpreting the relationship between morphology and photostability of PDA nanomaterials. These results reveal underlying complexity of polydopamine chemistry under light illumination that will deepen our understanding and benefit its further application.

  13. Synthesis and properties evaluation of sulfobetaine surfactant with double hydroxyl (United States)

    Zhou, Ming; Luo, Gang; Zhang, Ze; Li, Sisi; Wang, Chengwen


    A series of sulfobetaine surfactants {N-[(3-alkoxy-2-hydroxyl)propoxy] ethyl-N,N-dimethyl-N-(2-hydroxyl)propyl sulfonate} ammonium chloride were synthesized with raw materials containing linear saturated alcohol, N,N-dimethylethanolamine, sodium 3-chloro-2-hydroxyl propane sulfonic acid and epichlorohydrin. The molecule structures of sulfobetaine surfactants were characterized by FTIR, 1HNMR and elemental analysis. Surface tension measurements can provide us information about the surface tension at the CMC (γCMC), pC20, Γmax and Amin. The pC20 values of sulfobetaine surfactants increase with the hydrophobic chain length increasing. Amin values of the surfactants decrease with increasing hydrophobic chain length from 10 to 14. The critical micelle concentration (CMC) and surface tension (γCMC) values of the sulfobetaine surfactants decrease with increasing hydrophobic chain length from 10 to 16. The lipophilicity of surfactant was enhanced with the increase of the carbon chain, however, the ability of anti-hard water was weakened. The minimum oil/water interfacial tension of four kinds of sulfobetaine surfactants is 10-2-10-3 mN/m magnitude, which indicates that the synthesized bis-hydroxy sulfobetaine surfactants have a great ability to reduce interfacial tension in the surfactant flooding system. The surface tension (γCMC) values of synthesized surfactants were lower compared with conventional anionic surfactant sodium dodecyl sulfonate.

  14. Tyrosine Hydroxylation in Betalain Pigment Biosynthesis Is Performed by Cytochrome P450 Enzymes in Beets (Beta vulgaris.

    Directory of Open Access Journals (Sweden)

    Rasika Sunnadeniya

    Full Text Available Yellow and red-violet betalain plant pigments are restricted to several families in the order Caryophyllales, where betacyanins play analogous biological roles to anthocyanins. The initial step in betalain biosynthesis is the hydroxylation of tyrosine to form L-DOPA. Using gene expression experiments in beets, yeast, and Arabidopsis, along with HPLC/MS analysis, the present study shows that two novel cytochrome P450 (CYP450 enzymes, CYP76AD6 and CYP76AD5, and the previously described CYP76AD1 can perform this initial step. Co-expressing these CYP450s with DOPA 4,5-dioxygenase in yeast, and overexpression of these CYP450s in yellow beets show that CYP76AD1 efficiently uses L-DOPA leading to red betacyanins while CYP76AD6 and CYP76AD5 lack this activity. Furthermore, CYP76AD1 can complement yellow beetroots to red while CYP76AD6 and CYP76AD5 cannot. Therefore CYP76AD1 uniquely performs the beet R locus function and beets appear to be genetically redundant for tyrosine hydroxylation. These new functional data and ancestral character state reconstructions indicate that tyrosine hydroxylation alone was the most likely ancestral function of the CYP76AD alpha and beta groups and the ability to convert L-DOPA to cyclo-DOPA evolved later in the alpha group.

  15. Silver coordination polymers for prevention of implant infection: thiol interaction, impact on respiratory chain enzymes, and hydroxyl radical induction. (United States)

    Gordon, Oliver; Vig Slenters, Tünde; Brunetto, Priscilla S; Villaruz, Amer E; Sturdevant, Daniel E; Otto, Michael; Landmann, Regine; Fromm, Katharina M


    Prosthetic joint replacements are used increasingly to alleviate pain and improve mobility of the progressively older and more obese population. Implant infection occurs in about 5% of patients and entails significant morbidity and high social costs. It is most often caused by staphylococci, which are introduced perioperatively. They are a source of prolonged seeding and difficult to treat due to antibiotic resistance; therefore, infection prevention by prosthesis coating with nonantibiotic-type anti-infective substances is indicated. A renewed interest in topically used silver has fostered development of silver nanoparticles, which, however, present a potential health hazard. Here we present new silver coordination polymer networks with tailored physical and chemical properties as nanostructured coatings on metallic implant substrates. These compounds exhibited strong biofilm sugar-independent bactericidal activity on in vitro-grown biofilms and prevented murine Staphylococcus epidermidis implant infection in vivo with slow release of silver ions and limited transient leukocyte cytotoxicity. Furthermore, we describe the biochemical and molecular mechanisms of silver ion action by gene screening and by targeting cell metabolism of S. epidermidis at different levels. We demonstrate that silver ions inactivate enzymes by binding sulfhydryl (thiol) groups in amino acids and promote the release of iron with subsequent hydroxyl radical formation by an indirect mechanism likely mediated by reactive oxygen species. This is the first report investigating the global metabolic effects of silver in the context of a therapeutic application. We anticipate that the compounds presented here open a new treatment field with a high medical impact.

  16. PATRIMONIAL INTEGRITY, PERPETUITY, MEMORY. THE CONTRADICTIONS OF ENTAILED ESTATES IN EARLY MODERN VALENCIA Integridad patrimonial, perpetuidad, memoria. Contradicciones de los mayorazgos valencianos en la época moderna

    Directory of Open Access Journals (Sweden)

    Jorge Antonio Catalá Sanz


    Full Text Available The practice of entail, a key source of stability for the patrimony of thenobility over the centuries, nonetheless created its own contradictions. Several of thesearose, in the case of Valencia, from the normative changes that followed the decrees ofthe Nueva Planta, due to the differences between Castilian law and the abolished Valencian fueros. But many other contradictions resulted from the inconsistent regulation ofentail under the fueros; from debates over the law; from the sometimes confused stipulations of the founders; and even from uncertainty over the purpose of the entailedproperties. This article, drawing on disputes over entailed estates brought before theAudiencia of Valencia, will analyze problems including ambiguity in terminology; the contention between primogeniture and appeals for plural inheritance; the difficultyin defining the established order of succession; the incompatibility question; the extinction of inheritance for lack of descendants; the acceptance of illegitimate children and clerics;previously arranged disinheritance; the extension of the encumbrance in perpetuity; therecognition of real rights against entailed properties; and the alienation of parts of entailedestates under certain circumstances.Cimiento fundamental de la estabilidad patrimonial de la nobleza a través de los siglos, el mayorazgo generaba, no obstante, sus propias contradicciones. Algunas de ellas traían origen, en el caso valenciano, de los cambios normativos que siguieron a los decretos de Nueva Planta, al diferir en la determinación de ciertos aspectos las leyesde Castilla de los fueros abolidos. Pero otras muchas se derivaban de la escasa regulación foral en la materia, de las dudas de la doctrina, de las disposiciones, en ocasiones confusas, de los fundadores, e incluso de los mismos fines a que servía la propiedad vinculada. Apartir del estudio de los pleitos sobre posesión de vínculos sustanciados ante la Audiencia de Valencia se

  17. Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting

    Energy Technology Data Exchange (ETDEWEB)

    J Kiselar; M Chance


    Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposure of proteins to a 'white' X-ray beam for milliseconds provides sufficient oxidative modification to surface amino acid side chains, which can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular subdomains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review, we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that the selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal-to-noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis

  18. Short-interval leg movements during sleep entail greater cardiac activation than periodic leg movements during sleep in restless legs syndrome patients. (United States)

    Ferri, Raffaele; Rundo, Francesco; Silvani, Alessandro; Zucconi, Marco; Aricò, Debora; Bruni, Oliviero; Lanuzza, Bartolo; Ferini-Strambi, Luigi; Manconi, Mauro


    Periodic leg movements during sleep (PLMS) are sequences of ≥4 motor events with intermovement intervals (IMI) of 10-90 s. PLMS are a supportive diagnostic criterion for restless legs syndrome (RLS) and entail cardiac activation, particularly when associated with arousal. RLS patients also over-express short-interval leg movements during sleep (SILMS), which have IMI sleep. We assessed cardiac activation based on the R-R interval decrease with respect to baseline during NREM sleep without leg movements. We found that the duration of the R-R interval decrease with SILMS doublets was significantly longer than that with PLMS, whereas the maximal decrease in R-R interval was similar. Scoring SILMS in RLS patients may therefore be relevant from a cardiac autonomic perspective. © 2017 European Sleep Research Society.

  19. Tunable photoluminescence and spectrum split from fluorinated to hydroxylated graphene (United States)

    Gong, Peiwei; Wang, Jinqing; Sun, Weiming; Wu, Di; Wang, Zhaofeng; Fan, Zengjie; Wang, Honggang; Han, Xiuxun; Yang, Shengrong


    Tunable control over the functionalization of graphene is significantly important to manipulate its structure and optoelectronic properties. Yet the chemical inertness of this noble carbon material poses a particular challenge for its decoration without forcing reaction conditions. Here, a mild, operationally simple and controllable protocol is developed to synthesize hydroxylated graphene (HOG) from fluorinated graphene (FG). We successfully demonstrate that under designed alkali environment, fluorine atoms on graphene framework are programmably replaced by hydroxyl groups via a straightforward substitution reaction pathway. Element constituent analyses confirm that homogeneous C-O bonds are successfully grafted on graphene. Rather different from graphene oxide, the photoluminescence (PL) emission spectrum of the obtained HOG becomes split when excited with UV radiation. More interestingly, such transformation from FG facilitates highly tunable PL emission ranging from greenish white (0.343, 0.392) to deep blue (0.156, 0.094). Additionally, both experimental data and density function theory calculation indicate that the chemical functionalization induced structural rearrangement is more important than the chemical decoration itself in tuning the PL emission band tail and splitting energy gaps. This work not only presents a new way to effectively fabricate graphene derivatives with tunable PL performance, but also provides an enlightening insight into the PL origin of graphene related materials.Tunable control over the functionalization of graphene is significantly important to manipulate its structure and optoelectronic properties. Yet the chemical inertness of this noble carbon material poses a particular challenge for its decoration without forcing reaction conditions. Here, a mild, operationally simple and controllable protocol is developed to synthesize hydroxylated graphene (HOG) from fluorinated graphene (FG). We successfully demonstrate that under designed

  20. Modification of hydroxylated alumina and silica surfaces using sequential reactions with dimethylzinc and n-alkanethiols (United States)

    Boiadjiev, Vassil Iordanov


    This work demonstrates that it is possible to grow thin organic films chemically bound to hydroxylated alumina and silica surfaces by sequential adsorption of trimethylaluminum (TMA) and alcohols, and dimethylzinc and n-alkanethiols, at room temperature. The presence of the resulting alkoxide and thiolate species is demonstrated using infrared spectroscopy and, in the case of thiolates on silica, by nuclear magnetic resonance spectroscopy. The similarity between the reaction on high-surface area alumina and silica, and on planar surfaces allows the surface species to be identified in vacuo prior to attempting self-assembly on planar surfaces. Almost identical results obtained from chemical vapor deposition in vacuo and from sequential reaction in benzene solutions allow chemical grafting of low-vapor pressure, long-chain n-alkanethiols to the dimethylzinc-modified hydroxylated surfaces from solution. This is first studied on high-surface area silica substrates and then expanded to self-assembly on planar hydroxylated silicon substrate. The major reaction pathway for formation and thermal decomposition of aluminum alkoxide and Zn-bound ethanethiolate surface species on alumina and silica substrates is proposed based on the experimental results. It is suggested that initial adsorption of methanol on TMA-modified alumina covered by Al(CH3)2(ads), rapidly replaces a methyl by methoxy species at room temperature. Further reaction of methanol at ˜400 K replaces the second methyl species leading to Al(OCH3)2(ads) . This thermally decomposes on heating to yield primarily dimethyl ether and surface formate species. It is also very reactive with water and rapidly forms adsorbed alumina and methanol. Dimethylzinc reacts with hydroxylated alumina and silica at room temperature to form adsorbed monomethylzinc surface species and evolve methane. Temperature dependent studies reveal that these species are stable at room temperature and gradually decompose in vacuo. Adsorbed

  1. Influence of hydroxyl substitution on flavanone antioxidants properties. (United States)

    Masek, Anna; Chrzescijanska, Ewa; Latos, Malgorzata; Zaborski, Marian


    The aim of our study was to determine the effect of the position of the hydroxyl group on the antioxidant properties of flavonoid derivatives. For this purpose, we performed electrochemical analysis and quantum-mechanical calculations to describe the mechanisms of electrochemical oxidation, and we selected the two methods of ABTS (2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) and DPPH (2,2-diphenyl-1-picryl-hydrazyl-hydrate), which allowed us to determine the ability to scavenge free radicals. On the basis of the research, we found that the derivatives of flavonoids, which have a hydroxyl group substituted at the R-3 position on the C ring, have outstanding antioxidant activity. Flavone, which had an OH group substituted at the R-6 and R-7 position on the ring A, showed similar antioxidant activity to flavone without -OH groups in the structure and slightly higher activity than the di-substituted flavone on the ring A. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Direct Hydroxylation of Benzene to Phenol over TS-1 Catalysts

    Directory of Open Access Journals (Sweden)

    Yuecheng Luo


    Full Text Available We synthesized a TS-1 catalyst to directly hydroxylate benzene to phenol with H2O2 as oxidant and water as solvent. The samples were characterized by FT-IR (Fourier Transform Infrared, DR UV-Vis (Diffused Reflectance Ultraviolet Visible, XRD (X-ray diffraction, SEM(scanning electron microscope, TEM (Transmission Electron Microscope, XPS (X-ray photoelectron spectroscopy, ICP (inductively coupled plasma spectrum, and N2 adsorption-desorption. A desirable phenol yield of 39% with 72% selectivity was obtained under optimized conditions: 0.15 g (0.34 to the mass of benzene TS-1, 5.6 mmol C6H6, reaction time 45 min, 0.80 mL H2O2 (30%, 40.0 mL H2O, and reaction temperature 70 °C. The reuse of the TS-1 catalyst illustrated that the catalyst had a slight loss of activity resulting from slight Ti leaching from the first run and then kept stable. Almost all of the Ti species added in the preparation were successfully incorporated into the TS-1 framework, which were responsible for the good catalytic activity. Extraframework Ti species were not selective for hydroxylation.

  3. Aminosilane micropatterns on hydroxyl-terminated substrates: fabrication and applications. (United States)

    Li, Hai; Zhang, Juan; Zhou, Xiaozhu; Lu, Gang; Yin, Zongyou; Li, Gongping; Wu, Tom; Boey, Freddy; Venkatraman, Subbu S; Zhang, Hua


    The technique to pattern aminosilanes on hydroxyl-terminated substrates will open up extensive applications in many fields. There are some existing methods to pattern aminosilanes, in particular, (3-aminopropyl)triethoxysilane (APTES) on SiO(2) and glass substrates through indirect routes. However, few reports focus on the direct patterning of APTES by microcontact printing (microCP), due to the volatility of "inks" which consist of APTES and organic solvents. This report shows that high-quality APTES patterns on hydroxyl-terminated substrates can be directly obtained by microCP using an APTES aqueous solution as "ink". Gold nanoparticles (Au NPs) have been used to verify the presence and quality of APTES patterns on which they are selectively adsorbed. Thus-obtained Au NP patterns can serve as templates for the growth of ZnO nanostructures. Lectins are also successfully immobilized on the APTES patterns, with glutaraldehyde as linker. We believe that our method will serve as a general approach and find a wide range of applications in the fabrication of patterns and devices.

  4. Role of the hydroxyl radical in soot formation (United States)

    King, Galen B.; Laurendeau, Normand M.


    The goal of this project is to determine the role of the hydroxyl radical during formation of soot. Correlations will be sought between OH concentration and (1) the critical equivalence ratio for incipient soot formation and (2) soot yield as a function of higher equivalence ratios. The ultimate aim is the development of a quasi-global kinetic model for the pre-particulate chemistry leading to soot nucleation. Hydroxyl radical concentration profiles are measured directly in both laminar premixed and diffusion flames using the newly developed technique, laser saturated fluorescence (LSF). This method is capable of measuring OH in the presence of soot particles. Aliphatic and aromatic fuels will be used to assess the influence of fuel type on soot formation. The influence of flame temperature on the critical equivalence ratio and soot yield will be related to changes in the OH concentration profiles. LSF measurements will be augmented with auxiliary measurements of soot and PAH concentrations to allow the development of a quasi-global model for soot formation.

  5. The Haber Process Made Efficient by Hydroxylated Graphene

    CERN Document Server

    Chaban, Vitaly


    The Haber-Bosch process is the main industrial method for producing ammonia from diatomic nitrogen and hydrogen. Very demanding energetically, it uses an iron catalyst, and requires high temperature and pressure. Any improvement of the Haber process will have an extreme scientific and economic impact. We report a significant increase of ammonia production using hydroxylated graphene. Exploiting the polarity difference between N2/H2 and NH3, as well as the universal proton acceptor behavior of NH3, we demonstrate a strong shift of the equilibrium of the Haber-Bosch process towards ammonia. Hydroxylated graphene provides the polar environment favoring the forward reaction, and remain stable under the investigated thermodynamic conditions. Ca. 50 kJ mol-1 enthalpy gain and ca. 60-70 kJ mol-1 free energy gain are achieved at 298-1300 K and 1-1000 bar, strongly shifting the reaction equilibrium towards the product. A clear microscopic interpretation of the observed phenomenon is given using electronic structure ca...

  6. Consequences of IkappaB alpha hydroxylation by the factor inhibiting HIF (FIH). (United States)

    Devries, Ingrid L; Hampton-Smith, Rachel J; Mulvihill, Melinda M; Alverdi, Vera; Peet, Daniel J; Komives, Elizabeth A


    The factor inhibiting HIF-1 (FIH-1) hydroxylates many ankyrin repeat-containing proteins including IκBα. It is widely speculated that hydroxylation of IκBα has functional consequences, but the effects of hydroxylation have not been demonstrated. We prepared hydroxylated IκBα and compared it to the unhydroxylated protein. Urea denaturation and amide H/D exchange experiments showed no change in the "foldedness" upon hydroxylation. Surface plasmon resonance measurements of binding to NFκB showed no difference in the NFκB binding kinetics or thermodynamics. Ubiquitin-independent proteasomal degradation experiments showed no difference in the half-life of the protein. Thus, it appears that hydroxylation of IκBα by FIH-1 is inconsequential, at least for the functions we could assay in vitro. Copyright © 2010 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  7. Temperature and hydroxyl concentration dependences of diffusion coefficients of hydroxyl groups in vitreous silica at temperatures of 850–1200 °C (United States)

    Kuzuu, Nobu; Sato, Naoya; Arakawa, Yu; Horikoshi, Hideharu; Horii, Naohiro


    The hydroxyl concentration and temperature dependences of the diffusion coefficients of hydroxyl groups in vitreous silica were investigated by analyzing the change in the hydroxyl concentration distribution caused by heat treatment around the binding interface between silica glass plates with different hydroxyl concentrations. We confirmed experimentally that the diffusion coefficient is proportional to the hydroxyl concentration, which had been predicted theoretically, and obtained the empirical formula D(c OH) = [(4.9 ± 1.0) × 10‑14 m2/s·wt ppm] × exp[‑(8.1 ± 0.3) × 103 K/T] c OH with the hydroxyl concentration c OH and the absolute temperature T, which is valid at least in the temperature range of 850–1200 °C. Using the values calculated using this formula, we can reproduce the hydroxyl concentration profile after diffusion from a silica glass surface induced by heating in a water vapor atmosphere in the literature, which supports the validity of the empirical formula obtained in this study. The relationship between the effective diffusion coefficient in the literature and our result is discussed.

  8. Development of a reaxff reactive force field for silicon/oxygen/hydrogen/fluoride interactions and applications to hydroxylation and friction (United States)

    Yeon, Jejoon

    Molecular dynamics (MD) simulations with the ReaxFF reactive force field were carried out to find the atomistic mechanisms for tribo-chemical reactions occurring at the sliding interface of fully-hydroxylated amorphous silica and oxidized silicon as a function of interfacial water amount. The ReaxFF-MD simulations showed a significant amount of mass transfer across the interface occurs during the sliding. In the absence of water molecules, the interfacial mixing was initiated by dehydroxylation followed by the Si-O-Si bond formation bridging two solid surfaces. In the presence of sub-monolayer thick water, the dissociation of water molecules can provide additional reaction pathways to form the Si-O-Si bridge bonds and mass transfers across the interface. However, when the amount of interfacial water molecules was large enough to form full monolayer, the degree of mass transfer was substantially reduced since the silicon atoms at the sliding interface were terminated with hydroxyl groups rather than forming interfacial Si-O-Si bridge bonds. The ReaxFF-MD simulations clearly showed the role of water molecules in atomic scale mechano-chemical processes during the sliding and provided physical insights into tribochemical wear processes of silicon oxide surfaces observed experimentally. In addition to this, we performed reactive force field molecular dynamics simulation to observe the hydrolysis reactions between water molecules and locally strained SiO2 geometries. We improved the Si/O/H force field from Fogarty et al.1, to more accurately describe the hydroxylation reaction barrier for strained and non-strained Si-O structures, which are about 20 kcal/mol and 30 kcal/mol, respectively. After optimization, energy barrier for the hydroxylation shows a good agreement with DFT data. The observation of silanol formation at the high-strain region of a silica nano-rod also supports the concept that the adsorption of water molecule: hydroxyl formation favors the geometry with

  9. New hydroxylated metabolites of 4-monochlorobiphenyl in whole poplar plants

    Directory of Open Access Journals (Sweden)

    Zhai Guangshu


    Full Text Available Abstract Two new monohydroxy metabolites of 4-monochlorobiphenyl (CB3 were positively identified using three newly synthesized monohydroxy compounds of CB3: 2-hydroxy-4-chlorobiphenyl (2OH-CB3, 3-hydroxy-4-chlorobiphenyl (3OH-CB3 and 4-hydroxy-3-chlorobiphenyl (4OH-CB2. New metabolites of CB3, including 2OH-CB3 and 3OH-CB3, were confirmed in whole poplars (Populus deltoides × nigra, DN34, a model plant in the application of phytoremediation. Furthermore, the concentrations and masses of 2OH-CB3 and 3OH-CB3 formed in various tissues of whole poplar plants and controls were measured. Results showed that 2OH-CB3 was the major product in these two OH-CB3s with chlorine and hydroxyl moieties in the same phenyl ring of CB3. Masses of 2OH-CB3 and 3OH-CB3 in tissues of whole poplar plants were much higher than those in the hydroponic solution, strongly indicating that the poplar plant itself metabolizes CB3 to both 2OH-CB3 and 3OH-CB3. The total yield of 2OH-CB3 and 3OH-CB3, with chlorine and hydroxyl in the same phenyl ring of CB3, was less than that of three previously found OH-CB3s with chlorine and hydroxyl in the opposite phenyl rings of CB3 (2'OH-CB3, 3'OH-CB3, and 4'OH-CB3. Finally, these two newly detected OH-CB3s from CB3 in this work also suggests that the metabolic pathway was via epoxide intermediates. These five OH-CB3s clearly showed the complete metabolism profile from CB3 to monohydroxylated CB3. More importantly, it's the first report and confirmation of 2OH-CB3 and 3OH-CB3 (new metabolites of CB3 in a living organism.

  10. Self-hydroxylation of the splicing factor lysyl hydroxylase, JMJD6

    DEFF Research Database (Denmark)

    Mantri, M.; Webby, C.J.; Loik, N.D.


    The lysyl 5S-hydroxylase, JMJD6 acts on proteins involved in RNA splicing. We find that in the absence of substrate JMJD6 catalyses turnover of 2OG to succinate. H-NMR analyses demonstrate that consumption of 2OG is coupled to succinate formation. MS analyses reveal that JMJD6 undergoes self......-hydroxylation in the presence of Fe(ii) and 2OG resulting in production of 5S-hydroxylysine residues. JMJD6 in human cells is also found to be hydroxylated. Self-hydroxylation of JMJD6 may play a regulatory role in modulating the hydroxylation status of proteins involved in RNA splicing. This journal is...

  11. Oxidation of carboxylic acids regenerates hydroxyl radicals in the unpolluted and nighttime troposphere. (United States)

    da Silva, Gabriel


    The hydroxyl radical (OH) controls the removal of organic compounds from the troposphere. Atmospheric chemistry models significantly under-predict OH levels in unpolluted environments, implying that they are regenerated via some unknown mechanism(s). This work uses computational chemistry to demonstrate that the photochemical oxidation of alkyl carboxylic acids can efficiently regenerate the hydroxyl radical via unimolecular decomposition of alpha-carboxyalkylperoxy radicals. For acetic acid and propanoic acid the proposed mechanism is predicted to dominate in the unpolluted lower troposphere, and it may also operate to some extent in the mid to upper troposphere. Alkyl carboxylic acids are also predicted to act as a new source of nighttime OH throughout the planetary boundary layer, where OH levels are also under-predicted. The thermodynamic requirements for reactions of this class are discussed, and some candidate OH-reforming molecules particularly relevant to aromatic photooxidation are identified. Adopting a broader perspective, the alpha-carboxyalkyl radical precursors that react with O(2) to form the unstable alpha-carboxyalkylperoxy type radicals are also expected to form during combustion, in the interstellar medium, and from the gamma-irradiation of glycine and related amino acids, and the potential importance of this new chemistry in these environments is discussed. Master equation simulations suggest that alpha-carboxyalkyl + O(2) reactions provide a prompt OH source during the autoignition and combustion of biodiesel and other oxygenated biofuels, where carboxylic acids are formed as early stage oxidation products. Ketene combustion is also thought to proceed via these OH-reforming alpha-carboxyalkyl radicals. The in vivo formation of alpha-carboxyalkylperoxy radicals followed by oxidation to the highly reactive OH radical may induce oxidative stress in the human body, in a process initiated by gamma-rays. Finally, the reaction of ketenes with OH to

  12. Regioselective hydroxylation of cholecalciferol, cholesterol and other sterol derivatives by steroid C25 dehydrogenase. (United States)

    Rugor, A; Tataruch, M; Staroń, J; Dudzik, A; Niedzialkowska, E; Nowak, P; Hogendorf, A; Michalik-Zym, A; Napruszewska, D B; Jarzębski, A; Szymańska, K; Białas, W; Szaleniec, M


    Steroid C25 dehydrogenase (S25DH) from Sterolibacterium denitrificans Chol-1S is a molybdenum oxidoreductase belonging to the so-called ethylbenzene dehydrogenase (EBDH)-like subclass of DMSO reductases capable of the regioselective hydroxylation of cholesterol or cholecalciferol to 25-hydroxy products. Both products are important biologically active molecules: 25-hydroxycholesterol is responsible for a complex regulatory function in the immunological system, while 25-hydroxycholecalciferol (calcifediol) is the activated form of vitamin D3 used in the treatment of rickets and other calcium disorders. Studies revealed that the optimal enzymatic synthesis proceeds in fed-batch reactors under anaerobic conditions, with 6-9 % (w/v) 2-hydroxypropyl-β-cyclodextrin as a solubilizer and 1.25-5 % (v/v) 2-methoxyethanol as an organic co-solvent, both adjusted to the substrate type, and 8-15 mM K3[Fe(CN)6] as an electron acceptor. Such thorough optimization of the reaction conditions resulted in high product concentrations: 0.8 g/L for 25-hydroxycholesterol, 1.4 g/L for calcifediol and 2.2 g/L for 25-hydroxy-3-ketosterols. Although the purification protocol yields approximately 2.3 mg of pure S25DH from 30 g of wet cell mass (specific activity of 14 nmol min-1 mg-1), the non-purified crude extract or enzyme preparation can be readily used for the regioselective hydroxylation of both cholesterol and cholecalciferol. On the other hand, pure S25DH can be efficiently immobilized either on powder or a monolithic silica support functionalized with an organic linker providing NH2 groups for enzyme covalent binding. Although such immobilization reduced the enzyme initial activity more than twofold it extended S25DH catalytic lifetime under working conditions at least 3.5 times.

  13. Spectroscopic study of combustion diagnostics on hydroxyl radicals (United States)

    Hung, R. J.


    Experimental observations of propane-air flames were performed. Measurements of hydroxyl (OH) radical concentration were made using resonance line absorption techniques. A microwave-pumped low pressure discharge in argon and water vapor is employed to produce strong OH radical band radiation in the 308 nm region. This radiation is transmitted through the plume and absorption data are taken at various radical positions using an optical multichannel analyzer. This absorption data is used to compute OH number density using a model for the absorption band characteristics as a function of temperature based on an atlas of line strengths. A numerical computation of flow fields, temperature profile and OH number density is carried out by using a technique of computational fluid dynamics (CFD). The results of CFD computation are good compared with experimental observation with a good agreement.

  14. Spectroscopy and reaction dynamics of collision complexes containing hydroxyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lester, M.I. [Univ. of Pennsylvania, Philadelphia (United States)


    The DOE supported work in this laboratory has focused on the spectroscopic characterization of the interaction potential between an argon atom and a hydroxyl radical in the ground X{sup 2}II and excited A {sup 2}{summation}{sup +} electronic states. The OH-Ar system has proven to be a test case for examining the interaction potential in an open-shell system since it is amenable to experimental investigation and theoretically tractable from first principles. Experimental identification of the bound states supported by the Ar + OH (X {sup 2}II) and Ar + OH(A {sup 2}{summation}{sup +}) potentials makes it feasible to derive realistic potential energy surfaces for these systems. The experimentally derived intermolecular potentials provide a rigorous test of ab initio theory and a basis for understanding the dramatically different collision dynamics taking place on the ground and excited electronic state surfaces.

  15. Further Highly Hydroxylated Steroids from the Vietnamese Starfish Archaster typicus. (United States)

    Hanh, Tran Thi Hong; Vien, Le Thi; Vinh, Le Ba; Thanh, Nguyen Van; Cuong, Nguyen Xuan; Nam, Nguyen Hoai; Thung, Do Cong; Kiem, Phan Van; Minh, Chau Van


    Eight highly hydroxylated steroids (1-8), including three new compounds as sodium salts of (24S)-5α-cholestane-3β,4β,5,6α,7β,8,14,15α,24-nonaol 6-sulfate (1), (24E)-5α-cholest-24-ene-26-yde-3β,6α,8,14,15α-pentaol 15-sulfate (2), and 5α-cholest-3β,6α,8,14,15α,24,25,26-octaol 15-sulfate (3), were isolated and elucidated from the methanol extract of the Vietnamese starfish Archaster typicus. The structure elucidation was done by spectroscopic methods including one and two dimensional (1D-, 2D-)NMR and Fourier transform ion cyclotron resonance (FT-ICR)-MS. The isolated compounds can be used as chemical markers for taxonomic identification of the starfish A. typicus.

  16. Effective L-Tyrosine Hydroxylation by Native and Immobilized Tyrosinase. (United States)

    Cieńska, Małgorzata; Labus, Karolina; Lewańczuk, Marcin; Koźlecki, Tomasz; Liesiene, Jolanta; Bryjak, Jolanta


    Hydroxylation of L-tyrosine to 3,4-dihydroxyphenylalanine (L-DOPA) by immobilized tyrosinase in the presence of ascorbic acid (AH2), which reduces DOPA-quinone to L-DOPA, is characterized by low reaction yields that are mainly caused by the suicide inactivation of tyrosinase by L-DOPA and AH2. The main aim of this work was to compare processes with native and immobilized tyrosinase to identify the conditions that limit suicide inactivation and produce substrate conversions to L-DOPA of above 50% using HPLC analysis. It was shown that immobilized tyrosinase does not suffer from partitioning and diffusion effects, allowing a direct comparison of the reactions performed with both forms of the enzyme. In typical processes, additional aeration was applied and boron ions to produce the L-DOPA and AH2 complex and hydroxylamine to close the cycle of enzyme active center transformations. It was shown that the commonly used pH 9 buffer increased enzyme stability, with concomitant reduced reactivity of 76%, and that under these conditions, the maximal substrate conversion was approximately 25 (native) to 30% (immobilized enzyme). To increase reaction yield, the pH of the reaction mixture was reduced to 8 and 7, producing L-DOPA yields of approximately 95% (native enzyme) and 70% (immobilized). A three-fold increase in the bound enzyme load achieved 95% conversion in two successive runs, but in the third one, tyrosinase lost its activity due to strong suicide inactivation caused by L-DOPA processing. In this case, the cost of the immobilized enzyme preparation is not overcome by its reuse over time, and native tyrosinase may be more economically feasible for a single use in L-DOPA production. The practical importance of the obtained results is that highly efficient hydroxylation of monophenols by tyrosinase can be obtained by selecting the proper reaction pH and is a compromise between complexation and enzyme reactivity.

  17. Effective L-Tyrosine Hydroxylation by Native and Immobilized Tyrosinase.

    Directory of Open Access Journals (Sweden)

    Małgorzata Cieńska

    Full Text Available Hydroxylation of L-tyrosine to 3,4-dihydroxyphenylalanine (L-DOPA by immobilized tyrosinase in the presence of ascorbic acid (AH2, which reduces DOPA-quinone to L-DOPA, is characterized by low reaction yields that are mainly caused by the suicide inactivation of tyrosinase by L-DOPA and AH2. The main aim of this work was to compare processes with native and immobilized tyrosinase to identify the conditions that limit suicide inactivation and produce substrate conversions to L-DOPA of above 50% using HPLC analysis. It was shown that immobilized tyrosinase does not suffer from partitioning and diffusion effects, allowing a direct comparison of the reactions performed with both forms of the enzyme. In typical processes, additional aeration was applied and boron ions to produce the L-DOPA and AH2 complex and hydroxylamine to close the cycle of enzyme active center transformations. It was shown that the commonly used pH 9 buffer increased enzyme stability, with concomitant reduced reactivity of 76%, and that under these conditions, the maximal substrate conversion was approximately 25 (native to 30% (immobilized enzyme. To increase reaction yield, the pH of the reaction mixture was reduced to 8 and 7, producing L-DOPA yields of approximately 95% (native enzyme and 70% (immobilized. A three-fold increase in the bound enzyme load achieved 95% conversion in two successive runs, but in the third one, tyrosinase lost its activity due to strong suicide inactivation caused by L-DOPA processing. In this case, the cost of the immobilized enzyme preparation is not overcome by its reuse over time, and native tyrosinase may be more economically feasible for a single use in L-DOPA production. The practical importance of the obtained results is that highly efficient hydroxylation of monophenols by tyrosinase can be obtained by selecting the proper reaction pH and is a compromise between complexation and enzyme reactivity.

  18. Hydroxyl radical yields from reactions of terpene mixtures with ozone. (United States)

    Forester, C D; Wells, J R


    Chamber studies were conducted to quantify hydroxyl radical (OH·) yields and to determine whether water vapor affected OH· formation in the reactions of ozone (O(3)) with a single terpene, two-component terpene mixtures, and a commercial pine oil cleaning product (POC). Solid-phase microextraction fibers (SPME) were used for sampling the terpenes and the 2-butanone formation from the hydroxyl reaction with 2-butanol as a measure of OH· yields. Analyses were performed using gas chromatography with flame ionization detection. The individual terpenes' OH· yields from α-terpineol, limonene, and α-pinene were 64 ± 8%, 64 ± 6%, and 76 ± 6%, respectively. OH· yields were also measured from two-component mixtures of these terpenes. In each mixture that contained α-terpineol, the overall OH· yield was lower than the modeled OH· yields of the individual components that comprised the reaction mixture. Reactions of a commercial POC with O(3) were also studied to determine how the individual terpenes react in a complex mixture system, and an OH· formation yield of 51 ± 6% was measured. Relative humidity did not have a significant effect on the OH· formation in the mixtures studied here. The data presented here demonstrate that mixtures may react differently than the sum of their individual components. By investigating the chemistry of mixtures of chemicals in contrast to the chemistry of individual compounds, a better assessment can be made of the overall impact cleaning products have on indoor environments. © 2011 John Wiley & Sons A/S.

  19. Predicting tropospheric ozone and hydroxyl radical in a global, three-dimensional, chemistry, transport, and deposition model

    Energy Technology Data Exchange (ETDEWEB)

    Atherton, C.S.


    Two of the most important chemically reactive tropospheric gases are ozone (O{sub 3}) and the hydroxyl radical (OH). Although ozone in the stratosphere is a necessary protector against the sun`s radiation, tropospheric ozone is actually a pollutant which damages materials and vegetation, acts as a respiratory irritant, and is a greenhouse gas. One of the two main sources of ozone in the troposphere is photochemical production. The photochemistry is initiated when hydrocarbons and carbon monoxide (CO) react with nitrogen oxides (NO{sub x} = NO + NO{sub 2}) in the presence of sunlight. Reaction with the hydroxyl radical, OH, is the main sink for many tropospheric gases. The hydroxyl radical is highly reactive and has a lifetime on the order of seconds. Its formation is initiated by the photolysis of tropospheric ozone. Tropospheric chemistry involves a complex, non-linear set of chemical reactions between atmospheric species that vary substantially in time and space. To model these and other species on a global scale requires the use of a global, three-dimensional chemistry, transport, and deposition (CTD) model. In this work, I developed two such three dimensional CTD models. The first model incorporated the chemistry necessary to model tropospheric ozone production from the reactions of nitrogen oxides with carbon monoxide (CO) and methane (CH{sub 4}). The second also included longer-lived alkane species and the biogenic hydrocarbon isoprene, which is emitted by growing plants and trees. The models` ability to predict a number of key variables (including the concentration of O{sub 3}, OH, and other species) were evaluated. Then, several scenarios were simulated to understand the change in the chemistry of the troposphere since preindustrial times and the role of anthropogenic NO{sub x} on present day conditions.

  20. Modeling hydroxylated nanosilica: Testing the performance of ReaxFF and FFSiOH force fields (United States)

    Macià Escatllar, Antoni; Ugliengo, Piero; Bromley, Stefan T.


    We analyze the performance of the FFSiOH force field and two parameterisations of the ReaxFF force field for modeling hydroxylated nanoscale silica (SiO2). Such nanosystems are fundamental in numerous aspects of geochemistry and astrochemistry and also play a key role during the hydrothermal synthesis of technologically important nanoporous silicas (e.g., catalysts, absorbents, and coatings). We consider four aspects: structure, relative energies, vibrational spectra, and hydroxylation energies, and compare the results with those from density functional calculations employing a newly defined dataset (HND: Hydroxylated Nanosilica Dataset). The HND consists of three sets of (SiO2)16(H2O)N nanoparticles (NPs), each with a different degree of hydroxylation and each containing between 23 and 26 distinct isomers and conformers. We also make all HND reference data openly available. We further consider hydroxylated silica NPs of composition (SiO2)M(H2O)N with M = 4, 8, 16, and 24 and infinite surface slabs of amorphous silica, both with variable hydroxylation. For energetics, both ReaxFF and FFSiOH perform well for NPs with an intermediate degree of hydroxylation. For increased hydroxylation, the performance of FFSiOH begins to significantly decline. Conversely, for the lower degree of hydroxylation both parameterisations of ReaxFF do not perform well. For vibrational frequencies, FFSiOH performs particularly well and significantly better than ReaxFF. This feature also opens the door to inexpensively calculating Gibbs free energies of the hydroxylated nanosilica systems in order to efficiently correct density functional theory calculated electronic energies. We also show how some small changes to FFSiOH could improve its performance for higher degrees of hydroxylation.

  1. Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles (United States)

    Kaur, Jasmeet; Schoonen, Martin A.


    The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and

  2. Synthesis of some members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family. (United States)

    Padwa, Albert; Zhang, Hongjun


    The total synthesis of several members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family has been carried out. (+/-)-Lycoricidine and (+/-)-7-deoxypancratistatin were assembled through a one-pot Stille/intramolecular Diels-Alder cycloaddition cascade to construct the core skeleton. The initially formed [4+2]-cycloadduct undergoes nitrogen-assisted ring opening followed by a deprotonation/reprotonation of the resulting zwitterion to give a rearranged hexahydroindolinone on further heating at 160 degrees C. The stereochemical outcome of the IMDAF cycloaddition has the side arm of the tethered vinyl group oriented exo with respect to the oxygen bridge. The resulting cycloadduct was used for the stereocontrolled installation of the remaining functionality present in the C-ring of the target molecules. Key features of the synthetic strategy include (1) a lithium hydroxide induced tandem hydrolysis/decarboxylation/elimination sequence to introduce the required pi-bond in the C-ring of (+/-)-lycoricidine, and (2) conversion of the initially formed Diels-Alder adduct into an aldehyde intermediate which then undergoes a stereospecific decarbonylation reaction mediated by Wilkinson's catalyst to set the trans-B-C ring junction of (+/-)-7-deoxypancratistatin.

  3. Peroxidase Can Perform the Hydroxylation Step in the "oxidative Cascade" during Oxidation of Tea Catechins

    NARCIS (Netherlands)

    Verloop, Annewieke J.W.; Vincken, Jean Paul; Gruppen, Harry


    The formation of black tea thearubigins involves at least two of the following oxidation steps: (i) oligomerization, (ii) rearrangement, and (iii) hydroxylation. The first two are mainly catalyzed by polyphenol oxidase (PPO), whereas the enzyme responsible for hydroxylation has not yet been

  4. The effect of hydroxylation of linoleoyl amides on their cannabinomimetic properties

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Stelt, M. van der; Paoletti, A.M.; Maccarrone, M.; Nieuwenhuizen, W.F.; Bagetta, G.; Veldink, G.A.; Finazzi Agrò, A.


    As yet, the physiological significance of hydroxylation of anandamide and linoleoyl amides is unknown. Therefore, we investigated whether hydroxylation of ODNHEtOH and ODNH2 influences their binding abilities to the CB-1 receptor and whether it alters their reactivity towards a fatty acid amide

  5. Hydroxylation of the Herbicide Isoproturon by Fungi Isolated from Agricultural soil

    DEFF Research Database (Denmark)

    Rønhede, S.; Jensen, Bo; Rosendahl, Søren


    of these hydroxylated metabolites in soils treated with isoproturon. Isolates of Mortierella sp. strain Gr4, Phoma cf. eupyrena Gr61, and Alternaria sp. strain Gr174 hydroxylated isoproturon at the first position of the isopropyl side chain, yielding N-(4-(2-hydroxy-1-methylethyl)phenyl)-N',N'-dimethylurea, while Mucor...

  6. Mechanism of aromatic hydroxylation of lidocaine at a Pt electrode under acidic conditions

    NARCIS (Netherlands)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar P.


    Aromatic hydroxylation reactions, which are mainly catalyzed by cytochrome P450 (CYP) enzymes in vivo, are some of the most important reactions of Phase I metabolism, because insertion of a hydroxyl group into a lipophilic drug compound increases its hydrophilicity and prepares it for subsequent

  7. Solvent effects and improvements in the deoxyribose degradation assay for hydroxyl radical-scavenging. (United States)

    Li, Xican


    The deoxyribose degradation assay is widely used to evaluate the hydroxyl (OH) radical-scavenging ability of food or medicines. We compared the hydroxyl radical-scavenging activity of 25 antioxidant samples prepared in ethanol solution with samples prepared after removing the ethanol (residue). The data suggested that there was an approximately 9-fold difference between assay results for the ethanol solution and residue samples. This indicated a strong alcoholic interference. To further study the mechanism, the scavenging activities of 18 organic solvents (including ethanol) were measured by the deoxyribose assay. Most pure organic solvents (especially alcohols) could effectively scavenge hydroxyl radicals. As hydroxyl radicals have extremely high reactivities, they will quickly react with surrounding solvent molecules. This shows that any organic solvent should be completely evaporated before measurement. The proposed method is regarded as a reliable hydroxyl radical-scavenging assay, suitable for all types of antioxidants. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Cellulose based hybrid hydroxylated adducts for polyurethane foams (United States)

    De Pisapia, Laura; Verdolotti, Letizia; Di Mauro, Eduardo; Di Maio, Ernesto; Lavorgna, Marino; Iannace, Salvatore


    Hybrid flexible polyurethane foams (HPU) were synthesized by using a hybrid hydroxilated adduct (HHA) based on renewable resources. In particular the HHA was obtained by dispersing cellulose wastes in colloidal silica at room temperature, pressure and humidity. The colloidal silica was selected for its ability of modifying the cellulose structure, by inducing a certain "destructurization" of the crystalline phase, in order to allow cellulose to react with di-isocyanate for the final synthesis of the polyurethane foam. In fact, cellulose-polysilicate complexes are engaged in the reaction with the isocyanate groups. This study provides evidence of the effects of the colloidal silica on the cellulose structure, namely, a reduction of the microfiber cellulose diameter and the formation of hydrogen bonds between the polysilicate functional groups and the hydroxyl groups of the cellulose, as assessed by IR spectroscopy and solid state NMR. The HHA was added to a conventional polyol in different percentages (between 5 and 20%) to synthesize HPU in presence of catalysts, silicone surfactant and diphenylmethane diisocyanate (MDI). The mixture was expanded in a mold and cured for two hours at room temperature. Thermal analysis, optical microscopy and mechanical tests were performed on the foams. The results highlighted an improvement of thermal stability and a decrease of the cell size with respect neat polyurethane foam. Mechanical tests showed an improvement of the elastic modulus and of the damping properties with increasing HHA amount.

  9. An absolute calibration for gas-phase hydroxyl measurements. (United States)

    Hard, Thomas M; George, Linda A; O'Brien, Robert J


    We describe a new method of calibrating tropospheric hydroxyl (OH) instruments. Ozone-alkene mixtures produce steady-state OH radical concentrations. The steady state is governed by competition between OH production in the reaction of ozone with the alkene and OH removal by reactions with the alkene, ozone, and the reactor wall. In a flowtube reactor transporting an ozone-alkene mixture, the OH wall loss rate can be measured by varying the alkene concentration. Delivery of the reaction mixture to the sampling entry of an atmospheric OH measurement instrument provides an absolute calibration of the instrument's response to OH. The present precision of calibration is +/-8% (1-sigma), based on reproducibility over a wide range of ozone concentrations. The accuracy (+/-43%) is limited by uncertainties in kinetic rate coefficients and OH yield, which can be improved. The calibration requires no photon flux measurements or lamp-dependent absorption coefficients, which have inherent, variable, systematic uncertainties, and it has been tested in field experiments.

  10. Observational evidence for interhemispheric hydroxyl-radical parity. (United States)

    Patra, P K; Krol, M C; Montzka, S A; Arnold, T; Atlas, E L; Lintner, B R; Stephens, B B; Xiang, B; Elkins, J W; Fraser, P J; Ghosh, A; Hintsa, E J; Hurst, D F; Ishijima, K; Krummel, P B; Miller, B R; Miyazaki, K; Moore, F L; Mühle, J; O'Doherty, S; Prinn, R G; Steele, L P; Takigawa, M; Wang, H J; Weiss, R F; Wofsy, S C; Young, D


    The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7-10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004-2011 the model predicts an annual mean NH-SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.

  11. [Emission spectra of hydroxyl radical generated in air corona discharge]. (United States)

    Sun, Ming; Wu, Yan; Zhang, Jia-Liang; Li, Jie; Wang, Ning-Hui; Wu, Jiang; Shang, Ke-Feng


    In this paper, the relative emission intensity of the 309 nm transition band of hydroxyl radical (OH) was measured by a CCD imaging spectrometer in a pin-plane corona discharge scheme of one atmosphere pressure air injected with unsaturated water vapor from the central hole of the used pins. The influences of several factors on the OH radical production were investigated by relative emission intensity measurement. The production of OH radical increased with a limited increment of water vapor concentration in the mixed gas. Compared with positive DC corona discharges, more OH radicals were generated in positive pulsed corona discharges and less in negative DC corona discharges. The spatial distribution of OH radical production was also observed. Most OH radicals were produced within the range of 5 mm off the discharge pin electrode. In conclusion, this means of optical emission spectroscopy, compared with more sophisticated laser fluorescence measurements used for plasma OH production diagnostics investigation, is simpler and more effective for characterizing the OH radical potential for pollutant oxidation.

  12. Coumarin-fused coumarin: antioxidant story from N,N-dimethylamino and hydroxyl groups. (United States)

    Xi, Gao-Lei; Liu, Zai-Qun


    Two coumarin skeletons can form chromeno[3,4-c]chromene-6,7-dione by sharing with the C ═ C in lactone. The aim of the present work was to explore the antioxidant effectiveness of the coumarin-fused coumarin via six synthetic compounds containing hydroxyl and N,N-dimethylamino as the functional groups. The abilities to quench 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(+•)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical revealed that the rate constant for scavenging radicals was related to the amount of hydroxyl group in the scaffold of coumarin-fused coumarin. But coumarin-fused coumarin was able to inhibit DNA oxidations caused by (•)OH, Cu(2+)/glutathione (GSH), and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH) even in the absence of hydroxyl group. In particular, a hydroxyl and an N,N-dimethylamino group locating at different benzene rings increased the inhibitory effect of coumarin-fused coumarin on AAPH-induced oxidation of DNA about 3 times higher than a single hydroxyl group, whereas N,N-dimethylamino-substituted coumarin-fused coumarin possessed high activity toward (•)OH-induced oxidation of DNA without the hydroxyl group contained. Therefore, the hydroxyl group together with N,N-dimethylamino group may be a novel combination for the design of coumarin-fused heterocyclic antioxidants.

  13. Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence method. (United States)

    Hu, Yufei; Zhang, Zhujun; Yang, Chunyan


    Measurement methods for ultrasonic fields are important for reasons of safety. The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations. In this paper, a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence (CL) reaction of luminol-hydrogen peroxide (H2O2)-K5[Cu(HIO6)2](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H2O2. This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution. With flow injection (FI) technology, this novel CL reaction is sensitive enough to detect ultra trace amounts of H2O2 with a limit of detection (3sigma) of 4.1 x 10(-11) mol L(-1). The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied. The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power (measured by calculating the yield of hydroxyl radicals.

  14. Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same (United States)

    Rhein, R. A.; Ingham, J. D. (Inventor)


    Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

  15. Hydroxylation of steroids with 11 alpha-hydroxylase of Rhizopus nigricans. (United States)

    Zakelj-Mavric, M; Belic, I


    Three groups of 3-keto-4-ene steroids with different side chains were used as substrates for the induced 11 alpha-hydroxylase of Rhizopus nigricans. The highest total bioconversion as well as the highest yield of 11 alpha-hydroxylated product is found using progesterone as substrate. By changing the polarity of the side chain, much higher yields of 6 beta- and 7 beta-hydroxylated products relative to 11 alpha-hydroxylated product are obtained. Our results thus provide evidence for the importance of the side chain in steroid-enzyme interactions.

  16. Esophageal replacement by hydroxylated bacterial cellulose patch in a rabbit model. (United States)

    Zhu, Changlai; Liu, Fang; Qian, Wenbo; Wang, Yingjie; You, Qingsheng; Zhang, Tianyi; Li, Feng


    To repair esophageal defects by hydroxylated and kombucha-synthesized bacterial cellulose (HKBC) patch in a rabbit model. Semicircular esophageal defects 1 cm in length of the cervical esophagus were initially created in 18 Japanese big-ear rabbits and then repaired with HKBC patch grafts. The clinical outcomes including survival rate, weight change, food intake, and hematological and radiologic evaluation were observed. After X-ray evaluation, the rabbits were sacrificed sequentially at 1, 3, and 6 months for histopathologic analysis with light microscopy and scanning electron microscopy. Survival rate during the first month was 88.9% (n = 16). Two rabbits died from anastomotic leakage during the entire follow-up. Postoperatively, feeding function and body weight were gradually restored in the surviving animals. No hematological abnormalities were found, and no obvious anastomotic leakage, stenosis, or obstruction was observed under X-ray examination. The histopathologic results showed a progressive regeneration of the esophagus in the graft area, where the neo-esophagus tissue had characteristics similar to native esophageal tissue after 3 months of surgery. HKBC is beneficial for esophageal tissue regeneration and may be a promising material for esophageal reconstruction.

  17. Deciphering Carbamoylpolyoxamic Acid Biosynthesis Reveals Unusual Acetylation Cycle Associated with Tandem Reduction and Sequential Hydroxylation. (United States)

    Qi, Jianzhao; Wan, Dan; Ma, Hongmin; Liu, Yuanzhen; Gong, Rong; Qu, Xudong; Sun, Yuhui; Deng, Zixin; Chen, Wenqing


    Polyoxin, produced by Streptomcyes cacaoi var. asoensis and Streptomyces aureochromogenes, contains two non-proteinogenic amino acids, carbamoylpolyoxamic acid (CPOAA) and polyoximic acid. Although the CPOAA moiety is highly unusual, its biosynthetic logic has remained enigmatic for decades. Here, we address CPOAA biosynthesis by reconstitution of its pathway. We demonstrated that its biosynthesis is initiated by a versatile N-acetyltransferase, PolN, catalyzing L-glutamate (1) to N-acetyl glutamate (2). Remarkably, we verified that PolM, a previously annotated dehydrogenase, catalyzes an unprecedented tandem reduction of acyl-phosphate to aldehyde, and subsequently to alcohol. We also unveiled a distinctive acetylation cycle catalyzed by PolN to synthesize α-amino-δ-hydroxyvaleric acid (6). Finally, we report that PolL is capable of converting a rare sequential hydroxylation of α-amino-δ-carbamoylhydroxyvaleric acid (7) to CPOAA. PolL represents an intriguing family of Fe(II)-dependent α-ketoglutarate dioxygenase with a cupin fold. These data illustrate several novel enzymatic reactions, and also set a foundation for rational pathway engineering for polyoxin production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Theoretical study on the gas phase reaction of acrylonitrile with a hydroxyl radical. (United States)

    Sun, Jingyu; Wang, Rongshun; Wang, Baoshan


    The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).

  19. Bioluminescence inhibition assay for the detection of hydroxylated polychlorinated biphenyls. (United States)

    Teasley Hamorsky, Krystal; Ensor, C Mark; Dikici, Emre; Pasini, Patrizia; Bachas, Leonidas; Daunert, Sylvia


    Hydroxylated polychlorinated biphenyls (OH-PCBs) are an important class of contaminants that mainly originate from polychlorinated biphenyl metabolism. They may conceivably be as dangerous and persistent as the parent compounds; most prominently, OH-PCBs are endocrine disruptors. Due to increasing evidence of the presence of OH-PCBs in the environment and in living organisms, including humans, and of their toxicity, methods of detection for OH-PCBs are needed in the environmental and medical fields. Herein, we describe the development and optimization of a protein-based inhibition assay for the quantification of OH-PCBs. Specifically, the photoprotein aequorin was utilized for the detection of OH-PCBs. We hypothesized that OH-PCBs interact with aequorin, and we established that OH-PCBs actually inhibit the bioluminescence of aequorin in a dose-dependent manner. We took advantage of this phenomenon to develop an assay that is capable of detecting a wide variety of OH-PCBs with a range of detection limits, the best detection limit being 11 nM for the compound 2-hydroxy-2',3,4',5',6-pentachorobiphenyl. The viability of this system for the screening of OH-PCBs in spiked biological and environmental samples was also established. We envision the implementation of this novel bioluminescence inhibition assay as a rapid, sensitive, and cost-effective method for monitoring OH-PCBs. Furthermore, to the best of our knowledge, this is the first time aequorin has been employed to detect an analyte by the inhibition of its bioluminescence reaction. Hence, this strategy may prove to be a general approach for the development of a new generation of protein-based inhibition assays.

  20. CYP2E1 hydroxylation of aniline involves negative cooperativity. (United States)

    Hartman, Jessica H; Knott, Katie; Miller, Grover P


    CYP2E1 plays a role in the metabolic activation and elimination of aniline, yet there are conflicting reports on its mechanism of action, and hence relevance, in aniline metabolism. Based on our work with similar compounds, we hypothesized that aniline binds two CYP2E1 sites during metabolism resulting in cooperative reaction kinetics and tested this hypothesis through rigorous in vitro studies. The kinetic profile for recombinant CYP2E1 demonstrated significant negative cooperativity based on a fit of data to the Hill equation (n=0.56). Mechanistically, the data were best explained through a two-binding site cooperative model in which aniline binds with high affinity (K(s)=30 μM) followed by a second weaker binding event (K(ss)=1100 uM) resulting in a threefold increase in the oxidation rate. Binding sites for aniline were confirmed by inhibition studies with 4-methylpyrazole. Inhibitor phenotyping experiments with human liver microsomes validated the central role for CYP2E1 in aniline hydroxylation and indicated minor roles for CYP2A6 and CYP2C9. Importantly, inhibition of minor metabolic pathways resulted in a kinetic profile for microsomal CYP2E1 that replicated the preferred mechanism and parameters observed with the recombinant enzyme. Scaled modeling of in vitro CYP2E1 metabolism of aniline to in vivo clearance, especially at low aniline levels, led to significant deviations from the traditional model based on non-cooperative, Michaelis-Menten kinetics. These findings provide a critical mechanistic perspective on the potential importance of CYP2E1 in the metabolic activation and elimination of aniline as well as the first experimental evidence of a negatively cooperative metabolic reaction catalyzed by CYP2E1. Copyright © 2013 Elsevier Inc. All rights reserved.

  1. Hydroxyl temperature and intensity measurements during noctilucent cloud displays

    Directory of Open Access Journals (Sweden)

    M. J. Taylor

    Full Text Available Two Fourier transform spectrometers have been used to investigate the properties of the near-infrared hydroxyl (OH nightglow emission under high-latitude summertime conditions and any association with noctilucent clouds (NLCs. The measurements were made from Poker Flat Research Range, Alaska (65.1°N, 147.5°W, during August 1986. Simultaneous photographic observations of the northern twilight sky were made from Gulkana, Alaska (62.2°N, 145.5°W, approximately 340 km to the south to establish the presence of NLCs over the spectrometer site. Data exhibiting significant short-term variations in the relative intensity (as much as 50–100% and rotational temperature (typically 5–15 K were recorded on six occasions when NLCs were observed. Joint measurements were also obtained on several "cloud-free" nights. No obvious relationship was found linking the mean OH intensity or its variation with the occurrence of NLCs. However, a clear tendency was found for the mean OH temperature to be lower on NLC nights than on cloud-free nights. In particular, a significant fraction of the OH(3–1 band spectra recorded by each instrument (16–57% exhibited temperatures below ~154 K on NLC nights compared with <3% on cloud-free nights. This result is qualitatively consistent with current models for ice particle nucleation and growth, but the mean OH temperature on NLC nights (~156 K was significantly higher than would be expected for long-term particle growth in this region. These observations raise questions concerning the expected proximity of the high-latitude, summertime OH layer and the NLC growth region.

  2. Hydroxylated N-doped carbon nanotube-sulfur composites as cathodes for high-performance lithium-sulfur batteries (United States)

    Lee, Jun Seop; Manthiram, Arumugam


    Despite the higher energy density than the conventional Li-ion cells at a lower cost, commercialization of Lisbnd S batteries is hindered by the insulating nature of sulfur and the dissolution of intermediate polysulfides (Li2SX, 4 < X ≤ 8) into the electrolyte. We demonstrate here hydroxylated N-doped carbon nanotubes (H-NCNT) as sulfur containers in lithium-sulfur batteries to reduce polysulfide shuttling through an interaction between polysulfides and nitrogen and hydroxyl groups in the H-NCNT. This sulfur-carbon composite electrode with 2.2 mg cm-2 sulfur displays excellent performance with high rate capability (initial capacity of 1341 mAh g-1 at C/5 rate and 849 mAh g-1 at 5C rate), rate stability until 500 cycles (a decay of 0.06% per cycle). Furthermore, a stable reversible capacity of as high as ∼1081 mAh g-1 is realized with a higher sulfur loading of 5.1 mg cm-2.

  3. Hydroxylated polymethoxyflavones and methylated flavonoids in sweet orange (Citrus sinensis) peel. (United States)

    Li, Shiming; Lo, Chih-Yu; Ho, Chi-Tang


    Polymethoxyflavones (PMFs) from citrus genus have been of particular interest because of their broad spectrum of biological activities, including antiinflammatory, anticarcinogenic, and antiatherogenic properties. There have been increasing interests in the exploration of health beneficial properties of PMFs in citrus fruits. Therefore, the isolation and characterization of PMFs from sweet orange (Citrus sinensis) peel will lead to new applications of the byproducts from orange juice processes and other orange consumption in nutraceutical and pharmaceutical products. In our study, eight hydroxylated PMFs, six PMFs, one polymethoxyflavanone, one hydroxylated polymethoxyflavanone, and two hydroxylated polymethoxychalcones were isolated from sweet orange peel and their structures were elucidated by various MS, UV, and different NMR techniques. Some of the hydroxylated PMFs and chalcones are newly isolated from sweet orange peel.

  4. MLS/Aura L2 Hydroxyl (OH) Mixing Ratio V002 (United States)

    National Aeronautics and Space Administration — ML2OH is the EOS Aura Microwave Limb Sounder (MLS) standard product for hydroxyl derived from radiances measured by the THz radiometer. The current version is 2.2....

  5. MLS/Aura Level 2 Hydroxyl (OH) Mixing Ratio V004 (United States)

    National Aeronautics and Space Administration — ML2OH is the EOS Aura Microwave Limb Sounder (MLS) standard product for hydroxyl derived from radiances measured by the THz radiometer. The current version is 4.2....

  6. Scattering of state-selected and oriented hydroxyl radicals by halogen hydrides and xenon

    NARCIS (Netherlands)

    Moise, Angelica Valentina


    The interaction of the OH radical with atoms and other molecules is relevant for many physical and chemical processes involved in atmospheric, combustion and interstellar chemistry. Various experimental and theoretical studies have revealed information concerning the interaction of the hydroxyl

  7. Stratospheric ozone and hydroxyl radical measurements by balloon-borne lidar (United States)

    Heaps, W. S.; Mcgee, T. J.; Hudson, R. D.; Caudill, L. O.


    An experiment is reported in which a balloon-borne lidar system was used to measure ozone and the hydroxyl radical in the stratosphere by two lidar techniques. Ozone was measured in the 20-37 km altitude range using differential absorption lidar, and the hydroxyl radical was measured in the 34-37 km range using remote laser-induced fluorescence. Ozone concentrations were determined with a vertical resolution of 0.5 km, and in addition, horizontally resolved ozone measurements with 0.15-km resolution were obtained over a 2-km range. The temporal variation of the hydroxyl radical concentration ranged from 40 parts/trillion shortly after noon to about 5 parts/trillion two hours after sunset. Possible modifications to the system are discussed which can yield an improvement in the sensitivity of between one and two orders of magnitude, thus permitting measurements of the hydroxyl radical in the 20-30-km altitude range.

  8. Atmospheric hydroxyl radical production from electronically excited NO2 and H2O. (United States)

    Li, Shuping; Matthews, Jamie; Sinha, Amitabha


    Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

  9. Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

    CSIR Research Space (South Africa)

    Makgwane, PR


    Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

  10. MLS/Aura L2 Hydroxyl (OH) Mixing Ratio V003 (United States)

    National Aeronautics and Space Administration — ML2OH is the EOS Aura Microwave Limb Sounder (MLS) standard product for hydroxyl derived from radiances measured by the THz radiometer. The current version is...

  11. Rate constants of reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Abad, L.V. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)], E-mail:; Saiki, S.; Kudo, H.; Muroya, Y.; Katsumura, Y. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Rosa, A.M. de la [Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)


    The rate constants for the reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical was investigated by pulse radiolysis and laser photolysis. The kinetics of the reaction of hydrated electron indicates no seeming reaction with {kappa}-carrageenan. On the other hand, hydroxyl radical reacts very rapidly with {kappa}-carrageenan at a rate constant of approximately 1.2 x 10{sup 9} M{sup -1} s{sup -1}. This rate constant varies with pH.

  12. Presence of hydrogen peroxide, a source of hydroxyl radicals, in acid electrolyzed water.

    Directory of Open Access Journals (Sweden)

    Takayuki Mokudai

    Full Text Available BACKGROUND: Acid electrolyzed water (AEW, which is produced through the electrolysis of dilute sodium chloride (NaCl or potassium chloride solution, is used as a disinfectant in various fields because of its potent antimicrobial activity. The hydroxyl radical, an oxygen radical species, is often suggested as a putative active ingredient for AEW antimicrobial activity. METHODOLOGY/PRINCIPAL FINDINGS: The aim of the present study is to detect hydroxyl radicals in AEW. The hydroxyl radicals in AEW prepared under different conditions were determined using an electron spin resonance (ESR technique. A signal from 5,5-dimethyl-1-pyrroline N-oxide (DMPO-OH, an adduct of DMPO and the hydroxyl radical, was detected in AEW prepared by double or triple electrolyses of 1% NaCl but not of 0.1% NaCl solution. Then the presence of hydrogen peroxide as a proposed source of hydroxyl radicals was examined using a combination of ESR and a Fenton reaction. The DMPO-OH signal was clearly detected, even in AEW prepared by single electrolysis of 0.1% NaCl solution, when ferrous sulfate was added to induce a Fenton reaction, indicating the presence of hydrogen peroxide in the AEW. Since sodium formate, a hydroxyl radical scavenger, did not affect the bactericidal activity of AEW, it is concluded that the radical is unlikely to contribute to the antimicrobial activity of AEW, although a small amount of the radical is produced from hydrogen peroxide. Dimethyl sulfoxide, the other hydroxyl radical scavenger used in the present study, canceled the bactericidal activity of AEW, accompanied by complete depletion of free available chlorine, suggesting that hypochlorous acid is probably a major contributor to the antimicrobial activity. CONCLUSIONS: It is strongly suggested that although hydrogen peroxide is present in AEW as a source of hydroxyl radicals, the antimicrobial activity of AEW does not depend on these radicals.

  13. Thermochemistry of Hydroxyl and Hydroperoxide Substituted Furan, Methylfuran, and Methoxyfuran. (United States)

    Hudzik, Jason M; Bozzelli, Joseph W


    Reaction pathways are influenced by thermochemical properties, species stability, and chemical kinetics. Understanding these factors allows for an understanding of the reaction paths and formation of intermediate species. Enthalpies of formation (ΔHf,298(°)), entropies (S298(°)), heat capacities (Cp(T)), oxygen-hydrogen (O-H), oxygen-oxygen (O-O), and (R-O) bond dissociation energies (BDEs) are reported for hydroxyl and hydroperoxide substituted furan, methylfuran, and methoxyfuran species. Standard enthalpies of formation for parent and radical species have been determined using density functional theory B3LYP/6-31G(d,p), B3LYP/6-311G(2d,2p), and M06-2X/6-31G(d,p) along with higher-level CBS-QB3 and CBS-APNO composite methods. Isodesmic work reactions were employed to improve accuracy by canceling error and show consistency between the levels of theory. Corresponding O-H and O-O BDEs are determined and compared to other similar structures. The stability of the furan moiety coupled with the double-bond-forming capability of the oxygen moiety results in a number of bond energies significantly lower than one might have expected. Substituted hydroperoxides are calculated to have ROO-H BDEs between 86.9 and 94.2 kcal mol(-1), and their RO-OH BDEs show a large 49 kcal mol(-1) range of -2.3-46.8 kcal mol(-1). Substituted alcohols also show a wide 48 kcal mol(-1) range with RO-H BDEs, ranging from 59.3 to 106.9 kcal mol(-1). Bond lengths of parent and radical species are presented to highlight potential bonds of interest leading to furan ring opening. Group additivity is discussed, and groups for substituted furan, methylfuran, and methoxyfuran species are derived. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) density functional level and are used to determine the S298(°) and Cp(T) values.

  14. The hydroxyl-modified surfaces on glass support for fabrication of carbohydrate microarrays. (United States)

    Nan, Gang; Yan, Hua; Yang, Ganglong; Jian, Qiang; Chen, Chao; Li, Zheng


    Glycan-protein interactions play important biological roles in biological processes. But there is a lack of simple high-throughput methods to elucidate recognition events between carbohydrates and protein. Although, there have been a number of glycan arrays developed in recent years utilizing different strategies and for different purposes, the method presented in this paper, a direct covalent immobilization of sugars to hydroxyl-modified glass surface, can be a very useful general method. Here, two strategies have been developed for the production of carbohydrate microarrays by the underivatized sugars that efficiently immobilized on hydroxyl-functionalized glass surface by formation of glycosidic bond with the hemiacetal group at the reducing end of the suitable carbohydrates via condensation. Firstly, untreated glass slides were amino- and epoxy-silanized, respectively. Then, they were further hydroxyl functionalized with different surface chemistries. The carbohydrate microarrays were fabricated on hydroxyl-functionalized glass by robotic arrayer. Additionally, experiments for the characterization of carbohydrates-protein interaction were performed to compare these strategies. Overall best results in terms of conveniency and sensitivity were obtained with hydroxyl-functionalization on epoxysilanized surfaces. The hydroxyl-functionalized slide was used to detect the amount of mannose immobilized on the glass surface. The limit of detection of the fabricated mannose microarray was 100 nM.


    Directory of Open Access Journals (Sweden)

    Didik Prasetyoko


    Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

  16. Star polymers by ATRP of styrene and acrylates employing multifunctional initiators

    DEFF Research Database (Denmark)

    Jankova, Katja Atanassova; Bednarek, Melania; Hvilsted, Søren


    Multifunctional initiators for atom transfer radical polymerization (ATRP) are prepared by converting ditrimethylolpropane with four hydroxyl groups, dipentaerythritol with six hydroxyl groups, and poly(3-ethyl-3-hydroxymethyl-oxetane) with similar to 11 hydroxyl groups to the corresponding 2......-bromoisobutyrates or 2-bromopropionates as obtained by reaction with acid bromides. Star polystyrene (PS) is produced by using these macroinitiators and neat styrene in a controlled manner by ATRP at 110 degrees C, employing the catalytic system CuBr and bipyridine. M. up to 51,000 associated with narrow molecular...


    NARCIS (Netherlands)


    The synthesis and identification of 12 A-ring reduced 6 alpha-(and 6 beta-)hydroxylated compounds derived from 11-deoxycortisol (S), corticosterone (B) and 11-dehydrocorticosterone (A) are reported here. These steroids were prepared in two steps from the corresponding 6 6 alpha-(and 6

  18. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter (United States)

    Lindsey, M.E.; Tarr, M.A.


    Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical

  19. Detection and characterization of serine and threonine hydroxyl protons in Bacillus circulans xylanase by NMR spectroscopy. (United States)

    Brockerman, Jacob A; Okon, Mark; McIntosh, Lawrence P


    Hydroxyl protons on serine and threonine residues are not well characterized in protein structures determined by both NMR spectroscopy and X-ray crystallography. In the case of NMR spectroscopy, this is in large part because hydroxyl proton signals are usually hidden under crowded regions of (1)H-NMR spectra and remain undetected by conventional heteronuclear correlation approaches that rely on strong one-bond (1)H-(15)N or (1)H-(13)C couplings. However, by filtering against protons directly bonded to (13)C or (15)N nuclei, signals from slowly-exchanging hydroxyls can be observed in the (1)H-NMR spectrum of a uniformly (13)C/(15)N-labeled protein. Here we demonstrate the use of a simple selective labeling scheme in combination with long-range heteronuclear scalar correlation experiments as an easy and relatively inexpensive way to detect and assign these hydroxyl proton signals. Using auxtrophic Escherichia coli strains, we produced Bacillus circulans xylanase (BcX) labeled with (13)C/(15)N-serine or (13)C/(15)N-threonine. Signals from two serine and three threonine hydroxyls in these protein samples were readily observed via (3)JC-OH couplings in long-range (13)C-HSQC spectra. These scalar couplings (~5-7 Hz) were measured in a sample of uniformly (13)C/(15)N-labeled BcX using a quantitative (13)C/(15)N-filtered spin-echo difference experiment. In a similar approach, the threonine and serine hydroxyl hydrogen exchange kinetics were measured using a (13)C/(15)N-filtered CLEANEX-PM pulse sequence. Collectively, these experiments provide insights into the structural and dynamic properties of several serine and threonine hydroxyls within this model protein.

  20. Dioxygen reactivity of meso-hydroxylated hemes: intermediates in ...

    Indian Academy of Sciences (India)

    464. Scheme 2. in which the HO-bound heme could be converted to verdoheme and biliverdin by ascorbic acid or hydra- zine in the absence of NADPH and cytochrome. P450 reductase via the formation of similar interme- diates observed during the biological oxidation of heme by HO.2–7 The process involves initial meso.

  1. Post-translational hydroxylation by 2OG/Fe(II-dependent oxygenases as a novel regulatory mechanism in bacteria

    Directory of Open Access Journals (Sweden)

    Laura M van Staalduinen


    Full Text Available Protein hydroxylation has been well-studied in eukaryotic systems. The structural importance of hydroxylation of specific proline and lysine residues during collagen biosynthesis is well established while, recently, key roles for post-translational hydroxylation in signalling and degradation pathways have been discovered. The function of hydroxylation in signalling is highlighted by its role in the hypoxic response of eukaryotic cells, where oxygen dependent hydroxylation of the hypoxia inducible transcription factor both targets it for degradation and blocks its activation. In contrast, the role of protein hydroxylation has been largely understudied in prokaryotes. Recently, an evolutionarily conserved class of ribosomal oxygenases (ROX that catalyze the hydroxylation of specific residues in the ribosome has been identified in bacteria. ROX activity has been linked to cell growth, and has been found to have a direct impact on bulk protein translation. This discovery of ribosomal protein hydroxylation in bacteria could lead to new therapeutic targets for regulating bacterial growth, as well as, shed light on new prokaryotic hydroxylation signalling pathways. In this review, recent structural and functional studies will be highlighted and discussed, underscoring the regulatory potential of post-translational hydroxylation in bacteria.

  2. Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets (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.


    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.

  3. Induction of Extracellular Hydroxyl Radical Production by White-Rot Fungi through Quinone Redox Cycling▿ (United States)

    Gómez-Toribio, Víctor; García-Martín, Ana B.; Martínez, María J.; Martínez, Ángel T.; Guillén, Francisco


    A simple strategy for the induction of extracellular hydroxyl radical (OH) production by white-rot fungi is presented. It involves the incubation of mycelium with quinones and Fe3+-EDTA. Succinctly, it is based on the establishment of a quinone redox cycle catalyzed by cell-bound dehydrogenase activities and the ligninolytic enzymes (laccase and peroxidases). The semiquinone intermediate produced by the ligninolytic enzymes drives OH production by a Fenton reaction (H2O2 + Fe2+ → OH + OH− + Fe3+). H2O2 production, Fe3+ reduction, and OH generation were initially demonstrated with two Pleurotus eryngii mycelia (one producing laccase and versatile peroxidase and the other producing just laccase) and four quinones, 1,4-benzoquinone (BQ), 2-methoxy-1,4-benzoquinone (MBQ), 2,6-dimethoxy-1,4-benzoquinone (DBQ), and 2-methyl-1,4-naphthoquinone (menadione [MD]). In all cases, OH radicals were linearly produced, with the highest rate obtained with MD, followed by DBQ, MBQ, and BQ. These rates correlated with both H2O2 levels and Fe3+ reduction rates observed with the four quinones. Between the two P. eryngii mycelia used, the best results were obtained with the one producing only laccase, showing higher OH production rates with added purified enzyme. The strategy was then validated in Bjerkandera adusta, Phanerochaete chrysosporium, Phlebia radiata, Pycnoporus cinnabarinus, and Trametes versicolor, also showing good correlation between OH production rates and the kinds and levels of the ligninolytic enzymes expressed by these fungi. We propose this strategy as a useful tool to study the effects of OH radicals on lignin and organopollutant degradation, as well as to improve the bioremediation potential of white-rot fungi. PMID:19376892

  4. Sensitive determination of endogenous hydroxyl radical in live cell by a BODIPY based fluorescent probe. (United States)

    Lei, Kepeng; Sun, Mingtai; Du, Libo; Zhang, Xiaojie; Yu, Huan; Wang, Suhua; Hayat, Tasawar; Alsaedi, Ahmed


    The sensitive and selective fluorescence probe for hydroxyl radical analysis is of significance because hydroxyl radical plays key roles in many physiological and pathological processes. In this work, a novel organic fluorescence molecular probe OHP for hydroxyl radical is synthesized by a two-step route. The probe employs 4-bora-3a,4a-diaza-s-indacene (difluoroboron dipyrromethene, BODIPY) as the fluorophore and possesses relatively high fluorescence quantum yields (77.14%). Hydroxyl radical can rapidly react with the probe and quench the fluorescence in a good linear relationship (R2=0.9967). The limit of detection is determined to be as low as 11nM. In addition, it has been demonstrated that the probe has a good stability against pH and light illumination, low cytotoxicity and high biocompatibility. Cell culture experimental results show that the probe OHP is sensitive and selective for imaging and tracking endogenous hydroxyl radical in live cells. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. A comparison of fenuron degradation by hydroxyl and carbonate radicals in aqueous solution. (United States)

    Mazellier, Patrick; Busset, Cécile; Delmont, Anne; De Laat, Joseph


    A comparative study of the transformation of the herbicide fenuron (1,1-dimethyl-3-phenylurea) by hydroxyl radicals and carbonate radicals in aqueous solution (pH 7.2-phosphate buffer) has been undertaken. Hydroxyl radical was generated by the well-known photolysis of hydrogen peroxide at 254 nm and carbonate radical was formed by photolysis of Co(NH(3))(5)CO(3)(+) at 254 nm. Competitive kinetic experiments were performed with atrazine used as the main competitor for both processes. Accordingly, the second-order rate constant of reaction between fenuron and carbonate radical was found to be (7-12+/-3)x10(6)M(-1)s(-1) [(7+/-1)x10(9)M(-1)s(-1) for hydroxyl radical]. The formation of degradation products was studied by LC-MS in the two cases and a comparison has been performed. The reaction with carbonate radical leads to the formation of a quinone-imine derivative which appears as the major primary product together with ortho and para hydroxylated compounds. These two compounds represent the major products in the reaction with hydroxyl radicals. The reaction of both radicals also leads to the transformation of the dimethylurea moiety.

  6. Subterminal hydroxylation of lauric acid by microsomes from a marine fish. (United States)

    Lemaire, P; Lafaurie, M; Weissbart, D; Durst, F; Pflieger, P; Mioskowski, C; Salaün, J P


    Microsomes from the liver of sea bass (Dicentrarchus labrax) were shown to hydroxylate lauric acid at subterminal positions. The cytochrome P-450 system converted lauric acid to several mono-hydroxylated metabolites including omega-1 hydroxylaurate, which was the major metabolite (44% of total products). In addition, omega-2, omega-3, omega-4 and a small amount (2.3%) of omega hydroxylaurates were found. Reaction products were identified using thin-layer chromatography (TLC) and gas chromatography/mass spectrometry (GC/MS). Oxidation reactions were dependent upon O2 and NADPH, and did not occur with boiled microsomes or in the presence of a mixture of CO/O2. Hydroxylation proceeded linearly up to 20 min at 28 degrees C for protein concentrations below 380 micrograms. Treatment of fish with benzo(a)pyrene (BP) (20 mg/kg) drastically increased xenobiotic metabolism (ECOD, EROD and BPMO activities), but no difference in laurate hydroxylase activity was observed between untreated and treated fish. Starvation strongly enhanced laurate hydroxylase activity, and resumption of feeding reduced by half this increase of activity. In all of the experiments we did not observe any modification of the regioselectivity of lauric acid hydroxylation by this microsomal in-chain hydroxylating system. We suggest that cytochrome P-450 enzymes involved in lauric acid and xenobiotics metabolism are regulated independently.

  7. Palladium(II) complexes bearing a salicylaldiminato ligand with a hydroxyl group: Synthesis, structures, deprotonation, and catalysis


    Murata, Yusuke; Ohgi, Hiroyuki; Fujihara, Tetsuaki; Terao, Jun; Tsuji, Yasushi


    Palladium complexes with a salicylaldiminato ligand bearing a hydroxyl group (1a and 1b) have been synthesized and characterized. The structures of these complexes were confirmed by X-ray crystallography. A reversible deprotonation/protonation of the hydroxyl moiety on 1b was observed, while such behaviour was impossible with a related palladium complex (1c) bearing a methoxyl group in place of the hydroxyl group. The deprotonation affected its catalytic behaviour: the activity for polymeriza...

  8. Hydroxyl radical "footprinting": high-resolution information about DNA-protein contacts and application to lambda repressor and Cro protein.


    Tullius, T D; Dombroski, B A


    A method has been developed for making "footprints" of proteins bound to DNA. The hydroxyl radical, generated by reduction of hydrogen peroxide by iron(II), is the reagent used to cut the DNA. Hydroxyl radical breaks the backbone of DNA with almost no sequence dependence, so all backbone positions may be monitored for contact with protein. In addition to defining the DNA sequence in contact with the protein, hydroxyl radical footprints embody structural information about the DNA-protein compl...

  9. Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study (United States)

    Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.


    Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

  10. Influence of hydroxylation and glycosylation in ring A of soybean isoflavones on interaction with BSA (United States)

    Zhao, Jinyao; Ren, Fenglian


    In this paper, the influence of hydroxylation and glycosylation of soybean isoflavones in ring A on the interaction with BSA was investigated. Two soybean isoflavone aglycones (daidzein and genistein) and their glycosides (daidzin and genistin) were used to study their ability to bind BSA by quenching the BSA intrinsic fluorescence in solution. The hydroxylation and glycosylation of soybean isoflavones in ring A significantly affected the binding/quenching process; in general, the hydroxylation increases the binding affinity and the glycosylation decreased the binding affinity. For daidzein and daidzin, the binding constants for BSA were 5.2 × 10 4 and 5.58 × 10 3 L mol -1, respectively. For genistein and genistin, the binding constants were 8.40 × 10 5 and 1.44 × 10 5 L mol -1, respectively.

  11. Hydroxylation of steroids with nonpolar side chains with 11 alpha-hydroxylase of Rhizopus nigricans. (United States)

    Zakelj-Mavric, M; Kastelic-Suhadolc, T; Gottlieb, H E; Belic, I


    Steroids with nonpolar side chains with 2, 4 and 8 C atoms were used as substrates for the 11 alpha-hydroxylase of Rhizopus nigricans. Their bioconversion was compared to that of progesterone, which was found to be far the best substrate giving the highest total bioconversion. 3-keto-4-ene steroids with nonpolar side chains were converted to their hydroxylated products in a small yield or not at all. The absence of an oxygen function in the side chain did not affect the regio-specificity of the hydroxylation, but resulted in a much lower total bioconversion. The strong effect of the oxygen function and of the length of the side chain on hydroxylation with the 11 alpha-hydroxylase of Rhizopus nigricans was demonstrated.

  12. OH, the Places You'll Go! Hydroxylation, Gene Expression, and Cancer. (United States)

    Ploumakis, Athanasios; Coleman, Mathew L


    Hydroxylation is an emerging modification generally catalyzed by a family of ∼70 enzymes that are dependent on oxygen, Fe(II), ascorbate, and the Kreb's cycle intermediate 2-oxoglutarate (2OG). These "2OG oxygenases" sit at the intersection of nutrient availability and metabolism where they have the potential to regulate gene expression and growth in response to changes in co-factor abundance. Characterized 2OG oxygenases regulate fundamental cellular processes by catalyzing the hydroxylation or demethylation (via hydroxylation) of DNA, RNA, or protein. As such they have been implicated in various syndromes and diseases, but particularly cancer. In this review we discuss the emerging role of 2OG oxygenases in gene expression control, examine the regulation of these unique enzymes by nutrient availability and metabolic intermediates, and describe these properties in relation to the expanding role of these enzymes in cancer. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. The Reaction of Allyl Isothiocyanate with Hydroxyl/Water and β-Cyclodextrin Using Ultraviolet Spectrometry

    Directory of Open Access Journals (Sweden)

    Zi-Tao Jiang


    Full Text Available The reaction of allyl isothiocyanate (AITC with hydroxyl/water and β-cyclodextrin (β-CD in different acidic-alkaline media has been investigated by ultraviolet spectrometry. The kinetic parameters of the reaction were measured. It was found that after AITC translating into thiourea, the absorption peak shifted from 240 to 226 nm and the molar absorptivity increased about 16 times. The reaction can be seen as a pseudo first order reaction because the concentration of hydroxyl was constant. β-CD can inhibit the reaction of AITC with hydroxyl/water, i.e. the hydrolysis of AITC. The formation constant (Ka and thermodynamic parameters of the complex reaction were calculated. Ka decreased with the increase of temperature. The experimental results indicated that the inclusive process was an exothermic and enthalpy-driven process accompanied with a negative entropic contribution.

  14. Hydroxyl accessibility in wood cell walls as affected by drying and re-wetting procedures

    DEFF Research Database (Denmark)

    Thybring, Emil Engelund; Thygesen, Lisbeth Garbrecht; Burgert, Ingo


    The first drying of wood cell walls from the native state has sometimes been described as producing irreversible structural changes which reduce the accessibility to water, a phenomenon often referred to as hornification. This study demonstrates that while changes do seem to take place......, these are more complex than what has hitherto been described. The accessibility of wood cell wall hydroxyls to deuteration in the form of liquid water was not found to be affected by drying, since vacuum impregnation with liquid water restores the native cell wall accessibility. Contrary to this, hydroxyl...... to 1 day. Moreover, the decrease in hydroxyl accessibility to deuteration by water vapour induced by the first drying could be at least partially erased by subsequent vacuum impregnation with liquid water, indicating reversibility. For the drying of solid, non-degraded wood cell walls the results...

  15. Sarcoplasmic reticulum Ca(2+)-pump dysfunction in rat cardiomyocytes briefly exposed to hydroxyl radicals. (United States)

    Morris, T E; Sulakhe, P V


    The effects of hydroxyl radical exposure of intact cardiomyocytes on sarcoplasmic reticulum (SR) function were investigated. For this purpose, isolated rat heart myocytes were exposed briefly (1 min) to the hydroxyl radical generating system (H2O2/FeCl2 or FeSO4) or 5-5'-dithiobis-nitrobenzoic acid (DTNB), a sulfhydryl oxidizing reagent, and following this a SR-enriched fraction was isolated. Marked decreases in the SR calcium uptake activities were seen in the myocytes exposed to either the hydroxyl radical-generating system or DTNB. The exposure of myocytes to the hydroxyl radical, but not DTNB, markedly increased the amount of malonyldialdehyde (MDA) in the subsequently isolated SR. Total sulfhydryl group content in SR was decreased by exposure of myocytes to DTNB. Further, there was a significant decrease in [3H]-NEM binding to SR isolated from the hydoxyl radical-treated myocytes indicating that sulfhydryl groups are affected (oxidized). Both mannitol and catalase were found to offer complete protection against the inhibitory effect of peroxide +/- iron on calcium uptake. Also the above-mentioned alterations in both MDA and sulfhydryl group content were prevented by mannitol and catalase. Exogenously added cyclic AMP-dependent protein kinase (A-PK) or calmodulin (CAM) increased SR calcium uptake activity. In the SR isolated from the treated myocytes, the stimulatory effects of A-PK and CAM were also seen, although under all assay conditions calcium uptakes were of lower magnitude. The findings are consistent with the view that the damaging effect of the hydroxyl radical and DTNB on the functioning of SR occurs rapidly in the intact cardiomyocytes. The hydroxyl radical-provoked damage involves both protein sulfhydryl and lipid oxidation.

  16. A two-component monooxygenase catalyzes both the hydroxylation of p-nirophenol and the oxidative release of nitrite from 4-nitrocatechol in Bacillus sphaericus JS905

    Energy Technology Data Exchange (ETDEWEB)

    Kadiyala, V.; Spain, J.C. [Air Force Research Lab., Tyndall AFB, FL (United States)


    Bacteria that metabolize p-nitrophenol (PNP) oxidize the substrate to 3-ketoadipic acid via either hydroquinone or 1,2,4-trihydroxybenzene (THB); however, initial steps in the pathway for PNP biodegradation via THB are unclear. The product of initial hydroxylation of PNP could be either 4-nitrocatechol or 4-nitroresorcinol. Here the authors describe the complete pathway for aerobic PNP degradation by Bacillus sphaericus JS905 that was isolated by selective enrichment from an agricultural soil in India. Washed cells of PNP-grown JS905 released nitrite in stoichiometric amounts from PNP and 4-nitrocatechol. Experiments with extracts obtained from PNP-grown cells revealed that the initial reaction is a hydroxylation of PNP to yield 4-nitrocatechol. 4-nitrocatechol is subsequently oxidized to THB with the concomitant removal of the nitro group as nitrite. The enzyme that catalyzed the two sequential monooxygenations of PNP was partially purified and separated into two components by anion-exchange chromatography and size exclusion chromatography. Both components were required for NADH-dependent oxidative release of nitrite from PNP or 4-nitrocatechol. One of the components was identified as a reductase based on its ability to catalyze the NAD(P)H-dependent reduction of 2,6-dichlorophenolindophenol and nitroblue tetrazolium. Nitrite release from either PNP or 4-nitrocatechol was inhibited by the flavoprotein inhibitor methimazole. Their results indicate that the two monooxygenations of PNP to THB are catalyzed by a single two-component enzyme system comprising a flavoprotein reductase and an oxygenase.

  17. Divorce in the barn owl: securing a compatible or better mate entails the cost of re-pairing with a less ornamented female mate. (United States)

    Dreiss, A N; Roulin, A


    Two nonmutually exclusive hypotheses can explain why divorce is an adaptive strategy to improve reproductive success. Under the 'better option hypothesis', only one of the two partners initiates divorce to secure a higher-quality partner and increases reproductive success after divorce. Under the 'incompatibility hypothesis', partners are incompatible and hence they may both increase reproductive success after divorce. In a long-term study of the barn owl (Tyto alba), we address the question of whether one or the two partners derive fitness benefits by divorcing. Our results support the hypothesis that divorce is adaptive: after a poor reproductive season, at least one of the two divorcees increase breeding success up to the level of faithful pairs. By breeding more often together, faithful pairs improve coordination and thereby gain in their efficiency to produce successful fledglings. Males would divorce to obtain a compatible mate rather than a mate of higher quality: a heritable melanin-based signal of female quality did not predict divorce (indicating that female absolute quality may not be the cause of divorce), but the new mate of divorced males was less melanic than their previous mate. This suggests that, at least for males, a cost of divorce may be to secure a lower-quality but compatible mate. The better option hypothesis could not be formally rejected, as only one of the two divorcing partners commonly succeeded in obtaining a higher reproductive success after divorce. In conclusion, incompatible partners divorce to restore reproductive success, and by breeding more often together, faithful partners improve coordination. © 2014 The Authors. Journal of Evolutionary Biology © 2014 European Society For Evolutionary Biology.

  18. Effect of indole-3-acetic acid on pea root growth, peroxidase profiles and hydroxyl radical formation

    Directory of Open Access Journals (Sweden)

    Kukavica Biljana


    Full Text Available Changes in growth, peroxidase profiles, and hydroxyl radical formation were examined in IAA (0.5-10 mg/l treated pea plants grown hydroponically and in isolated roots in liquid in vitro culture. IAA inhibited root elongation, both in hydroponically grown pea plants and in isolated roots in vitro. A remarkable increase in the number of POD iso­forms was noticed in isolated roots grown in vitro, compared to the roots from plants grown hydroponically. IAA induced both disappearance of several root POD isoforms and hydroxyl radical formation in the root and the root cell wall.

  19. Autocatalytic surface hydroxylation of MgO(100) terrace sites observed under ambient conditions

    DEFF Research Database (Denmark)

    Newberg, J.T.; Mysak, E.R.; Bluhm, H.


    We have investigated the reaction of water vapor with the MgO(100) surface using ambient pressure X-ray photoelectron spectroscopy (AP-XPS), which permits the study of the chemical composition of the MgO/water vapor interface at p(H2O) in the Torr range. Water dissociation on thin MgO(100) films...... interacting with a fully hydroxylated interface on MgO(100). The observed onset of hydroxylation near 0.01% RH is suggested to be due to water molecules aggregating at the surface, leading to an autocatalytic dissociation of water at MgO(100) terrace sites....

  20. Formation of hydroxyl radicals in the human lens is related to the severity of nuclear cataract

    DEFF Research Database (Denmark)

    Garner, B; Davies, Michael Jonathan; Truscott, R J


    Recent studies have identified specific hydroxylated amino acid oxidation products which strongly suggest the presence of hydroxyl radical (HO.)-damaged proteins in human cataractous lenses. In the present study, the ability of early stage (type II) and advanced (type IV) nuclear cataractous lens....... formation and not DMPO-OOH degradation. The metal ion chelator, diethylenetriaminepentaacetic acid, also inhibited HO. formation, indicating that lenticular metal ions play a key role in HO. formation. Cataractous lens homogenates also stimulated ascorbyl radical production, further suggesting the presence...

  1. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme (United States)

    Koch, Daniel J.; Arnold, Frances H.


    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  2. N-hydroxylation of 4-aminobiphenyl by CYP2E1 produces oxidative stress in a mouse model of chemically induced liver cancer. (United States)

    Wang, Shuang; Sugamori, Kim S; Tung, Aveline; McPherson, J Peter; Grant, Denis M


    4-Aminobiphenyl (ABP) is a trace component of cigarette smoke and hair dyes, a suspected human carcinogen and a potent rodent liver carcinogen. Postnatal exposure of mice to ABP results in a higher incidence of liver tumors in males than in females, paralleling the sex difference in human liver cancer incidence. A traditional model of ABP tumorigenesis involves initial CYP1A2-mediated N-hydroxylation, which eventually leads to production of mutagenic ABP-DNA adducts that initiate tumor growth. However, several studies have found no correlation between sex or CYP1A2 function and the DNA-damaging, mutagenic, or tumorigenic effects of ABP. Oxidative stress may be an important etiological factor for liver cancer, and it has also been linked to ABP exposure. The goals of this study were to identify novel enzyme(s) that contribute to ABP N-oxidation, and to investigate a potential role for oxidative stress in ABP liver tumorigenicity. Isozyme-selective inhibition experiments using liver microsomes from wild-type and genetically modified mice identified CYP2E1 as a major ABP N-hydroxylating enzyme. The N-hydroxylation of ABP by transiently expressed CYP2E1 produced oxidative stress in cultured mouse hepatoma cells. In vivo postnatal exposure of mice to a tumorigenic dose of ABP also produced oxidative stress in male wild-type mice, but not in male Cyp2e1(-/-) mice or in female mice. However, a stronger NRF2-associated antioxidant response was observed in females. Our results identify CYP2E1 as a novel ABP-N-oxidizing enzyme, and suggest that sex differences in CYP2E1-dependent oxidative stress and antioxidant responses to ABP may contribute to the observed sex difference in tumor incidence. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail:

  3. Carbazole hydroxylation by the filamentous fungi of the Cunninghamella species. (United States)

    Zawadzka, K; Bernat, P; Felczak, A; Lisowska, K


    Nitrogen heterocyclic compounds, especially carbazole, quinolone, and pyridine are common types of environmental pollutants. Carbazole has a toxic influence on living organisms, and the knowledge of its persistence and bioconversion in ecosystems is still not complete. There is an increasing interest in detoxification of hazardous xenobiotics by microorganisms. In this study, the ability of three filamentous fungi of the Cunninghamella species to eliminate carbazole was evaluated. The Cunninghamella elegans IM 1785/21Gp and Cunninghamella echinulata IM 2611 strains efficiently removed carbazole. The IM 1785/21Gp and IM 2611 strains converted 93 and 82 % of the initial concentration of the xenobiotic (200 mg L(-1)) after 120 h incubation. 2-Hydroxycarbazole was for the first time identified as a carbazole metabolite formed by the filamentous fungi of the Cunninghamella species. There was no increase in the toxicity of the postculture extracts toward Artemia franciscana. Moreover, we showed an influence of carbazole on the phospholipid composition of the cells of the tested filamentous fungi, which indicated its harmful effect on the fungal cell membrane. The most significant modification of phospholipid levels after the cultivation of filamentous fungi with the addition of carbazole was showed for IM 1785/21Gp strain.

  4. Oxygen activation at the plasma membrane: relation between superoxide and hydroxyl radical production by isolated membranes. (United States)

    Heyno, Eiri; Mary, Véronique; Schopfer, Peter; Krieger-Liszkay, Anja


    Production of reactive oxygen species (hydroxyl radicals, superoxide radicals and hydrogen peroxide) was studied using EPR spin-trapping techniques and specific dyes in isolated plasma membranes from the growing and the non-growing zones of hypocotyls and roots of etiolated soybean seedlings as well as coleoptiles and roots of etiolated maize seedlings. NAD(P)H mediated the production of superoxide in all plasma membrane samples. Hydroxyl radicals were only produced by the membranes of the hypocotyl growing zone when a Fenton catalyst (FeEDTA) was present. By contrast, in membranes from other parts of the seedlings a low rate of spontaneous hydroxyl radical formation was observed due to the presence of small amounts of tightly bound peroxidase. It is concluded that apoplastic hydroxyl radical generation depends fully, or for the most part, on peroxidase localized in the cell wall. In soybean plasma membranes from the growing zone of the hypocotyl pharmacological tests showed that the superoxide production could potentially be attributed to the action of at least two enzymes, an NADPH oxidase and, in the presence of menadione, a quinone reductase.

  5. Glutathione conjugation of busulfan produces a hydroxyl radical-trapping dehydroalanine metabolite. (United States)

    Peer, Cody J; Younis, Islam R; Leonard, Stephen S; Gannett, Peter M; Minarchick, Valerie C; Kenyon, Allison J; Rojanasakul, Yon; Callery, Patrick S


    The Phase 2 drug metabolism of busulfan yields a glutathione conjugate that undergoes a β-elimination reaction. The elimination product is an electrophilic metabolite that is a dehydroalanine-containing tripeptide, γ-glutamyldehydroalanylglycine (EdAG). In the process, glutathione lacks thiol-related redox properties and gains a radical scavenging dehydroalanine group. EdAG scavenged hydroxyl radical generated in the Fenton reaction in a concentration-dependent manner was monitored by electron paramagnetic resonance (EPR) spectroscopy. The apparent rate of hydroxyl radical scavenging was in the same range as published values for known antioxidants, including N-acyl dehydroalanines. A captodatively stabilized carbon-centered radical intermediate was spin trapped in the reaction of EdAG with hydroxyl radical. The proposed structure of a stable product in the Fenton reaction with EdAG was consistent with that of a γ-glutamylserylglycyl dimer. Observation of the hydroxyl trapping properties of EdAG suggests that the busulfan metabolite EdAG may contribute to or mitigate redox-related cytotoxicity associated with the therapeutic use of busulfan, and reaffirms indicators that support a role in free radical biology for dehydroalanine-containing peptides and proteins.

  6. Advances in the synthesis mulitmetallic systems: hydroxyl group protection in aryldiamine platinum species

    NARCIS (Netherlands)

    Koten, G. van; Davies, P.J.; Grove, D.M.


    A multimetallic system containing three platinum atoms has been synthesized through use of an (aryldiamine)platinum complex with a protected hydroxyl group which, after deprotection, is coupled with the trisubstituted aryl molecule 1,3,5-tris(chlorocarbonyl)benzene that provides the core moiety. The

  7. Hydroxylated fullerenes inhibit neutrophil function in fathead minnow (Pimephales promelas Rafinesque, 1820). (United States)

    Jovanović, Boris; Anastasova, Lora; Rowe, Eric W; Palić, Dušan


    Hydroxylated fullerenes act as potent inhibitors of cytochrome P450-dependent monooxygenases, and are reported to be very strong antioxidants quenching reactive oxygen species (ROS) production. Effects of nanosized hydroxylated fullerenes on fish neutrophil function and immune gene transcription was investigated using fathead minnow (Pimephales promelas). Neutrophil function assays were used to determine the effects of fullerene exposure in vitro and in vivo on oxidative burst, degranulation and extracellular trap (NETs) release, and the innate immune gene transcription was determined with quantitative PCR (qPCR). Application of fullerenes (0.2-200 microgmL(-1)in vitro) caused concentration dependent inhibition of oxidative burst and suppressed the release of NETs and degranulation of primary granules (up to 70, 40, and 50% reduction in activity compared to non-treated control, respectively). Transcription of interleukin 11 and myeloperoxidase genes was significantly increased and transcription of elastase 2 gene was significantly decreased in fish exposed to hydroxylated fullerenes for 48h in vivo (12 and 3 fold increase, and 5 fold decrease, respectively). Observed changes in gene transcription and neutrophil function indicate potential for hydroxylated fullerenes to interfere with the evolutionary conserved innate immune system responses and encourages the use of fish models in studies of nanoparticle immunotoxicity. 2010 Elsevier B.V. All rights reserved.

  8. Prediction of hydroxyl concentrations in cement pore water using a numerical cement hydration model

    NARCIS (Netherlands)

    van Eijk, R.J.; Brouwers, Jos


    In this paper, a 3D numerical cement hydration model is used for predicting alkali and hydroxyl concentrations in cement pore water. First, this numerical model is calibrated for Dutch cement employing both chemical shrinkage and calorimetric experiments. Secondly, the strength development of some

  9. Biological production of hydroxylated aromatics : Optimization strategies for Pseudomonas putida S12

    NARCIS (Netherlands)

    Verhoef, A.


    To replace environmentally unfriendly petrochemical production processes, the demand for bio-based production of organic chemicals is increasing. This thesis focuses on the biological production of hydroxylated aromatics from renewable substrates by engineered P. putida S12 including several cases

  10. Mechanism of the N-Hydroxylation of Primary and Secondary Amines by Cytochrome P450

    DEFF Research Database (Denmark)

    Seger, Signe T.; Rydberg, Patrik; Olsen, Lars


    Cytochrome P450 enzymes (CYPs) metabolize alkyl- and arylamines, generating several different products. For the primary and secondary amines, some of these reactions result in hydroxylated amines, which may be toxic. Thus, when designing new drugs containing amine groups, it is important to be able...

  11. 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.

  12. Environmentally persistent free radicals (EPFRs)-2. Are free hydroxyl radicals generated in aqueous solutions? (United States)

    Khachatryan, Lavrent; Dellinger, Barry


    A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (·OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: (1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.

  13. Fetal exposure to PCBs and their hydroxylated metabolites in a Dutch cohort

    NARCIS (Netherlands)

    Soechitram, S.D.; Athanasiadou, M.; Hovander, L.; Bergman, A.; Sauer, P. J. J.


    Polychlorinated biphenyls (PCBs) are still the most abundant pollutants in wildlife and humans. Hydroxylated PCB metabolites (OH-PCBs) are known to be formed in humans and wildlife. Studies in animals show that these metabolites cause endocrine-related toxicity. The health effects in humans have not

  14. In Vivo Cell Wall Loosening by Hydroxyl Radicals during Cress Seed Germination and Elongation Growth

    NARCIS (Netherlands)

    Muller, K.; Linkies, A.; Vreeburg, R.A.M.; Fry, S.C.; Krieger-Liszkay, A.; Leubner-Metzger, G.


    Loosening of cell walls is an important developmental process in key stages of the plant life cycle, including seed germination, elongation growth, and fruit ripening. Here, we report direct in vivo evidence for hydroxyl radical (·OH)-mediated cell wall loosening during plant seed germination and

  15. Environmentally Persistent Free Radicals (EPFRs) - 2. Are Free Hydroxyl Radicals Generated in Aqueous Solutions? (United States)

    Khachatryan, Lavrent


    A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (.OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: 1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, 2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and 3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/ml EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μl phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals. PMID:21942783

  16. The haloperoxidase of the agaric fungus Agrocybe aegerita hydroxylates toluene and naphthalene. (United States)

    Ullrich, René; Hofrichter, Martin


    The mushroom Agrocybe aegerita secretes a peroxidase (AaP) that catalyzes halogenations and hydroxylations. Phenol was brominated to 2- and 4-bromophenol (ratio 1:4) and chlorinated to a lesser extent to 2-chlorophenol. The purified enzyme was found to oxidize toluene via benzyl alcohol and benzaldehyde into benzoic acid. A second fraction of toluene was hydroxylated to give p-cresol as well as o-cresol and methyl-p-benzoquinone. The UV-Vis absorption spectrum of purified AaP showed high similarity to a resting state cytochrome P450 with the Soret band at 420 nm and additional maxima at 278, 358, 541 and 571 nm; the AaP CO-complex had a distinct absorption maximum at 445 nm that is characteristic for heme-thiolate proteins. AaP regioselectively hydroxylated naphthalene to 1-naphthol and traces of 2-naphthol (ratio 36:1). H2O2 was necessarily required for AaP function and hence the hydroxylations catalyzed by AaP can be designated as peroxygenation and the enzyme as an extracellular peroxygenase.

  17. Aromatic hydroxylation of methylenedioxybenzene (MDB) and methylenedioxymethamphetamine (MDMA) by rabbit liver microsomes. (United States)

    Kumagai, Y; Schmitz, D A; Cho, A K


    1. Metabolites formed during incubation of methylenedioxybenzene (MDB) and methylenedioxymethamphetamine (MDMA) with rabbit liver microsomes were examined by h.p.l.c.-electrochemical detection and g.l.c.-mass spectrometry. 2. The trifluoroacetyl derivative of metabolite M-1, obtained from MDB, had a molecular ion at m/z 234 and was identified as 3,4-methylenedioxy-6-hydroxybenzene (sesamol) by comparison with authentic material. 3. The trifluoroacetyl derivative of metabolite M-2, obtained from MDMA, exhibited a molecular ion at m/z 401. Experiments with the deuterium substituted variants of MDMA indicated that the product was hydroxylated on the aromatic ring. 4. The formation of these hydroxylated metabolites required NADPH and was inhibited by carbon monoxide, indicating the possible participation of cytochrome P-450. Phenobarbital (PB) induction caused a marked enhancement of MDP hydroxylase activity whereas MDMA hydroxylation was not affected. 5. The aromatic hydroxylation of MDB and MDMA was also observed in a reconstituted system with cytochrome P-450 isozyme IIB4.

  18. Methyl-esterified 3-hydroxybutyrate oligomers protect bacteria from hydroxyl radicals (United States)

    Bacteria rely mainly on enzymes, glutathione and other low-molecular weight thiols to overcome oxidative stress. However, hydroxyl radicals are the most cytotoxic reactive oxygen species, and no known enzymatic system exists for their detoxification. We now show that methyl-esterified dimers and tri...

  19. Acute toxicity variation of hydroxyl benzophenone UV filters during photoinduction-chlorination disinfection processes. (United States)

    Yu, Qi; Wei, Dongbin; Liu, Wei; Du, Yuguo


    Benzophenones (BPs), a group of widely used UV filters, exert multiple, significant toxicity effects. The 11 BPs were selected as target compounds, and the photobacterium acute toxicity test and an index for acute toxicity formation potential (ATFP) were used to evaluate the toxicity variation of BPs before and after a photoinduction-chlorination disinfection process. Orthogonal experiments were performed at different pH values and chlorine dosages. The characteristics of ATFP values for 11 BPs after a photoinduction-chlorination process can be summarized as follows: (1) The ATFPs decreased as the hydroxyl group number increased in BPs molecules. (2) For those BPs with the same hydroxyl group number, the ATFPs were higher when the hydroxyl groups were located at the 3- or 4-position than those at the 2-position; the BPs with hydroxyl groups distributed on two benzene rings had higher ATFPs than those on one ring. (3) Introducing a methoxyl group and sulfonic acid group into BP molecules increased the ATFP values. (4) The ATFPs were pH-dependent, the values of which were lowest at the neutral condition and highest at the acid condition. (5) The ATFPs increased and then decreased as the chlorine dosage increased. The results can be used as a reference to scientifically evaluate the environmental fate and potential risk of BPs in photoinduction-chlorination disinfection processes. Copyright © 2016. Published by Elsevier B.V.

  20. Divergent copper-mediated dimerization and hydroxylation of benzamides involving C-H bond functionalization. (United States)

    Wang, Mingliang; Hu, Yimin; Jiang, Zhe; Shen, Hong C; Sun, Xun


    Convenient methods were developed for copper-mediated oxidative C-H activation of aminoquinoline benzamides. The reaction conditions can be tuned to give either hydroxylation or dimerization compounds as the major products efficiently. Preliminary mechanistic studies suggested that different coordination states of copper may lead to different reaction outcomes.

  1. Microbial formation of hydroxylated aromatic compounds from 4-chloro- and 4-nitrobenzoate

    NARCIS (Netherlands)

    Groenewegen, P.


    In the introduction of this thesis several aspects of the production of hydroxylated aromatic compounds are described. These compounds are applied in the production of pharmaceuticals, polymers, flavors and dyes, but their chemical synthesis is rather difficult in preparative organic

  2. Evidence for formation of hydroxyl radicals during reperfusion after global cerebral ischaemia in rats using salicylate trapping and microdialysis

    DEFF Research Database (Denmark)

    Christensen, Thomas; Bruhn, T; Balchen, T


    Systemic administration of salicylate (SA) to rats (100 mg kg-1 i.p. ) was used as an in vivo trap of hydroxyl radicals (.OH). In the brain SA reacts with hydroxyl radicals to form the stable adducts 2, 3- and 2,5 dihydroxybenzoic acid (DHBAs) which can thus be taken as an index of .OH formation...

  3. Urocanic acid isomers are good hydroxyl radical scavengers: a comparative study with structural analogues and with uric acid

    NARCIS (Netherlands)

    Kammeyer, A.; Eggelte, T. A.; Bos, J. D.; Teunissen, M. B.


    UV-exposure of the epidermis leads to the isomerisation of trans-UCA into cis-UCA as well as to the generation of hydroxyl radicals. This study shows by means of the deoxyribose degradation test that UCA isomers are more powerful hydroxyl radical scavengers than the other 4-(5-)substituted imidazole

  4. Influence of hydroxyl content of binders on rheological properties of cerium-gadolinium oxide (CGO) screen printing inks

    DEFF Research Database (Denmark)

    Marani, Debora; Gadea, Christophe; Hjelm, Johan


    The influence of hydroxyl content of binders on rheological properties of screen printing inks is investigated. The actual amount of hydroxyl groups is correlated to the level of hyper-entanglement that characterizes the binders in solution. Three of the most used binders (ethyl cellulose, and two...

  5. Monitoring equilibrium changes in RNA structure by 'peroxidative' and 'oxidative' hydroxyl radical footprinting. (United States)

    Bachu, Ravichandra; Padlan, Frances-Camille S; Rouhanifard, Sara; Brenowitz, Michael; Schlatterer, Jörg C


    RNA molecules play an essential role in biology. In addition to transmitting genetic information, RNA can fold into unique tertiary structures fulfilling a specific biologic role as regulator, binder or catalyst. Information about tertiary contact formation is essential to understand the function of RNA molecules. Hydroxyl radicals (•OH) are unique probes of the structure of nucleic acids due to their high reactivity and small size. When used as a footprinting probe, hydroxyl radicals map the solvent accessible surface of the phosphodiester backbone of DNA and RNA with as fine as single nucleotide resolution. Hydroxyl radical footprinting can be used to identify the nucleotides within an intermolecular contact surface, e.g. in DNA-protein and RNA-protein complexes. Equilibrium and kinetic transitions can be determined by conducting hydroxyl radical footprinting as a function of a solution variable or time, respectively. A key feature of footprinting is that limited exposure to the probe (e.g., 'single-hit kinetics') results in the uniform sampling of each nucleotide of the polymer. In this video article, we use the P4-P6 domain of the Tetrahymena ribozyme to illustrate RNA sample preparation and the determination of a Mg(II)-mediated folding isotherms. We describe the use of the well known hydroxyl radical footprinting protocol that requires H(2)O(2) (we call this the 'peroxidative' protocol) and a valuable, but not widely known, alternative that uses naturally dissolved O(2)(we call this the 'oxidative' protocol). An overview of the data reduction, transformation and analysis procedures is presented.

  6. The effect of hydroxylation on CNT to form Chitosan-CNT composites: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Rui [China-America Cancer Research Institute, Key Laboratory for Medical Molecular Diagnostics of Guangdong Province, Guangdong Medical University, Dongguan, Guangdong 523808 (China); Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Ran, Maofei [College of Chemistry & Environment Protection Engineering, Southwest University for Nationalities, Chengdu 610041, Sichuan (China); Wen, Jie [College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan (China); Sun, Wenjing, E-mail: [China-America Cancer Research Institute, Key Laboratory for Medical Molecular Diagnostics of Guangdong Province, Guangdong Medical University, Dongguan, Guangdong 523808 (China); Chu, Wei; Jiang, Chengfa [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); He, Zhiwei, E-mail: [China-America Cancer Research Institute, Key Laboratory for Medical Molecular Diagnostics of Guangdong Province, Guangdong Medical University, Dongguan, Guangdong 523808 (China)


    Graphical abstract: - Highlights: • The effect of hydroxylation on CNT to form Chitosan-CNT composites was studied. • The adsorption of Chitosan on CNTs is very weak by electrostatic interactions. • Chitosan loads onto CNT-OH{sub n} via hydrogen-bond interactions. • Chitosan transfers electron to CNT-OH{sub n} and thus improves the reactivity of CNT. - Abstract: The effect of types of CNTs (pristine and hydroxylated) on the synthesis of Chitosan-CNT (CS-CNT) composites was investigated theoretically. The adsorption energy (E{sub ads}) of CS on the pristine CNT and hydroxylated CNTs (CNT-OH{sub n}, n = 1–6) as well as the structural and electronic properties of said composites have been investigated. Results show that the adsorption of CS on CNT and CNT-OH{sub n} is thermodynamically favored. The E{sub ads} of CS on CNTs was calculated to be −20.387 kcal/mol from electrostatic interactions. For CS adsorbed into CNT-OH{sub n}, E{sub ads} ranges from −20.612 to −37.567 kcal/mol. Hydroxyl groups on CNT are the main adsorption sites for CS loading onto CNT-OH{sub n} via hydrogen-bond interactions. The CS-CNT-OH{sub 3} is the most sable composite among tested complexes. The energy gap (ΔE{sub gap}) of CS-CNT-OH{sub 3} was calculated less than pristine CNT and CNT-OH{sub 3}, indicative of the composites being more reactive than that of pristine CNTs and CNT-OH{sub 3}. It was proved that CS can transfer electron to the hydroxylated CNTs, thus overcoming the drawbacks of CNTs being chemically inert.

  7. Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants. (United States)

    Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John


    The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77

  8. Reactions of hydroxyl radicals with alkenes in low-temperature matrices. (United States)

    Feltham, E J; Almond, M J; Marston, G; Wiltshire, K S; Goldberg, N


    The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H2O2, and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices--methanol, ethanol, ethanol-d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol (iso-butyl alcohol), 2-methylpropan-2-ol (tert-butyl alcohol), 2-methylbutan-2-ol (tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows--from ethene, 2-hydroxyethyl radical: from cis- or trans-but-2-ene. 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene. 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene (iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2-hydroxyethyl

  9. Hydroxyl radical induced oxidation of theophylline in water: a kinetic and mechanistic study. (United States)

    Sunil Paul, M M; Aravind, U K; Pramod, G; Saha, A; Aravindakumar, C T


    Oxidative destruction and mineralization of emerging organic pollutants by hydroxyl radicals (˙OH) is a well established area of research. The possibility of generating hazardous by-products in the case of ˙OH reaction demands extensive investigations on the degradation mechanism. A combination of pulse radiolysis and steady state photolysis (H2O2/UV photolysis) followed by high resolution mass spectrometric (HRMS) analysis have been employed to explicate the kinetic and mechanistic features of the destruction of theophylline, a model pharmaceutical compound and an identified pollutant, by ˙OH in the present study. The oxidative destruction of this molecule, for intermediate product studies, was initially achieved by H2O2/UV photolysis. The transient absorption spectrum corresponding to the reaction of ˙OH with theophylline at pH 6, primarily caused by the generation of (T8-OH)˙, was characterised by an absorption band at 330 nm (k2 = (8.22 ± 0.03) × 10(9) dm(3) mol(-1) s(-1)). A significantly different spectrum (λmax: 340 nm) was observed at highly alkaline pH (10.2) due to the deprotonation of this radical (pKa∼ 10.0). Specific one electron oxidants such as sulphate radical anions (SO4˙(-)) and azide radicals (N3˙) produce the deprotonated form (T(-H)˙) of the radical cation (T˙(+)) of theophylline (pKa 3.1) with k2 values of (7.51 ± 0.04) × 10(9) dm(3) mol(-1) s(-1) and (7.61 ± 0.02) × 10(9) dm(3) mol(-1) s(-1) respectively. Conversely, oxide radicals (O˙(-)) react with theophylline via a hydrogen abstraction protocol with a rather slow k2 value of (1.95 ± 0.02) × 10(9) dm(3) mol(-1) s(-1). The transient spectral studies were complemented by the end product profile acquired by HRMS analysis. Various transformation products of theophylline induced by ˙OH were identified by this technique which include derivatives of uric acids (i, iv & v) and xanthines (ii, iii & vi). Further breakdown of the early formed product due to ˙OH attack leads to

  10. Oxidation Products of Semi-volatile Alkanes by Hydroxyl Radicals (United States)

    Zhang, H.; Worton, D. R.; Nah, T.; Goldstein, A. H.; Wilson, K. R.


    Alkanes are ubiquitous in the atmosphere and are important components that influence atmospheric chemistry. Semi-volatile alkanes are partitioned between the gas- and the particle-phases and can be readily oxidized in both phases. Previous studies have demonstrated that reaction rates and the products of OH oxidation are very different for organic compounds in the gas- and particle phases. In the present study, n-octadecane (C18H38), n-eicosane (C20H42), n-docosane (C22H46), n-tricosane (C24H50), and n-pentadecylcyclohexane (C21H42) were chosen as model compounds for semi-volatile alkanes to examine their OH-initiated oxidation reactions in a flow tube reactor. OH exposure was varied in the experiments, equivalent to oxidation of up to one week in the atmosphere. Oxidation products were collected on filters and analyzed using two-dimensional gas chromatography coupled to a high-resolution time-of-flight electron impact ionization and vacuum ultraviolet photoionization mass spectrometer. Most of the oxygenated higher molecular weight isomers were separated and quantified. Our results suggest that aerosol samples formed in the n-octadecane experiment were more oxidized than the other model compounds (i.e., functionalization products with three oxygen atoms per molecule compared to two oxygen atoms per molecule) at similar OH exposures and aerosol mass loadings. This is likely due to the concentration of n-octadecane in the gas phase where oxidation is more rapid. We find that the first-generation gas-phase oxidation products quickly partition to the particle phase after which higher-generation oxidation likely occurs in the particle phase. Interestingly, functionalized carbonyl isomers for the normal alkanes were only observed on the 4 carbon positions closest to the molecule end in all cases, which is in contrast to structure-reactivity relationship (SRR) predictions for gas-phase reactions. For n-octadecane, the concentrations of first-generation functionalization

  11. Extending quantum mechanics entails extending special relativity (United States)

    Aravinda, S.; Srikanth, R.


    The complementarity between signaling and randomness in any communicated resource that can simulate singlet statistics is generalized by relaxing the assumption of free will in the choice of measurement settings. We show how to construct an ontological extension for quantum mechanics (QMs) through the oblivious embedding of a sound simulation protocol in a Newtonian spacetime. Minkowski or other intermediate spacetimes are ruled out as the locus of the embedding by virtue of hidden influence inequalities. The complementarity transferred from a simulation to the extension unifies a number of results about quantum non-locality, and implies that special relativity has a different significance for the ontological model and for the operational theory it reproduces. Only the latter, being experimentally accessible, is required to be Lorentz covariant. There may be certain Lorentz non-covariant elements at the ontological level, but they will be inaccessible at the operational level in a valid extension. Certain arguments against the extendability of QM, due to Conway and Kochen (2009) and Colbeck and Renner (2012), are attributed to their assumption that the spacetime at the ontological level has Minkowski causal structure.

  12. What comparative family law should entail

    NARCIS (Netherlands)

    Boele-Woelki, K.


    Since globalization is not only restricted to economic and political relationships, but literally ‘hits home’, it has become indispensable to look beyond national boundaries and to take international developments into account in the field of family law. Hence, comparative family law is blooming. The

  13. Computing approximate diagnoses by using approximate entailment

    NARCIS (Netherlands)

    Teije, A. ten; Harmelen, van F.A.H.


    The most widely accepted models of diagnostic reasoning are all phrased in terms of the logical consequence relations. In work in recent years, Schaerf and Cadoli have proposed efficient approximations of the classical consequence relation. The central idea of this paper is to parameterise the

  14. Space Supervenience and Entailment | Gibb | Philosophical Papers

    African Journals Online (AJOL)

    Given this thesis of supervenience, relationism is implausible. I argue that the problem that Le Poidevin raises for relationism should be rejected, because the thesis of supervenience is false. The latter rests upon what Le Poidevin refers to as 'The explanatory principle', a principle which he claims to be a natural extension ...

  15. What does entailment for PTL mean?

    CSIR Research Space (South Africa)

    Booth, R


    Full Text Available the propositions b, f, p and o stand for, respectively, “Tweety is a bird”, “Tweety flies”, “Tweety is a penguin” and “Tweety is an ostrich”. The following are examples of L‚-sentences: ‚b, o Ñ ‚ b, pp_ oq Ø pb^ ‚ fq. The semantics of PTL is in terms of structures... (“penguins are birds” and “birds typically fly”). Given just this infor- mation about birds and penguins, it is reasonable to assume that penguins are typical birds and expect ‚p Ñ f to fol- low from K1 (Sections 4 and 6 contain a formalization...

  16. Hydroxyl radical involvement in the decomposition of hydrogen peroxide by ferrous and ferric-nitrilotriacetate complexes at neutral pH. (United States)

    Dao, Yen Hai; De Laat, Joseph


    The relative rates of degradation of three hydroxyl radical probe compounds (atrazine, fenuron and parachlorobenzoic acid (pCBA)) by Fe(III)/H(2)O(2) (pH = 2.85), Fe(III)NTA/H(2)O(2) (neutral pH), Fe(II)/O(2), Fe(II)NTA/O(2), Fe(II)/H(2)O(2) and Fe(II)NTA/H(2)O(2) (neutral pH) have been investigated using the competitive kinetic method. Experiments were carried out in batch and in semi-batch reactors, in the dark, at 25 °C. The data showed that the three probe compounds could be degraded by all the systems studied, and in particular by Fe(II)NTA/H(2)O(2) and Fe(III)NTA/H(2)O(2) at neutral pH. The relative rate constants of degradation of the three probe compounds obtained for all the systems tested were identical and equal to 1.45 ± 0.03 and 0.47 ± 0.02 for k(Atrazine)/k(pCBA) and k(Fenuron)/k(pCBA), respectively. These values as well as the decrease of the rates of degradation of the probe compounds upon the addition of hydroxyl radical scavengers (tert-butanol, bicarbonate ions) suggest that the degradation of atrazine, fenuron and pCBA by Fe(II)NTA/O(2), Fe(II)NTA/H(2)O(2) and Fe(III)NTA/H(2)O(2) is initiated by hydroxyl radicals. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Effect of thyme/cumin essential oils and butylated hydroxyl anisole/butylated hydroxyl toluene on physicochemical properties and oxidative/microbial stability of chicken patties. (United States)

    Sariçoban, Cemalettin; Yilmaz, Mustafa Tahsin


    In this study, effects of thyme/cumin essential oils (EO) and butylated hydroxyl anisole (BHA)/butylated hydroxyl toluene (BHT) on physicochemical properties and storage stability of chicken patties were compared in different storage periods (0, 3, 7, 14, 21, and 28 d). It was found that there were significant (P < 0.05) differences between physicochemical properties of patty samples treated with EO and the synthetic antioxidants. The EO showed similar performance to those of BHA and BHT in limiting TBARS values of chicken patty samples. Similarity in performance was also the case for microbial stability (total aerobic mesophilic, psychrotrophic, lactic acid, and coliform bacteria as well as molds and yeasts); namely, their effects were significant (P < 0.05). Effect of thyme EO was significant (P < 0.05) and remarkable, not allowing any coliform bacteria to grow in the samples. Given that EO were obtained from natural sources, the data suggested that the EO might be more useful than their synthetic counterparts, BHA and BHT, as additives for chicken patties to maintain oxidative/microbial stability and increase shelf life.

  18. Impact of Micro Silica Surface Hydroxyl Groups on the Properties of Calcium Silicate Products

    DEFF Research Database (Denmark)

    Haastrup, Sonja; Jørgensen, Bianca; Yu, Donghong


    of calcium silicate. We increase the hydroxyl groups by dispersing the micro silica in 10wt% H2O2 (CS10%), and we remove the hydroxyl groups by drying the micro silica at 650°C and then disperse it in water (CS650). A reference sample is also prepared from as-received micro silica dispersed in water (CSref...... for sample CS10% and the crystal phase tobermorite increase compared to CSref. Sample CS650 is mainly composed of Ca(OH)2 after reaction, and hardly any xonotlite and tobermorite crystal phase found. The compressive strength is found to increase for CS10%. The linear shrinkage also increases, which is caused...

  19. Preparation of large-size graphene oxide-like with hydroxyl groups and its optoelectronic properties (United States)

    Zhang, Chao-Zhi; Liu, Ling-Ling


    Laser materials are very important for fabricating laser devices. In this paper, a new type of graphene oxide-like with hydroxyl groups (GOLH) was synthesized for developing pulse laser devices. GOLH was characterized by fourier transform infrared, X-ray diffraction, elemental analysis, scanning electron microscopy, Raman spectra and dynamic light scattering. Experimental results showed that GOLH contained mainly one kind of substituent, hydroxyl group. Average size of GOLH was about 1.5 μm. Its optoelectronic properties were studied by a Q-switched pulse laser. Experimental results suggested that GOLH would be employed as a saturable absorber. A Q-switched pulse laser with the GOLH materials exhibited stable signal intensity and narrow pulse duration, 0.8 μs. Therefore, GOLH would be potential pulse laser materials.

  20. Interaction of hydrogen with ZnO nanopowders--evidence of hydroxyl group formation. (United States)

    Wong, Kester W J; Field, Matthew R; Ou, Jian Zhen; Latham, Kay; Spencer, Michelle J S; Yarovsky, Irene; Kalantar-zadeh, Kourosh


    There have been many investigations to reveal the nature of the hydrogen gas and ZnO nanopowder interaction at elevated temperatures, while at present no conclusive description of such an interaction has been confidently reported. In this work, we demonstrate that a hydroxyl group is formed during this interaction, depending on size and relative crystallinity of nanopowders. Our in situ Raman spectroscopy investigations show that the interaction directly affects the intensity of the Raman signal at 483 cm(-1), relative to the peak at 519 cm(-1). Ex situ x-ray diffraction (XRD) and infrared spectroscopy also show extra peaks at 44° and 1618 cm(-1), respectively, after hydrogenation. These peaks were all identified as surface hydroxyl groups, which can be related to the formation of water on the ZnO nanopowder surfaces.

  1. Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups. (United States)

    Zhang, Yu-Chen; Jiang, Fei; Wang, Shu-Liang; Shi, Feng; Tu, Shu-Jiang


    The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.

  2. Hydroxylated polychlorinated biphenyls decrease circulating steroids in female polar bears (Ursus maritimus)

    DEFF Research Database (Denmark)

    Gustavson, Lisa; Ciesielski, Tomasz M; Bytingsvik, Jenny


    As a top predator in the Arctic food chain, polar bears (Ursus maritimus) are exposed to high levels of persistent organic pollutants (POPs). Because several of these compounds have been reported to alter endocrine pathways, such as the steroidogenesis, potential disruption of the sex steroid...... synthesis by POPs may cause implications for reproduction by interfering with ovulation, implantation and fertility. Blood samples were collected from 15 female polar bears in Svalbard (Norway) in April 2008. The concentrations of nine circulating steroid hormones; dehydroepiandrosterone (DHEA......-metabolites (hydroxylated PCBs [OH-PCBs] and hydroxylated PBDEs [OH-PBDEs]), steroid hormones, biological and capture variables in female polar bears. Inverse correlations were found between circulating levels of PRE and AN, and circulating levels of OH-PCBs. There were no significant relationships between the steroid...

  3. Stereochemistry of hydroxylation of some chiral spiro-[2,5]octan-4-ones (United States)

    Gella, I. M.; Drushlyak, T. G.; Pivnenko, N. S.; Zubatyuk, R. I.; Turov, A. V.; Konovalova, I. S.; Novikova, N. B.; Shishkin, O. V.


    Stereoselective oxidative alpha hydroxylation of (1R,5R,8R,3R)-1-aryl-5-isopropyl-8-methyl-3-spiro-[2,5]octan-4-ones has been found as a secondary process in the cyclopropanation of 2-arylidene isomenthanones with trimethylsulfoxonium iodide in DMSO/NaOH or DMF/NaOH system. Three stereoisomeric hydroxy ketones have been isolated from a reaction mixture of cyclopropanation reaction, but the reaction of oxidation carried out with isolated spiro-[2,5]octan-4-ones was stereoselective. The advantages of this method of stereoselective hydroxylation are room temperature of reaction and absence of expensive catalysts. The reduction of obtained hydroxy ketones was also stereoselective and gave the only trans-(4R,5S)-dioles. The structures have been confirmed with 1D and 2D 1H and 13C NMR, MS spectra and for stereoisomeric hydroxy ketones with X-ray analysis also.

  4. Analyzing the structure of macromolecules in their native cellular environment using hydroxyl radical footprinting. (United States)

    Chea, Emily E; Jones, Lisa M


    Hydroxyl radical footprinting (HRF) has been successfully used to study the structure of both nucleic acids and proteins. The method utilizes hydroxyl radicals to oxidize solvent accessible sites in macromolecules. In recent years, the method has shown some utility for live cell analysis. In this review, we will survey the current state of the field for footprinting macromolecules in living cells. The field is relatively new, particularly for protein studies, with only a few publications on the development and application of HRF on live cells. DNA-protein interaction sites and information on the secondary and tertiary structure of RNA has been characterized. In addition, the conformational changes of membrane-spanning channels upon opening and activation have also been studied by in-cell HRF. In this review, we highlight examples of these applications.

  5. Study on the surface hydroxyl group on solid breeding materials by infrared absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Satoru; Taniguchi, Masaki [Tokyo Univ. (Japan). Faculty of Engineering


    Hydroxyl groups on the surface of Li{sub 2}O were studied by using a diffuse reflectance method with Fourier transform infrared absorption spectroscopy at high temperature up to 973K under controlled D{sub 2}O or D{sub 2} partial pressure. It was found that hydroxyl groups could exist on Li{sub 2}O surface up to 973K under Ar atmosphere. Under D{sub 2}O containing atmosphere, only the sharp peak at 2520cm{sup -1} was observed at 973K in the O-D stretching vibration region. Below 973K, multiple peaks due to the surface -OD were observed and they showed different behavior with temperature or atmosphere. Multiple peaks mean that surface is not homogeneous for D{sub 2}O adsorption. Assignment of the observed peaks to the surface bonding structure was also discussed. (author)

  6. Optical measurement of static temperature and hydroxyl radical profiles in a hydrogen-fueled supersonic combustor (United States)

    Gaugler, R. E.


    Profiles of static temperature and hydroxyl radical concentration were measured in a two-dimensional supersonic combustor test section 22.8 cm downstream of hydrogen injection. A high-pressure gas generator supplied vitiated air to the test section at Mach 2.44, atmospheric pressure, and a total temperature of about 2240 K. Room-temperature hydrogen was injected through a 0.40-cm step slot at Mach 1 and matched pressure. The measurements utilized a noninterfering spectral line absorption technique in which narrow ultraviolet emission lines of the hydroxyl electronic transition are absorbed by the broader absorption lines in the combustion gas. Comparison of the measured temperature profiles with theoretical calculations showed good agreement.

  7. Microbial carbonylation and hydroxylation of 20(R)-panaxadiol by Aspergillus niger. (United States)

    Yan, Bin; Chen, Zhihua; Zhai, Xuguang; Yin, Guibo; Ai, Yafei; Chen, Guangtong


    20(R)-panaxadiol (PD) was metabolised by the fungus Aspergillus niger AS 3.3926 to its C-3 carbonylated metabolite and five other hydroxylated metabolites (1-6). Their structures were elucidated as 3-oxo-20(R)-panaxadiol (1), 3-oxo-7β-hydroxyl- 20(R)-panaxadiol (2), 3-oxo-7β,23α-dihydroxyl-20(R)-panaxadiol (3), 3,12-dioxo- 7β,23β-dihydroxyl-20(R)-panaxadiol (4), 3-oxo-1α,7β-dihydroxyl-20(R)-panaxadiol (5) and 3-oxo-7β,15β-dihydroxyl-20(R)-panaxadiol (6) by spectroscopic analysis. Among them, compounds 2-6 were new compounds. Pharmacological studies revealed that compound 6 exhibited significant anti-hepatic fibrosis activity.

  8. XPS study of PBO fiber surface modified by incorporation of hydroxyl polar groups in main chains

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Tao; Hu Dayong; Jin Junhong; Yang Shenglin [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620 (China); Li Guang, E-mail: [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620 (China); Jiang Jianming [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620 (China)


    Dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO), a modified poly(p-phenylene benzoxazole) (PBO) polymer containing double hydroxyl groups in polymer chains, was synthesized by copolymerization of 4,6-diamino resorcinol dihydrochloride (DAR), purified terephthalic acid (TA) and 2,5-dihydroxyterephthalic acid (DHTA). DHPBO fibers were prepared by dry-jet wet-spinning method. The effects of hydroxyl polar groups on the surface elemental compositions of PBO fiber were investigated by X-ray photoelectron spectroscopy (XPS). The results show that the ratio of oxygen/carbon on the surface of DHPBO fibers is higher than that on the surface of PBO fibers, which indicates the content of polar groups on the surface of DHPBO fiber increase compared with PBO fiber.

  9. Cp* Iridium Complexes Give Catalytic Alkane Hydroxylation with Retention of Stereochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Meng [Yale Univ., New Haven, CT (United States); Schley, Nathan D [Yale Univ., New Haven, CT (United States); Crabtree, Robert H [Yale Univ., New Haven, CT (United States)


    A series of Cp*Ir complexes can catalyze C-H oxidation, with ceric ammonium nitrate as the terminal oxidant and water as the source of oxygen. Remarkably the hydroxylation of cis-decalin and 1,4-dimethylcyclohexane proceeds with retention of stereochemistry. With H2O18, cis-decalin oxidation gave 18O incorporation into the product cis-decalol.

  10. Oxidative hydroxylation of phosphine in aqueous alcohol solutions of p-benzoquinone (United States)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Ergozhin, E. E.; Mukhitdinova, B. A.


    The oxidation of phosphine in aqueous alcohol solution of benzoquinone in the presence of iodide ions is studied. Kinetic measurements, redox potentiometry, and gas chromatography are used to determine the kinetic regularities of the oxidative hydroxylation of phosphine, and a single-stage redox mechanism is proposed for this reaction. It is found that the iodine resulting from the oxidation of I- ions by quinone is the reagent responsible for the formation of phosphorus-containing products.

  11. The juxtaposition of ribose hydroxyl groups: the root of biological catalysis and the RNA world? (United States)

    Bernhardt, Harold S


    We normally think of enzymes as being proteins; however, the RNA world hypothesis suggests that the earliest biological catalysts may have been composed of RNA. One of the oldest surviving RNA enzymes we are aware of is the peptidyl transferase centre (PTC) of the large ribosomal RNA, which joins amino acids together to form proteins. Recent evidence indicates that the enzymatic activity of the PTC is principally due to ribose 2'-OHs. Many other reactions catalyzed by RNA and/or in which RNA is a substrate similarly utilize ribose 2'-OHs, including phosphoryl transfer reactions that involve the cleavage and/or ligation of the ribose-phosphate backbone. It has recently been proposed by Yakhnin (2013) that phosphoryl transfer reactions were important in the prebiotic chemical evolution of RNA, by enabling macromolecules composed of polyols joined by phosphodiester linkages to undergo recombination reactions, with the reaction energy supplied by the phosphodiester bond itself. The almost unique juxtaposition of the ribose 2'-hydroxyl and 3'-oxygen in ribose-containing polymers such as RNA, which gives ribose the ability to catalyze such reactions, may have been an important factor in the selection of ribose as a component of the first biopolymer. In addition, the juxtaposition of hydroxyl groups in free ribose: (i) allows coordination of borate ions, which could have provided significant and preferential stabilization of ribose in a prebiotic environment; and (ii) enhances the rate of permeation by ribose into a variety of lipid membrane systems, possibly favouring its incorporation into early metabolic pathways and an ancestral ribose-phosphate polymer. Somewhat more speculatively, hydrogen bonds formed by juxtaposed ribose hydroxyl groups may have stabilized an ancestral ribose-phosphate polymer against degradation (Bernhardt and Sandwick 2014). I propose that the almost unique juxtaposition of ribose hydroxyl groups constitutes the root of both biological

  12. Degradation pathways of lamotrigine under advanced treatment by direct UV photolysis, hydroxyl radicals, and ozone. (United States)

    Keen, Olya S; Ferrer, Imma; Michael Thurman, E; Linden, Karl G


    Lamotrigine is recently recognized as a persistent pharmaceutical in the water environment and wastewater effluents. Its degradation was studied under UV and ozone advanced oxidation treatments with reaction kinetics of lamotrigine with ozone (≈4 M(-1)s(-1)), hydroxyl radical [(2.1 ± 0.3) × 10(9)M(-1)s(-1)] and by UV photolysis with low and medium pressure mercury vapor lamps [quantum yields ≈0 and (2.7 ± 0.4)× 10(-4) respectively] determined. All constants were measured at pH 6 and at temperature ≈20°C. The results indicate that lamotrigine is slow to respond to direct photolysis or oxidation by ozone and no attenuation of the contaminant is expected in UV or ozone disinfection applications. The compound reacts rapidly with hydroxyl radicals indicating that advanced oxidation processes would be effective for its treatment. Degradation products were identified under each treatment process using accurate mass time-of-flight spectrometry and pathways of decay were proposed. The main transformation pathways in each process were: dechlorination of the benzene ring during direct photolysis; hydroxyl group addition to the benzene ring during the reaction with hydroxyl radicals; and triazine ring opening after reaction with ozone. Different products that form in each process may be to a varying degree less environmentally stable than the parent lamotrigine. In addition, a novel method of ozone quenching without addition of salts is presented. The new quenching method would allow subsequent mass spectrometry analysis without a solid phase extraction clean-up step. The method involves raising the pH of the sample to approximately 10 for a few seconds and lowering it back and is therefore limited to applications for which temporary pH change is not expected to affect the outcome of the analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. High resolution hydroxyl radical footprinting of the binding of mithramycin and related antibiotics to DNA.


    Cons, B M; Fox, K R


    The preferred binding sites for mithramycin on three different DNA fragments have been determined by hydroxyl radical footprinting. Sequences which appear as one long protected region using DNAase I as a footprinting probe are resolved into several discrete binding domains. Each drug molecule protects three bases from radical attack, though adjacent regions show attenuated cleavage. Mithramycin and the other related compounds induce similar footprinting patterns and appear to recognise GC ric...

  14. Reassigning the most stable surface of hydroxyapatite to the water resistant hydroxyl terminated (010) surface (United States)

    Zeglinski, Jacek; Nolan, Michael; Thompson, Damien; Tofail, Syed A. M.


    Understanding the surface stability and crystal growth morphology of hydroxyapatite is important to comprehend bone growth and repair processes and to engineer protein adsorption, cellular adhesion and biomineralization on calcium phosphate based bone grafts and implant coatings. It has generally been assumed from electronic structure calculations that the most stable hydroxyapatite surface is the (001) surface, terminated just above hydroxyl ions perpendicular to the {001} crystal plane. However, this is inconsistent with the known preferential growth direction of hydroxyapatite crystals and previous experimental work which indicates that, contrary to currently accepted theoretical predictions, it is actually the (010) surface that is preferentially exposed. The surface structure of the (010) face is still debated and needs reconciliation. In this work, we use a large set of density functional theory calculations to model the interaction of water with hydroxyapatite surfaces and probe the surface stability and resistance to hydrolytic remodeling of a range of surface faces including the (001) surface and the phosphate-exposed, calcium-exposed, and hydroxyl-exposed terminations of the (010) surface. For the (001) surface and the phosphate-exposed (010) surface, dissociative water adsorption is favorable. In contrast, the hydroxyl-terminated (010) surface will not split water and only molecular adsorption of water is possible. Our calculations show, overall, that the hydroxyl-terminated (010) surface is the most stable and thus should be the predominant form of the hydroxyapatite surface exposed in experiments. This finding reconciles discrepancies between the currently proposed surface terminations of hydroxyapatite and the experimentally observed crystal growth direction and surface stability, which may aid efforts to accelerate biomineralization and better control bone-repair processes on hydroxyapatite surfaces.

  15. Novel spectroscopic sensor for the hydroxyl radical scavenging activity measurement of biological samples. (United States)

    Bekdeşer, Burcu; Özyürek, Mustafa; Güçlü, Kubilay; Apak, Reşat


    A novel spectroscopic sensor was developed and validated for hydroxyl radical scavenging (HRS) activity estimation using terephthalate (TP) as probe. This sensor was designed by electrostatic immobilization of the chromogenic oxidizing agent of the CUPric Reducing Antioxidant Capacity (CUPRAC) method, Cu(II)-Neocuproine (Cu(II)-Nc) complex, on a Nafion cation-exchange membrane, and the spectrophotometric assay developed in aqueous-alcoholic solutions was integrated to the CUPRAC sensor. Hydroxyl radicals ((•)OH) generated from an equivalent mixture of Fe(II)+EDTA with hydrogen peroxide attacked both the probe and the (•)OH scavengers in 37 °C-incubated solutions for 1/2h. The HRS activity was measured using the decrease in CUPRAC absorbance at 450 nm - arising from the reduction of Cu(II)-Nc reagent to the Cu(I)-neocuproine chelate - of the hydroxylated probe (TP) undergoing radical attack in the presence of (•)OH scavengers. The HRS activity was evaluated as the second-order rate constants of biologically active compounds for (•)OH scavenging and also as the percentage scavenging of a measured compound or sample relative to a reference compound. Using this reaction, a kinetic approach was adopted to assess the HRS activity of amino acids, plasma- and thiol-antioxidants. This assay, applicable to small molecule antioxidants and tissue homogenates, proved to be efficient for serine and albumin for which the widely used TBARS (thiobarbituric acid-reactive substances) test is nonresponsive. Under optimal conditions, about half of the probe (TP) was converted into 2-hydroxyterephthalate (hTP), and this monohydroxylated derivative, being the only product of hydroxylation, was a more specific marker of (•)OH than the non-specific malondialdehyde end-product of the TBARS test. The sensor gave a linear response to scavenger concentration in the competition kinetic equation. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Hydroxyl and water molecule orientations in trypsin: Comparison to molecular dynamics structures

    Energy Technology Data Exchange (ETDEWEB)

    McDowell, R.S.; Kossiakoff, A.A. [Genentech, Inc., South San Francisco, CA (United States)


    A comparison is presented of experimentally observed hydroxyl and water hydrogens in trypsin determined from neutron density maps with the results of a 140ps molecular dynamics (MD) simulation. Experimental determination of hydrogen and deuterium atom positions in molecules as large as proteins is a unique capability of neutron diffraction. The comparison addresses the degree to which a standard force-field approach can adequately describe the local electrostatic and van der Waals forces that determine the orientations of these hydrogens. Neutron densities, derived from 2.1{Angstrom} D{sub 2}O-H{sub 2}O difference Fourier maps, provide a database of 27 well-ordered hydroxyl hydrogens. Most of the simulated hydroxyl orientations are within a standard deviation of the experimentally-observed positions, including several examples in which both the simulation and the neutron density indicate that a hydroxyl group is shifted from a {open_quote}standard{close_quote} rotamer. For the most highly ordered water molecules, the hydrogen distributions calculated from the trajectory were in good agreement with neutron density; simulated water molecules that displayed multiple hydrogen bonding networks had correspondingly broadened neutron density profiles. This comparison was facilitated by development of a method to construct a pseudo 2{Angstrom} density map based on the hydrogen atom distributions from the simulation. The degree of disorder of internal water molecules is shown to result primarily from the electrostatic environment surrounding that water molecule as opposed to the cavity size available to the molecule. A method is presented for comparing the discrete observations sampled in a dynamics trajectory with the time- averaged data obtained from X-ray or neutron diffraction studies. This method is particularly useful for statically-disordered water molecules, in which the average location assigned from a trajectory may represent a site of relatively low occupancy.

  17. Resolution and reconstitution of cytochrome P-450 containing steroid hydroxylation system of Rhizopus nigricans. (United States)

    Breskvar, K; Cresnar, B; Hudnik-Plevnik, T


    11 alpha-hydroxylation of progesterone in the eucaryotic filamentous fungus Rhizopus nigricans is catalyzed by a monooxygenase. Three components of this multienzyme system, cytochrome P-450, rhizoporedoxin and a FAD containing rhizoporedoxin reductase have been separated from the postmitochondrial fraction on DEAE cellulose. Using NADPH as electron donor we showed that the presence of all three components was necessary for the reconstitution of the active electron transport chain.

  18. Facile synthesis of highly water-soluble fullerenes more than half-covered by hydroxyl groups. (United States)

    Kokubo, Ken; Matsubayashi, Kenji; Tategaki, Hiroshi; Takada, Hiroya; Oshima, Takumi


    Using a novel hydrogen peroxide heating method, we synthesized milky white, water-soluble polyhydroxylated fullerenes (fullerenols) with 36-40 hydroxyl groups (estimated average) along with 8-9 secondary bound water molecules. The fullerenols exhibited high water solubility up to 58.9 mg/mL in a neutral (pH = 7) condition. Dynamic light scattering analysis showed a high dispersion property, to give a narrow particle size distribution within 0.7-2.0 nm.

  19. Hydroxyl radical reactions with volatile organic compounds under simulated tropospheric conditions: tropospheric lifetimes

    Energy Technology Data Exchange (ETDEWEB)

    Semadeni, M.


    Kinetic investigations of the hydroxyl radical reaction with volatile organic compounds (VOC) are important to estimate the potential of VOCs in air pollution. The temperature dependence of the rate coefficients of the hydroxyl radical reaction with members of two classes of organic compounds have been measured under simulated tropospheric conditions using a competitive technique rebuilt in this laboratory. A thermostat flow reactor was employed, which was specially constructed to investigate gas-phase reactions under atmospheric pressure. The hydroxyl radical reactions of the organic test compounds have been measured in the presence of given reference compounds over the temperature range (273-373) K using GC/FID. The rate coefficients obtained in the present study range from 11-42x10[sup -12] cm[sup 3] molecule[sup -1] s[sup -1] and from 1-52x10[sup -12] cm[sup 3] molecule[sup -1] s[sup -1] for the following ethers and aromatic compounds respectively: diethyl ether, methyl n-butyl ether, ethyl n-butyl ether, di-n-butyl ether, di-n-pentyl ether and benzene, toluene, benzaldehyde, phenol, o-cresol, m-cresol, p-cresol, arranged according to their increasing reactivity within their class. The temperature dependence of the hydroxyl radical with methyl n-butyl ether, di-n-butyl ether, m-cresol, p-cresol and benzaldehyde have been determined for the first time in this study. The Arrhenius parameters obtained confirm the negative temperature dependence often observed in this type of reaction. The results of the present study show, that the experimental system employed can provide accurate kinetic data and discrepancies occurred in previous studies have been resolved. (author) figs., tabs., refs.

  20. Steroid Hydroxylation by Basidiomycete Peroxygenases: a Combined Experimental and Computational Study (United States)

    Babot, Esteban D.; del Río, José C.; Cañellas, Marina; Sancho, Ferran; Lucas, Fátima; Guallar, Víctor; Kalum, Lisbeth; Lund, Henrik; Gröbe, Glenn; Scheibner, Katrin; Ullrich, René; Hofrichter, Martin; Martínez, Angel T.


    The goal of this study is the selective oxyfunctionalization of steroids under mild and environmentally friendly conditions using fungal enzymes. With this purpose, peroxygenases from three basidiomycete species were tested for the hydroxylation of a variety of steroidal compounds, using H2O2 as the only cosubstrate. Two of them are wild-type enzymes from Agrocybe aegerita and Marasmius rotula, and the third one is a recombinant enzyme from Coprinopsis cinerea. The enzymatic reactions on free and esterified sterols, steroid hydrocarbons, and ketones were monitored by gas chromatography, and the products were identified by mass spectrometry. Hydroxylation at the side chain over the steroidal rings was preferred, with the 25-hydroxyderivatives predominating. Interestingly, antiviral and other biological activities of 25-hydroxycholesterol have been reported recently (M. Blanc et al., Immunity 38:106–118, 2013, However, hydroxylation in the ring moiety and terminal hydroxylation at the side chain also was observed in some steroids, the former favored by the absence of oxygenated groups at C-3 and by the presence of conjugated double bonds in the rings. To understand the yield and selectivity differences between the different steroids, a computational study was performed using Protein Energy Landscape Exploration (PELE) software for dynamic ligand diffusion. These simulations showed that the active-site geometry and hydrophobicity favors the entrance of the steroid side chain, while the entrance of the ring is energetically penalized. Also, a direct correlation between the conversion rate and the side chain entrance ratio could be established that explains the various reaction yields observed. PMID:25862224

  1. Prevention of hydroxyl radical formation: a critical concept for improving cardioplegia. Protective effects of deferoxamine. (United States)

    Menasche, P; Grousset, C; Gauduel, Y; Mouas, C; Piwnica, A


    The hydroxyl radical is one of the most damaging oxygen metabolites that are thought to be produced during ischemia and reperfusion of cardiac tissue. Therefore, we used the isolated, isovolumetric, buffer-perfused rat heart preparation of cardioplegic arrest to assess the effects of interventions targeted at inhibiting production of the hydroxyl radical by decreasing either the availability of one of its precursors (hydrogen peroxide) or that of the metal catalyst (ferric iron) involved in the radical formation. Sixty hearts were studied and, except for nonischemic controls, were subjected to 3 hr of hypothermic (15 degrees to 18 degrees C) cardioplegic arrest, followed by 45 min of reperfusion. The following interventions were tested: pretreatment with peroxidase, a scavenger of hydrogen peroxide, pretreatment with a combination of peroxidase and the iron chelator deferoxamine, pretreatment with peroxidase followed by supplementation of the cardioplegic solution with deferoxamine, and supplementation of the cardioplegic solution with deferoxamine without preischemic enzymatic treatment. Based on comparisons of postreperfusion pressure development, maximal ventricular dP/dt, left ventricular compliance, and coronary flow, deferoxamine-containing cardioplegic solution alone afforded the best myocardial protection. This may be due to the ability of deferoxamine to act both as an iron chelator and as a direct scavenger of superoxide anion, an activated oxygen species that participates in hydroxyl radical formation. This study confirms that an important component of the cardiac damage sustained during global ischemia and reperfusion may involve injury caused by the hydroxyl radical. Furthermore, our results point out the potential therapeutic usefulness of deferoxamine in the context of cardioplegic protection during open-heart procedures.

  2. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo


    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  3. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation. (United States)

    Minakata, Daisuke; Crittenden, John


    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

  4. Experimental Studies on the Synthesis and Performance of Boron-containing High Temperature Resistant Resin Modified by Hydroxylated Tung Oil (United States)

    Zhang, J. X.; Y Ren, Z.; Zheng, G.; Wang, H. F.; Jiang, L.; Fu, Y.; Yang, W. Q.; He, H. H.


    In this work, hydroxylated tung oil (HTO) modified high temperature resistant resin containing boron and benzoxazine was synthesized. HTO and ethylenediamine was used to toughen the boron phenolic resin with specific reaction. The structure of product was studied by Fourier-transform infrared spectroscopy(FTIR), and the heat resistance was tested by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis(TGA). The results indicated that the conjugated triene structure of HTO was involved in the crosslinking of the heating curing progress, and in addition, the open-loop polymerization reaction of benzoxazine resin during heating can effectively reduce the curing temperature of the resin and reduce the release of small molecule volatiles, which is advantageous to follow-up processing. DSC data showed that the initial decomposition temperature of the resin is 350-400 °C, the carbon residue rate under 800 °C was 65%. It indicated that the resin has better heat resistance than normal boron phenolic resin. The resin can be used as an excellent ablative material and anti-friction material and has a huge application market in many fields.

  5. Oh where OH where is Oh? Measuring the Elusive Hydroxyl Radical in the Atmosphere Using Laser-Induced Fluorescence (United States)

    Stevens, Philip S.


    The hydroxyl radical (OH) plays a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change and stratospheric ozone depletion, the OH radical initiates the oxidation of carbon monoxide and volatile organic compounds which in the presence of nitrogen oxides can lead to the production of ground-level ozone and secondary organic aerosols, the primary components of photochemical smog. Accurate measurements of OH radical concentrations in the atmosphere can provide critical tests of our understanding of atmospheric chemistry and ground-level ozone production in urban and rural areas. Because of its high reactivity, mixing ratios of OH in the atmosphere are extremely low (typically less than 0.1 parts per trillion) and its chemical lifetime very short (less than 1 second). As a result, measurements of OH present a serious analytical challenge, especially on the timescale necessary to test our understanding of the fast photochemistry of the atmosphere. This presentation will describe the Indiana University laser-induced fluorescence instrument for the sensitive detection of OH radicals in the atmosphere, including recent results from several measurement campaigns in both urban and rural environments.

  6. JMJD6 promotes colon carcinogenesis through negative regulation of p53 by hydroxylation.

    Directory of Open Access Journals (Sweden)

    Feng Wang


    Full Text Available Jumonji domain-containing 6 (JMJD6 is a member of the Jumonji C domain-containing family of proteins. Compared to other members of the family, the cellular activity of JMJD6 is still not clearly defined and its biological function is still largely unexplored. Here we report that JMJD6 is physically associated with the tumor suppressor p53. We demonstrated that JMJD6 acts as an α-ketoglutarate- and Fe(II-dependent lysyl hydroxylase to catalyze p53 hydroxylation. We found that p53 indeed exists as a hydroxylated protein in vivo and that the hydroxylation occurs mainly on lysine 382 of p53. We showed that JMJD6 antagonizes p53 acetylation, promotes the association of p53 with its negative regulator MDMX, and represses transcriptional activity of p53. Depletion of JMJD6 enhances p53 transcriptional activity, arrests cells in the G1 phase, promotes cell apoptosis, and sensitizes cells to DNA damaging agent-induced cell death. Importantly, knockdown of JMJD6 represses p53-dependent colon cell proliferation and tumorigenesis in vivo, and significantly, the expression of JMJD6 is markedly up-regulated in various types of human cancer especially in colon cancer, and high nuclear JMJD6 protein is strongly correlated with aggressive clinical behaviors of colon adenocarcinomas. Our results reveal a novel posttranslational modification for p53 and support the pursuit of JMJD6 as a potential biomarker for colon cancer aggressiveness and a potential target for colon cancer intervention.

  7. Antimicrobial Intervention by Photoirradiation of Grape Pomace Extracts via Hydroxyl Radical Generation

    Directory of Open Access Journals (Sweden)

    Yoshimi Niwano


    Full Text Available The annual production of grape worldwide amounts to almost 70 million tons, and around 80% is used for winemaking. The two major wastes from winemaking process, pomace and lees account for 20 and 7% of the grapes, respectively. They have been expected as a valuable resource to be recycled because they are rich in polyphenols. Polyphenols possess prooxidatve activity as well as antioxidative one just like a two sides of a coin. A typical example of the prooxidative activity is antibacterial activity of catechins. The activity is exerted through oxidation of phenolic hydroxyl moiety coulpled with reduction of dissolved oxygen leading to hydrogen peroxide (H2O2 generation. In addition, once the oxidation of phenolic hydroxyl moiety is augmented by photoirradiation, highly reactive hydroxyl radical (·OH is generated. Accordingly, there have been several reports showing that photoirardiation of polyphenols exerts bactericidal activity via ·OH generation. This review focuses mainly on antimicrobial intervention by photoirradiation of grape pomace extract in relation to ·OH generation analyzed by an electron spin resonance-spin trapping method.

  8. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals. (United States)

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng


    A systematic study of the antioxidation mechanisms behind hydroxyl (•OH) and hydroperoxyl (•OOH) radical scavenging activity of piceatannol (PIC) and isorhapontigenin (ISO) was carried out using density functional theory (DFT) method. Two reaction mechanisms, abstraction (ABS) and radical adduct formation (RAF), were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB) are considerable in determining the antioxidant activity of PIC and ISO.

  9. Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds (United States)

    Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang


    The novel class of luminescent Al3 +-based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2‧:6‧,2″-terpyridine]-4‧-ylbenzoic acid (Hcptpy) with Al3 + under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467 nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0 μM with a detection limit of 4.64 μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA.

  10. Stochastic adhesion of hydroxylated atomic force microscopy tips to supported lipid bilayers. (United States)

    Apetrei, Aurelia; Sirghi, Lucel


    This work reports results of an atomic force microscopy (AFM) study of adhesion force between hydroxylated AFM tips and supported lipid bilayers (SLBs) of phosphatidylcholine in phosphate buffer saline solution at neutral pH. Silicon nitride AFM probes were hydroxylated by treatment in water vapor plasma and used in force spectroscopy measurements of adhesion force on SLBs with control of contact loading force and residence time. The measurements showed a stochastic behavior of adhesion force that was attributed to stochastic formation of hydrogen bonds between the hydroxyl groups on the AFM tip and oxygen atoms from the phosphate groups of the phosphatidylcholine molecules. Analysis of a large number of force curves revealed a very low probability of hydrogen bond formation, a probability that increased with the increase of contact loading force and residence time. The variance and mean values of adhesion force showed a linear dependence on each other, which indicated that hydrogen bond formation obeyed the Poisson distribution of probability. This allowed for the quantitative determination of the rupture force per hydrogen bond of about 40 pN and showed the absence of other nonspecific interaction forces.

  11. Synthesis and gas transport properties of hydroxyl-functionalized polyimides with intrinsic microporosity

    KAUST Repository

    Ma, Xiaohua


    A newly designed diamine monomer, 3,3,3′,3′-tetramethyl-1, 1′-spirobisindane-5,5′-diamino-6,6′-diol, was successfully used to synthesize two types of polyimides for membrane-based gas separation applications. The novel polymers integrate significant microporosity and polar hydroxyl groups, showing the combined features of polymers of intrinsic microporosity (PIMs) and functional polyimides (PIs). They possess high thermal stability, good solubility, and easy processability for membrane fabrication; the resulting membranes exhibit good permeability owing to the intrinsic microporosity introduced by the highly contorted PIM segments as well as high CO 2/CH 4 selectivity that arises from the hydroxyl groups. The membranes show CO 2/CH 4 selectivities of >20 when tested with a 1:1 CO 2/CH 4 mixture for feed pressures up to 50 bar. In addition, the incorporation of hydroxyl groups and microporosity in the polymers enhances their affinity to water, leading to remarkable water sorption capacities of up to 22 wt % at 35 °C and 95% relative humidity. © 2012 American Chemical Society.

  12. Reaction mechanisms of DNT with hydroxyl radicals for advanced oxidation processes-a DFT study. (United States)

    Zhou, Yang; Yang, Zhilin; Yang, Hong; Zhang, Chaoyang; Liu, Xiaoqiang


    In advanced oxidation processes (AOPs), the detailed degradation mechanisms of a typical explosive of 2,4-dinitrotoluene (DNT) can be investigated by the density function theory (DFT) method at the SMD/M062X/6-311+G(d) level. Several possible degradation routes for DNT were explored in the current study. The results show that, for oxidation of the methyl group, the dominant degradation mechanism of DNT by hydroxyl radicals (•OH) is a series of sequential H-abstraction reactions, and the intermediates obtained are in good agreement with experimental findings. The highest activation energy barrier is less than 20 kcal mol(-1). Other routes are dominated by an addition-elimination mechanism, which is also found in 2,4,6-trinitrotoluene, although the experiment did not find the corresponding products. In addition, we also eliminate several impossible mechanisms, such as dehydration, HNO3 elimination, the simultaneous addition of two •OH radials, and so on. The information gained about these degradation pathways is helpful in elucidating the detailed reaction mechanism between nitroaromatic explosives and hydroxyl radicals for AOPs. Graphical Abstract The degradation mechanism of an important explosive, 2,6-dinitrotoluene (DNT), by the hydroxyl radical for advanced oxidation progresses.

  13. Regio- and enantioselective microbial hydroxylation and evaluation of cytotoxic activity of β-cyclocitral-derived halolactones.

    Directory of Open Access Journals (Sweden)

    Marcelina Mazur

    Full Text Available Three β-cyclocitral-derived halolactones, which exhibit antifeedant activity towards storage product pests, were subjected to microbial transformation processes. Among the thirty tested strains of filamentous fungi and yeast, the most effective biocatalysts were Absidia cylindrospora AM336, Mortierella isabellina AM212 and Mortierella vinaceae AM149. As a result of regio- and enantioselective hydroxylation four new oxygenated derivatives were obtained. Regardless of the biocatalyst applied, the δ-iodo- and δ-bromo-γ-lactones were hydroxylated in an inactivated position C-5 of cyclohexane ring. The analogous transformation of chlorolactone was observed in Mortierella isabellina AM212 culture but in the case of two other biocatalysts the hydroxy group was introduced at C-3 position. All obtained hydroxylactones were enantiomerically pure (ee = 100% or enriched (ee = 50%. The highest enantioselectivity of hydroxylation was observed for M. isabellina AM212. The cytotoxic activity of halolactones was also examined by WST-1 assay wherein tested compounds did not exhibit significant effect on the viability of tumor HeLa and normal CHO-K1 cells.

  14. A simple electrochemical method for the determination of hydroxyl free radicals without separation process. (United States)

    Hu, Yu-Lin; Lu, Yu; Zhou, Guo-Jun; Xia, Xing-Hua


    Generally speaking, measurement of hydroxylated radical products of salicylic acid requires a fussy separation process. In this study, we describe a simple method to electrochemically detect hydroxyl radicals (*OH) using 4-hydroxybenzoic acid (4-HBA) as the *OH trap. The *OH is generated by the Fenton reaction from iron (II) sulfate and hydrogen peroxide in a phosphate buffer solution. Experimental results show that our method can detect the OH with high sensitivity without any separation process. The differential pulse voltammetric responses show a linear dependence on the concentration of *OH in a range of 2.0x10(-6) and 1.0x10(-3)M with a determination limit down to 5.0x10(-7)M. As a demonstration, the kinetics of the Fenton reaction was mapped by measuring the reaction product of hydroxyl radical trapped by 4-HBA. The result is in good agreement with that reported previously. All the results show that the present approach could provide a simple, inexpensive and promising method for biomedicine and iatrology.

  15. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals.

    Directory of Open Access Journals (Sweden)

    Yang Lu

    Full Text Available A systematic study of the antioxidation mechanisms behind hydroxyl (•OH and hydroperoxyl (•OOH radical scavenging activity of piceatannol (PIC and isorhapontigenin (ISO was carried out using density functional theory (DFT method. Two reaction mechanisms, abstraction (ABS and radical adduct formation (RAF, were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB are considerable in determining the antioxidant activity of PIC and ISO.

  16. Complex Cure Kinetics of the Hydroxyl-Epoxide Reaction in DGEBA Epoxy Hardened with Diethanolamine (United States)

    Ancipink, Windy; McCoy, John; Kropka, Jamie; Celina, Mathias

    The curing of a diglycidyl ether of bisphenol-A Epoxy (Epon 828) with diethanolamine (DEA) involves a fast amine-epoxide reaction followed by a slower hydroxyl-epoxide reaction. At curing temperatures below 100°C, the time scales of these two reactions are well separated, and the hydroxyl addition can be studied as an ''isolated'' reaction. The hydroxyl-epoxide reaction is of great interest due to the complex kinetics involved, which are brought about by competing reactions. The reaction kinetics are believed to be tertiary amine catalyzed and are well fit to a modified form of the Kamal-type equation. Here we study the complex long term reaction kinetics at various temperatures, by using isothermal modulated differential scanning calorimetry, micro calorimetry, and infrared spectroscopy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  17. FIH Regulates Cellular Metabolism through Hydroxylation of the Deubiquitinase OTUB1.

    Directory of Open Access Journals (Sweden)

    Carsten C Scholz


    Full Text Available The asparagine hydroxylase, factor inhibiting HIF (FIH, confers oxygen-dependence upon the hypoxia-inducible factor (HIF, a master regulator of the cellular adaptive response to hypoxia. Studies investigating whether asparagine hydroxylation is a general regulatory oxygen-dependent modification have identified multiple non-HIF targets for FIH. However, the functional consequences of this outside of the HIF pathway remain unclear. Here, we demonstrate that the deubiquitinase ovarian tumor domain containing ubiquitin aldehyde binding protein 1 (OTUB1 is a substrate for hydroxylation by FIH on N22. Mutation of N22 leads to a profound change in the interaction of OTUB1 with proteins important in cellular metabolism. Furthermore, in cultured cells, overexpression of N22A mutant OTUB1 impairs cellular metabolic processes when compared to wild type. Based on these data, we hypothesize that OTUB1 is a target for functional hydroxylation by FIH. Additionally, we propose that our results provide new insight into the regulation of cellular energy metabolism during hypoxic stress and the potential for targeting hydroxylases for therapeutic benefit.

  18. Suppression of LPS-induced inflammatory responses by the hydroxyl groups of dexamethasone. (United States)

    Chuang, Ting-Yun; Cheng, An-Jie; Chen, I-Ting; Lan, Tien-Yun; Huang, I-Hsuan; Shiau, Chung-Wai; Hsu, Chia-Lin; Liu, Ya-Wen; Chang, Zee-Fen; Tseng, Ping-Hui; Kuo, Jean-Cheng


    The innate immune response is a central process that is activated during pathogenic infection in order to maintain physiological homeostasis. It is well known that dexamethasone (Dex), a synthetic glucocorticoid, is a potent immunosuppressant that inhibits the cytokine production induced by bacterial lipopolysaccharides (LPS). Nevertheless, the extent to which the functional groups of Dex control the excessive activation of inflammatory reactions remains unknown. Furthermore, importantly, the role of Dex in the innate immune response remains unclear. Here we explore the mechanism of LPS-induced TNF-α secretion and reveal p38 MAPK signaling as a target of Dex that is involved in control of tumor necrosis factor-α (TNF-α)-converting enzyme (TACE) activity; that later mediates the shedding of TNF-α that allows its secretion. We further demonstrate that the 11-hydroxyl and 21-hydroxyl groups of Dex are the main groups that are involved in reducing LPS-induced TNF-α secretion by activated macrophages. Blockage of the hydroxyl groups of Dex inhibits immunosuppressant effect of Dex during LPS-induced TNF-α secretion and mouse mortality. Our findings demonstrate Dex signaling is involved in the control of innate immunity.

  19. Determination of phthalate esters in airborne particulates by heterogeneous photo-Fenton catalyzed aromatic hydroxylation fluorimetry. (United States)

    Zeng, He-Hua; Li, Xue-Qin; Hao, Wen-Li; Zhang, Li-Zhong; Wei, Ting; Zhao, Xiu-Feng; Liu, Yu-Yan; Li, Jian-Hui


    The environmental contaminants phthalic acid esters (PAEs) were determined by aromatic hydroxylation fluorimetry combined with heterogeneous photo-Fenton process in the presence of vermiculite supported BiFeO3 (VMT-BiFeO3). In strong alkaline solution, PAEs were hydrolyzed into phthalates with no fluorescence, which then reacted with hydroxyl free radicals produced in photo-Fenton process catalyzed by VMT-BiFeO3 to form the fluorescent hydroxyl phthalates. The fluorescence intensity was proportional to the concentration of PAEs with the maximum excitation and emission wavelength of 300nm and 417nm, respectively. A good linear relationship can be obtained in the range of 3.8×10-7 to 4.8×10-5molL-1 for DEP with correlation coefficient of 0.9997, and the sensitivity of the method was high with detection limit of 5.43×10-8molL-1. The method has been successfully applied to determine total PAEs in airborne particulates with satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Measurement of hydroxyl radical density generated from the atmospheric pressure bioplasma jet (United States)

    Hong, Y. J.; Nam, C. J.; Song, K. B.; Cho, G. S.; Uhm, H. S.; Choi, D. I.; Choi, E. H.


    Atmospheric pressure bioplasmas are being used in a variety of bio-medical and material processing applications, surface modifications of polymers. This plasma can generate the various kinds of radicals when it contacs with the water. Especially, hydroxyl radical species have very important role in the biological and chemical decontamination of media in this situation. It is very important to investigate the hydroxyl radical density in needle-typed plasma jet since it plays a crucial role in interaction between the living body and plasma. We have generated the needle-typed plasma jet bombarding the water surface by using an Ar gas flow and investigated the emission lines by OES (optical emission spectroscopy). It is noted that the electron temperature and plasma density are measured to be about 1.7 eV and 3.4 × 1012 cm-3, respectively, under Ar gas flow ranged from 80 to 300 sccm (standard cubic centimeter per minute) in this experiment. The hydroxyl radical density has also been investigated and measured to be maximum value of 2.6 × 1015 cm-3 for the gas flow rate of 150 sccm in the needle-typed plasma jet by the ultraviolet optical absorption spectroscopy.

  1. Initial Study

    DEFF Research Database (Denmark)

    Torp, Kristian


    increased. In the initial study presented here, the time it takes to pass an intersection is studied in details. Two major signal-controlled four-way intersections in the center of the city Aalborg are studied in details to estimate the congestion levels in these intersections, based on the time it takes...

  2. The effect of O 2 and NO 2 on the ring retaining products of the reaction of toluene with hydroxyl radicals (United States)

    Moschonas, Nektarios; Danalatos, Demetrios; Glavas, Sotirios

    The reaction of toluene with hydroxyl radicals produces ring retaining products either from H-atom abstraction from the methyl group: benzaldehyde and benzylalcohol or from the addition of the hydroxyl radical to the aromatic ring: o-, m+ p-cresol. The yields obtained in experiments carried out in nitrogen and in air matrix were statistically not significantly different. The addition of NO 2 to the reactants had no effect on the formed o-cresol, indicating that reaction of the hydroxy-methylcyclohexadienyl radical with NO 2 is not contributing significantly to the formation of o-cresol. This is in agreement with recent studies postulating the more stable toluene oxide as the intermediate resulting from the reaction of hydroxy-methylcyclohexadienyl with oxygen rather than the peroxy radical. m-nitrotoluene was the major nitrotoluene formed in the presence of NO 2, increasing linearly with increasing the initial concentration of NO 2 with zero intercept. The observed 2-methyl 1,4 benzoquinone and traces of phenol and benzene were determined to be secondary products.

  3. Pulse radiolysis studies on reactions of hydroxyl radicals with selenocystine derivatives. (United States)

    Mishra, B; Kumbhare, L B; Jain, V K; Priyadarsini, K I


    Reactions of hydroxyl radicals (*OH) with selenocystine (SeCys) and two of its analogues, diselenodipropionic acid (SeP) and selenocystamine (SeA), have been studied in aqueous solutions at pHs of 1, 7, and 10 using the pulse radiolysis technique coupled with absorption detection. All of these diselenides react with *OH radicals with rate constants of approximately 10(10) M(-1) s(-1), producing diselenide radical cations ( approximately 1-5 micros after the pulse), with an absorption maximum at 560 nm, by elimination of H(2)O or OH(-) from hydroxyl radical adducts. Assignment of the 560 nm band to the diselenide radical cation was made by comparing the transient spectra with those produced upon reaction of diselenides with specific one-electron oxidants, Cl(2)(*-) (pH 1) and Br(2)(*-) radicals (pHs of 7 and 10). SeP having a carboxylic acid functionality showed quantitative conversion of hydroxyl radical adducts to radical cations. The compounds SeCys and SeA, having an amino functional group, in addition to the radical cations, produced a new transient with lambda(max) at 460 nm, at later time scales ( approximately 20-40 micros after the pulse). The rate and yield of formation of the 460 nm band increased with increasing concentrations of either SeCys or SeA. In analogy with similar studies reported for analogous disulfides, the 460 nm transient absorption band has been assigned to a triselenide radical adduct. The one-electron reduction potentials of the compounds were estimated to be 0.96, 1.3, and 1.6 V versus NHE, respectively, for SeP, SeCys, and SeA at pH 7. From these studies, it has been concluded that the electron-donating carboxylic acid group decreases the reduction potential and facilitates quantitative conversion of hydroxyl radical adducts to radical cations, while the electron-withdrawing NH(3)(+) group not only increases the reduction potential but also leads to fragmentation of the hydroxyl radical adduct to selenyl radicals, which are converted

  4. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Munoz, Jose Luis [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Berna, Jose [Grupo de Quimica Organica Sintetica, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Garcia-Molina, Maria del Mar; Garcia-Molina, Francisco [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Garcia-Ruiz, Pedro Antonio [QCPAI - Grupo de Quimica de Carbohidratos, Polimeros y Aditivos Industriales, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Varon, Ramon [Departamento de Quimica-Fisica, Escuela de Ingenieros Industriales de Albacete, Universidad de Castilla la Mancha, Avda. Espana s/n. Campus Universitario, E-02071 Albacete (Spain); and others


    Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that

  5. Aqueous photochemical degradation of hydroxylated PAHs: Kinetics, pathways, and multivariate effects of main water constituents

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Chen, Chang-Er [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Li, Jun [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); College of Marine Science, Shanghai Ocean University, Shanghai 201306 (China); Ju, Maowei; Wang, Ying; Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)


    Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are contaminants of emerging concern in the aquatic environment, so it is of great significance to understand their environmental transformation and toxicity. This study investigated the aqueous photochemical behavior of four OH-PAHs, 9-Hydroxyfluorene (9-OHFL), 2-Hydroxyfluorene, 9-Hydroxyphenanthrene and 1-Hydroxypyrene, under simulated sunlight irradiation (λ > 290 nm). It was observed that their photodegradation followed the pseudo-first-order kinetics. Based on the determined quantum yields, their calculated solar apparent photodegradation half-lives in surface waters at 45° N latitude ranged from 0.4 min for 9-Hydroxyphenanthrene to 7.5 × 10{sup 3} min for 9-OHFL, indicating that the OH-PAHs would intrinsically photodegrade fast in sunlit surface waters. Furthermore, 9-OHFL as an example was found to undergo direct photolysis, and self-sensitized photooxidation via ·OH rather than {sup 1}O{sub 2} in pure water. The potential photoreactions involved photoinduced hydroxylation, dehydrogenation and isomerization based on product identification by GC–MS/MS. 9-OHFL photodegraded slower in natural waters than in pure water, which was attributed to the integrative effects of the most photoreactive species, such as Fe(III), NO{sub 3}{sup −}, Cl{sup −} and humic acid. The photomodified toxicity was further examined using Vibrio fischeri, and it was found that the toxicity of photolyzed 9-OHFL did not decrease significantly (p > 0.05) either in pure water or in seawater, implying the comparable or higher toxicity of some intermediates. These results are important for assessing the fate and risks of OH-PAHs in surface waters. - Graphical abstract: Aqueous photochemical behavior of 4 hydroxylated PAHs is first reported on revealing the kinetics, mechanisms, toxicity, and multivariate effects of water constituents. - Highlights: • It is first reported on aqueous photochemical behavior of 4 hydroxylated

  6. New fluorescent probes of the hydroxyl radical: characterisation and modelization of the reactivity of coumarin derivatives with HO; Developpement de sondes fluorescentes du radical hydroxyle: caracterisation et modelisation de la reactivite de molecules derivees de la coumarine avec HO

    Energy Technology Data Exchange (ETDEWEB)

    Louit, G.


    The hydroxyl radical is involved in a wide range of different fields, from oxidative stress to atmospheric chemistry. In addition to the study of oxidative damage in biological media, the hydroxyl radical detection allows to perform a dosimetry when it is produced by ionising radiation. The aims of this work have been double: - to improve the detection of the hydroxyl radical by the design of new probes - to improve knowledge on the reactive pathways in which the hydroxyl radical is involved. We have studied the coumarin molecule, as well as 6 derivatives that we have synthesised, as fluorescent probes of the hydroxyl radical. Firstly, fluorescence spectroscopy and HPLC chromatography have allowed the evaluation of the sensibility and selectivity of detection of the probes. Consequently to this study, two applications have been developed, concerning the determination of rate constants by competition kinetics and bidimensional dosimetry. Secondly, we have studied the reactivity of the hydroxyl radical through the regioselectivity of its addition on the aromatic cycle. This problem was addressed by the combined use of experimental methods such as time resolved kinetics and HPLC along with interpretation from classical and ab initio modelization. (author)

  7. Quantitative measurement of hydroxyl radical induced DNA double-strand breaks and the effect of N-acetyl-L-cysteine. (United States)

    Su, Meihong; Yang, Yao; Yang, Guoliang


    Reactive oxygen species, such as hydroxyl or superoxide radicals, can be generated by exogenous agents as well as from normal cellular metabolism. Those radicals are known to induce various lesions in DNA, including strand breaks and base modifications. These lesions have been implicated in a variety of diseases such as cancer, arteriosclerosis, arthritis, neurodegenerative disorders and others. To assess these oxidative DNA damages and to evaluate the effects of the antioxidant N-acetyl-L-cysteine (NAC), atomic force microscopy (AFM) was used to image DNA molecules exposed to hydroxyl radicals generated via Fenton chemistry. AFM images showed that the circular DNA molecules became linear after incubation with hydroxyl radicals, indicating the development of double-strand breaks. The occurrence of the double-strand breaks was found to depend on the concentration of the hydroxyl radicals and the duration of the reaction. Under the conditions of the experiments, NAC was found to exacerbate the free radical-induced DNA damage.

  8. Measurement of Absolute Hydroxyl Radical Concentration in Lean Fuel-Air Mixtures Excited by Nanosecond Pulsed Discharge. (United States)

    Yin, Z.; Lempert, W. R.; Adamovich, I. V.


    The focus in plasma assisted combustion research has been on the evaluation of conventional plasma/combustion mechanisms in predicting oxidation and ignition processes initiated and/or sustained by non-equilibrium, nanosecond discharges. Accurate quantitative data such as temperature and species concentration are needed for assessing and improving numerical modeling. As an important intermediate species, the concentration of hydroxyl radical (OH) is very sensitive to the combustion environment (e.g., temperature, equivalence ratio), and therefore is of great interest to kinetic study. In this work, Laser-Induced Fluorescence (LIF) was used for time-resolved temperature and OH number density measurements in lean H_2-, CH_4-, C_2H_4-, and C_3H_8- air mixtures in a plasma flow reactor inside a tube furnace. The premixed fuel-air flow in the reactor, initially at T_0=500 K and P=100 torr, was excited by a burst of repetitive nanosecond electric pulses in a dielectric-barrier plane-to-plane geometry (˜28 kV peak voltage and ˜5 nsec pulse width, estimated 1.25 mJ/pulse coupled energy). Laser was timed to probe after the discharge burst was over to avoid strong plasma emission interference. Relative fluorescence signal was put on an absolute scale by calibrating against Rayleigh scattering signal in the same flow reactor. Experimental results were compared to predictions from a 0-D plasma/combustion chemistry model employing several well-established combustion mechanisms. 2-D temperature and OH concentration distributions in the discharge volume were obtained by planar LIF and was used to quantitatively evaluate plasma uniformity in the reactor. These results were used to determine the validity of the 0-D model. thanks

  9. Biocatalytic hydroxylation of n-butane with in situ cofactor regeneration at low temperature and under normal pressure

    Directory of Open Access Journals (Sweden)

    Svenja Staudt


    Full Text Available The hydroxylation of n-alkanes, which proceeds in the presence of a P450-monooxygenase advantageously at temperatures significantly below room temperature, is described. In addition, an enzymatic hydroxylation of the “liquid gas” n-butane with in situ cofactor regeneration, which does not require high-pressure conditions, was developed. The resulting 2-butanol was obtained as the only regioisomer, at a product concentration of 0.16 g/L.

  10. Inhibition of microsomal oxidation of alcohols and of hydroxyl-radical-scavenging agents by the iron-chelating agent desferrioxamine.


    Cederbaum, A I; Dicker, E


    Rat liver microsomes (microsomal fractions) catalyse the oxidation of straight-chain aliphatic alcohols and of hydroxyl-radical-scavenging agents during NADPH-dependent electron transfer. The iron-chelating agent desferrioxamine, which blocks the generation of hydroxyl radicals in other systems, was found to inhibit the following microsomal reactions: production of formaldehyde from either dimethyl sulphoxide or 2-methylpropan-2-ol (t-butylalcohol); generation of ethylene from 4-oxothiomethyl...

  11. Structure-guided unravelling: Phenolic hydroxyls contribute to reduction of acrylamide using multiplex quantitative structure-activity relationship modelling. (United States)

    Zhang, Yu; Huang, Mengmeng; Wang, Qiao; Cheng, Jun


    We reported a structure-activity relationship study on unravelling phenolic hydroxyls instead of alcoholic hydroxyls contribute to the reduction of acrylamide formation by flavonoids. The dose-dependent study shows a close correlation between the number of phenolic hydroxyls of flavonoids and their reduction effects. In view of positions of hydroxyls, the 3',4'(ortho)-dihydroxyls in B cycle, 3-hydroxyl or hydroxyls of 3-gallate in C cycle, and 5,7(meta)-dihydroxyls in A cycle of flavonoid structures play an important role in the reduction of acrylamide. Flavone C-glycosides are more effective at reducing the formation of acrylamide than flavone O-glycosides when sharing the same aglycone. The current multiplex quantitative structure-activity relationship (QSAR) equations effectively predict the inhibitory rates of acrylamide using selected chemometric parameters (R(2): 0.835-0.938). This pioneer study opens a broad understanding on the chemoprevention of acrylamide contaminants on a structural basis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Radiation damage to human erythrocytes. Relative contribution of hydroxyl and chloride radicals in N{sub 2}O-saturated buffers

    Energy Technology Data Exchange (ETDEWEB)

    Krokosz, Anita [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90 237 Lodz (Poland)], E-mail:; Komorowska, Magdalena A.; Szweda-Lewandowska, Zofia [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90 237 Lodz (Poland)


    The erythrocyte suspensions in Na-phosphate buffered isotonic NaCl solution (PBS) or Na-phosphate isotonic buffer (PB) (hematocrit 1%) were irradiated with the dose of 400 Gy under N{sub 2}O. Erythrocytes were incubated in the medium in which the cells were irradiated or in fresh PBS. The level of damage to cells was estimated on the basis of the course of post-radiation hemolysis and hemoglobin (Hb) oxidation. The medium in which the cells were irradiated and incubated influenced the course of the post-radiation hemolysis and Hb oxidation as well as some other parameters. We discussed the contribution of hydroxyl and chloride radicals in the initiation of erythrocyte damage and oxygen modification of these processes.

  13. Diffusion of hydroxyl ions from calcium hydroxide and Aloe vera pastes. (United States)

    Batista, Victor Eduardo de Souza; Olian, Douglas Dáquila; Mori, Graziela Garrido


    This study evaluated the diffusion through the dentinal tubules of hydroxyl ions from different calcium hydroxide (CH) pastes containing Aloe vera. Sixty single-rooted bovine teeth were used. The tooth crowns were removed, the root canals were instrumented and the specimens were assigned to 4 groups (n=15) according to the intracanal medication: Group CH/S - CH powder and saline paste; Group CH/P - CH powder and propylene glycol paste; Group CH/A - calcium hydroxide powder and Aloe vera gel paste; Group CH/A/P - CH powder, Aloe vera powder and propylene glycol paste. After placement of the root canal dressings, the teeth were sealed coronally and apically with a two-step epoxy adhesive. The teeth were placed in identified flasks containing deionized water and stored in an oven with 100% humidity at 37 °C. After 3 h, 24 h, 72 h, 7 days, 15 days and 30 days, the deionized water in the flasks was collected and its pH was measured by a pH meter. The obtained data were subjected to statistical analysis at a significance level of 5%. The results demonstrated that all pastes provided diffusion of hydroxyl ions through the dentinal tubules. The combination of Aloe vera and CH (group CH/A) provided a constant release of calcium ions. Group CH/A/P showed the highest pH at 24 and 72 h. In conclusion, the experimental pastes containing Aloe vera were able to enable the diffusion of hydroxyl ions through the dentinal tubules.

  14. Genetic basis of inter- and intrastrain differences in diazepam p-hydroxylation in rats. (United States)

    Sakai, Noriaki; Saito, Konomu; Sakamoto, Kentaro Q; Ishizuka, Mayumi; Fujita, Shoichi


    Diazepam (7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one) is widely used as a sedative, hypnotic, and anti-anxiety drug. At low diazepam concentrations, p-hydroxylation is the major metabolic pathway in rat liver microsomes. However, there are marked ( approximately 300-fold) inter- and intrastrain differences in the activity among Sprague-Dawley, Brown Norway, Dark Agouti, and Wistar rats. In our previous study, we determined that a deficiency of CYP2D3 protein, not CYP2D2, was responsible for the inter- and intrastrain differences in diazepam p-hydroxylation (Drug Metab Dispos 33:1657-1660, 2005). Quantitative real-time polymerase chain reaction (PCR) did not provide enough evidence to explain the inter- and intrastrain differences in the expression of CYP2D3 protein. Nucleotide sequence analysis revealed the insertion of a thymine in exon 8 of the CYP2D3 gene in the poor diazepam metabolizers. This single nucleotide mutation caused a shift in the reading frame and introduced a premature termination signal. It is noteworthy that the heme binding region, which is essential to maintain proper heme binding and active cytochrome P450 enzymes, was consequently deleted by the premature termination signal. In contrast, no mutation was detected in the CYP2D3 gene of extensive metabolizers. Thus, the truncated CYP2D3 must be a nonfunctional enzyme in poor metabolizers. In addition, we developed a convenient and specific genotyping assay using PCR-restriction, fragment-length polymorphism to distinguish homozygotes from heterozygotes. The genotyping gave results fully consistent with those of the inter- and intrastrain differences in diazepam p-hydroxylation.

  15. Assessing the hydroxyl radical and volatilization roles in aquatic fate estimations of sulfur heterocycles: Dibenzothiophene derivatives. (United States)

    Saranjampour, Parichehr; Armbrust, Kevin L; Marx, Brian D


    Polycyclic aromatic sulfur heterocycles (PASHs) and their alkyl derivatives can be released into aquatic systems via crude oil spills or runoff from petroleum-treated areas, such as asphalt. Dibenzothiophene (DBT) and its derivatives (C1-DBT, C2-DBT, and C4-DBT) were chosen as model compounds to investigate the relative impact of volatilization and hydroxyl radical degradation on estimates of their overall dissipation after entry into aquatic ecosystems as a function of depth using the exposure analysis modeling system (EXAMS). The hydroxyl radical rate constant (K · OH ) and Henry's law constant of PASHs were determined in distilled water. The analogue C1-DBT reacted fastest with · OH relative to other PASHs. The C2-DBT and C4-DBT analogues had higher Henry's law constants compared with other derivatives. Steric hindrance by alkyl substituents on the sulfur moiety most strongly impacted measured rate and Henry's law constants between DBT and individual alkyl derivatives. These steric effects do not appear to be considered in the physical property estimation software EPI Suite. Simulated dissipation of PASHs using EXAMS suggests that volatilization is a dominant fate pathway for the higher molecular weight and less polar C2-DBT and C4-DBT at all depths and DBT and C1-DBT at 0.1-m. However, model scenarios suggest that hydroxyl radical degradation may significantly contribute to the degradation of more polar DBT and C1-DBT at 1-m and 2-m depths. Environ Toxicol Chem 2017;36:1998-2004. © 2017 SETAC. © 2017 SETAC.

  16. Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals. (United States)

    Liu, Fobang; Lai, Senchao; Tong, Haijie; Lakey, Pascale S J; Shiraiwa, Manabu; Weller, Michael G; Pöschl, Ulrich; Kampf, Christopher J


    Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

  17. Effects of phenothiazine neuroleptics on the rate of caffeine demethylation and hydroxylation in the rat liver. (United States)

    Daniel, W A; Syrek, M; Ryłko, Z; Kot, M


    The primary metabolic pathways of caffeine are 3-N-demethylation to paraxanthine (CYP1A2), 1-N-demethylation to theobromine and 7-N-demethylation to theophylline (CYP1A2 and other enzymes), and 8-hydroxylation to 1,3,7-trimethyluric acid (CYP3A). The aim of the present study was to investigate the influence of phenothiazine neuroleptics (chlorpromazine, levomepromazine, thioridazine, perazine) on cytochrome P-450 activity measured by caffeine oxidation in rat liver microsomes. The obtained results showed that all the investigated neuroleptics competitively inhibited caffeine oxidation in the rat liver, though their potency to inhibit particular metabolic pathways was not equal. Levomepromazine exerted the most potent inhibitory effect on caffeine oxidation pathways, the effect on 8-hydroxylation being the most pronounced. This indicates inhibition of CYP 1 A2 (inhibition of 3-N- and 1-N-demethylation; Ki = 36 and 32 microM, respectively), CYP3A2 (inhibition of 8-hydroxylations; Ki = 20 microM), and possibly other CYP isoenzymes (inhibition of 7-N-demethylation; Ki = 58 microM) by the neuroleptics. The potency of inhibition of caffeine oxidation by perazine was similar to levomepromazine. Thioridazine was a weaker inhibitor of caffeine 3-N- and 7-N-demethylation, while chlorpromazine was weaker in inhibiting caffeine 1-N- and 7-N-demethylation, compared to levomepromazine. In summary, the obtained results showed that all the investigated neuroleptics had a broad spectra of CYP inhibition in the rat liver. The isoenzymes CYP1A2 and CYP3A2 were distinctly inhibited by all the investigated neuroleptics, while other CYP isoenzymes (CYP2B and/or 2E1) by perazine and levomepromazine. The CYP3A2 inhibition was most pronounced. (Ki = 20-40 microM).

  18. The 4'-hydroxyl group of resveratrol is functionally important for direct activation of PPARα.

    Directory of Open Access Journals (Sweden)

    Yoshie Takizawa

    Full Text Available Long-term moderate consumption of red wine is associated with a reduced risk of developing lifestyle-related diseases such as cardiovascular disease and cancer. Therefore, resveratrol, a constituent of grapes and various other plants, has attracted substantial interest. This study focused on one molecular target of resveratrol, the peroxisome proliferator activated receptor α (PPARα. Our previous study in mice showed that resveratrol-mediated protection of the brain against stroke requires activation of PPARα; however, the molecular mechanisms involved in this process remain unknown. Here, we evaluated the chemical basis of the resveratrol-mediated activation of PPARα by performing a docking mode simulation and examining the structure-activity relationships of various polyphenols. The results of experiments using the crystal structure of the PPARα ligand-binding domain and an analysis of the activation of PPARα by a resveratrol analog 4-phenylazophenol (4-PAP in vivo indicate that the 4'-hydroxyl group of resveratrol is critical for the direct activation of PPARα. Activation of PPARα by 5 μM resveratrol was enhanced by rolipram, an inhibitor of phosphodiesterase (PDE and forskolin, an activator of adenylate cyclase. We also found that resveratrol has a higher PDE inhibitory activity (IC50 = 19 μM than resveratrol analogs trans-4-hydroxystilbene and 4-PAP (IC50 = 27-28 μM, both of which has only 4'-hydroxyl group, indicating that this 4'-hydroxyl group of resveratrol is not sufficient for the inhibition of PDE. This result is consistent with that 10 μM resveratrol has a higher agonistic activity of PPARα than these analogs, suggesting that there is a feedforward activation loop of PPARα by resveratrol, which may be involved in the long-term effects of resveratrol in vivo.

  19. Postischemic hypothermia inhibits the generation of hydroxyl radical following transient forebrain ischemia in rats. (United States)

    Horiguchi, Takashi; Shimizu, Katsuyoshi; Ogino, Masahiro; Suga, Sadao; Inamasu, Joji; Kawase, Takeshi


    A small reduction of body temperature during reperfusion following cerebral ischemia has been known to ameliorate neuronal injury. However, the mechanisms underlying postischemic hypothermia-induced neuroprotection are poorly understood. The burst of reactive oxygen species (ROS) formation that occurs during reperfusion has been documented to be involved in ischemic neuronal degeneration. In this study, we investigated the effect of postischemic hypothermia on ROS production following transient forebrain ischemia using an in vivo microdialysis technique. Forebrain ischemia was induced by bilateral carotid artery occlusion combined with hemorrhagic hypotension for 20 min in male Wistar rats. The body temperature was kept at 37 degrees C during ischemia and controlled at either 32 degrees C or 37 degrees C after reperfusion. The amount of hydroxyl radical produced in striatum was evaluated by measurement of 2,3- and 2,5-dihydroxybenzoic acid (DHBA), which is generated by salicylate hydroxylation. We also measured the extracellular concentration of xanthine, while determining striatal blood flow by the hydrogen clearance technique. In animals whose postischemic body temperature was maintained at 37 degrees C, the levels of 2,3- and 2,5-DHBA significantly increased after reperfusion. The peak levels of 2,3- and 2,5- DHBA were 2.9-fold and 2.7-fold increased above the corresponding baseline values, respectively. Postischemic hypothermia completely inhibited the hydroxyl radical formation. Likewise, xanthine formation was also inhibited by postischemic hypothermia. In contrast, striatal cerebral blood flow was not altered by temperature modulation during reperfusion. These results suggest that inhibition of ROS production accompanied with suppression of xanthine formation is implicated in the neuroprotection of postischemic hypothermia.

  20. New rhodamine nitroxide based fluorescent probes for intracellular hydroxyl radical identification in living cells. (United States)

    Yapici, Nazmiye B; Jockusch, Steffen; Moscatelli, Alberto; Mandalapu, Srinivas Rao; Itagaki, Yasuhiro; Bates, Dallas K; Wiseman, Sherri; Gibson, K Michael; Turro, Nicholas J; Bi, Lanrong


    The synthesis, characteristics, and biological applications of a series of new rhodamine nitroxide fluorescent probes that enable imaging of hydroxyl radicals (•OH) in living cells are described. These probes are highly selective for •OH in aqueous solution, avoiding interference from other reactive oxygen species (ROS), and they facilitate •OH imaging in biologically active samples. The robust nature of these probes (high specificity and selectivity, and facile synthesis) offer distinct advantages over previous methods for •OH detection. © 2011 American Chemical Society

  1. Chemoselective Methylation of Phenolic Hydroxyl Group Prevents Quinone Methide Formation and Repolymerization During Lignin Depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kwang Ho; Dutta, Tanmoy; Walter, Eric D.; Isern, Nancy G.; Cort, John R.; Simmons, Blake A.; Singh, Seema


    Chemoselective blocking of the phenolic hydroxyl (Ar-OH) group by methylation was found to suppress secondary repolymerization and charring during lignin depolymerization. Methylation of Ar-OH prevents formation of reactive quinone methide intermediates, which are partly responsible for undesirable secondary repolymerization reactions. Instead, this structurally modified lignin produces more relatively low molecular weight products from lignin depolymerization compared to unmodified lignin. This result demonstrates that structural modification of lignin is desirable for production of low molecular weight phenolic products. This approach could be directed toward alteration of natural lignification processes to produce biomass more amenable to chemical depolymerization.

  2. Reaction of hydroxyl radicals with ammonia in liquid water at elevated temperatures

    DEFF Research Database (Denmark)

    Hickel, B.; Sehested, K.


    The reaction of hydroxyl radical with ammonia in aqueous solutions has been studied by pulse radiolysis in the temperature range 20-200-degrees-C. The rate constant of the reaction was determined by monitoring the decay of the OH radical absorption at 260 nm for different concentrations of ammonia....... At room temperature the rate constant is (9.7 +/- 1) x 10(7) dm3 mol-1 s-1. In the whole range of temperatures the Tate constant follows Arrhenius law with an activation energy of (5.7 +/- 1) kJ mol-1. The protective effect of dissolved hydrogen on the radiolytic decomposition of ammon a is discussed....

  3. Lack of Hydroxylated Fullerene Toxicity after Intravenous Administration to Female Sprague-Dawley Rats (United States)

    Monteiro-Riviere, Nancy A.; Linder, Keith E.; Inman, Alfred O.; Saathoff, John G.; Xia, Xin-Rui; Riviere, Jim E.


    Hydroxylated fullerenes (C60OHx) or fullerols are water-soluble carbon nanoparticles that have been explored for potential therapeutic applications. This study assessed acute in vivo tolerance in 8 week old female Sprague Dawley rats to intravenous administration (IV) of 10 mg/kg of well-characterized C60(OH)30. Complete histopathology and clinical chemistries were assessed at 8, 24, and 48 hr after dosing. Minor histopathology changes were seen, primarily in one animal. No clinically significant chemistry changes were observed after treatment. These experiments suggest that this fullerol was well tolerated after IV administration to rats. PMID:22524592

  4. Inducible hydroxylation and demethylation of the herbicide isoproturon by Cunninghamella elegans. (United States)

    Hangler, Martin; Jensen, Bo; Rønhede, Stig; Sørensen, Sebastian R


    A screening of 27 fungal strains for degradation of the phenylurea herbicide isoproturon was performed and yielded 15 strains capable of converting the herbicide to polar metabolites. The zygomycete fungus Cunninghamella elegans strain JS/2 isolated from an agricultural soil converted isoproturon to several known hydroxylated metabolites. In addition, unknown metabolites were produced in minor amounts. Inducible degradation was indicated by comparing resting cells pregrown with or without isoproturon. This shows that strain JS/2 is capable of partially degrading isoproturon and that one or more of the enzymes involved are inducible upon isoproturon exposure.

  5. Retention of polyphenyls and substituted polycyclic aromatic hydrocarbons in the system hydroxylated silica - n-hexane

    Energy Technology Data Exchange (ETDEWEB)

    Nikitin, Y.S.; Lanin, S.N. [Dept. of Chemistry, M.V. Lomonosov State Univ. of Moscow (Russian Federation); Al-Ahmed, A. [University of Aleppo (Syrian Arab Republic)


    The regularity of retention of unsubstituted and methyl-substituted polyphenyls and condensed polycyclic aromatic hydrocarbons in normal-phase (NP) HPLC with a non-polar mobile phase (n-hexane) on hydroxylated silica has been studied. It was shown that chromatographic retention of aromatic hydrocarbons depends not only on number of aromatic rings and methyl groups in a molecule, but also on a nature of the bond between the aromatic rings of polyphenyls and condensed polycyclic aromatic hydrocarbons. A structure - retention relationship has been proposed for description of the retention regularity of the aromatic hydrocarbons studied. (orig.)

  6. Hydroxylation at carbon-2 of ent-16-oxo-17-norkauran-19-oic acid by Fusarium proliferatum. (United States)

    Rocha, Alessandra Duarte; dos Santos, Geandson Coelho; Fernandes, Nelson Gonçalves; Pfenning, Ludwig Heinrich; Takahashi, Jacqueline Aparecida; Boaventura, Maria Amélia Diamantino


    A new product of biotransformation of ent-16-oxo-17-norkauran-19-oic acid (1) by Fusarium proliferatum was isolated and identified as a 2beta-hydroxy derivative (2). The structure of 2 was elucidated on the basis of spectroscopic data interpretation and single-crystal X-ray diffraction analysis. The allelopathic activity of compound 2 was evaluated on the growth of radicals and shoots of Lactuca sativa (lettuce). This is the first time that fungal hydroxylation at position C-2 has been reported on an ent-kaurane diterpene skeleton.

  7. Effect of indole-3-acetic acid on pea root growth, peroxidase profiles and hydroxyl radical formation


    Kukavica Biljana; Mitrović Aleksandra; Mojović M.; Veljović-Jovanović Sonja


    Changes in growth, peroxidase profiles, and hydroxyl radical formation were examined in IAA (0.5-10 mg/l) treated pea plants grown hydroponically and in isolated roots in liquid in vitro culture. IAA inhibited root elongation, both in hydroponically grown pea plants and in isolated roots in vitro. A remarkable increase in the number of POD iso­forms was noticed in isolated roots grown in vitro, compared to the roots from plants grown hydroponically. IAA induced both disappearance of several r...

  8. Effects of trimethylaluminium and tetrakis(ethylmethylamino) hafnium in the early stages of the atomic-layer-deposition of aluminum oxide and hafnium oxide on hydroxylated GaN nanoclusters. (United States)

    León-Plata, Paola A; Coan, Mary R; Seminario, Jorge M


    We calculate the interactions of two atomic layer deposition (ALD) reactants, trimethylaluminium (TMA) and tetrakis(ethylmethylamino) hafnium (TEMAH) with the hydroxylated Ga-face of GaN clusters when aluminum oxide and hafnium oxide, respectively, are being deposited. The GaN clusters are suitable as testbeds for the actual Ga-face on practical GaN nanocrystals of importance not only in electronics but for several other applications in nanotechnology. We find that TMA spontaneously interacts with hydroxylated GaN; however it does not follow the atomic layer deposition reaction path unless there is an excess in potential energy introduced in the clusters at the beginning of the optimization, for instance, using larger bond lengths of various bonds in the initial structures. TEMAH also does not interact with hydroxylated GaN, unless there is an excess in potential energy. The formation of a Ga-N(CH3)(CH2CH3) bond during the ALD of HfO2 using TEMAH as the reactant without breaking the Hf-N bond could be the key part of the mechanism behind the formation of an interface layer at the HfO2/GaN interface.

  9. The effect of laparotomy on hydroxyl radicals, singlet oxygen and antioxidants measured by EPR method in the tails of rats. (United States)

    Fricova, Jitka; Stopka, Pavel; Krizova, Jana; Yamamotova, Anna; Rokyta, Richard


    The aim of the study was to demonstrate that direct measurement of hydroxyl radicals and singlet oxygen in the tail of living rats is possible. The basic level of hydroxyl radicals and singlet oxygen were measured and the effects of antioxidants on their levels were studied in the tail of living anaesthetized rats after acute postoperative pain. Laparotomy was performed as the source of acute abdominal pain. After closure of the abdominal cavity, the animals began to awaken within 30-60 minutes. They were left to recover for 2-3 hours; then they were reanesthetized and the effect of antioxidants was measured on the numbers of hydroxyl radicals and singlet oxygen via blood in the tail. The laparotomy was preformed under general anesthesia (Xylazin and Ketamin) using Wistar rats. After recovery and several hours of consciousness they were reanaesthetized and free radicals and singlet oxygen were measured. An antioxidant mixture (vitamins A, C, D and Selenium) was administered intramuscularly prior to the laparotomy. All measurements were done on the tail of anaesthetized animals. In this particular article, the effect of antioxidants is only reported for hydroxyl radicals. After laparotomy, which represented both somatic and visceral pain, hydroxyl radicals and singlet oxygen were increased. Antioxidant application prior to laparotomy decreased the numbers of hydroxyl radicals. Results are in agreement with our previous finding regarding the increase in hydroxyl free radicals and singlet oxygen following nociceptive stimulation, in this case a combination of both somatic and visceral pain. The administered antioxidants mitigated the increase. This is further confirmation that direct measurement of free radicals and singlet oxygen represents a very useful method for the biochemical evaluation of pain and nociception.

  10. Inhibition of microsomal oxidation of alcohols and of hydroxyl-radical-scavenging agents by the iron-chelating agent desferrioxamine. (United States)

    Cederbaum, A I; Dicker, E


    Rat liver microsomes (microsomal fractions) catalyse the oxidation of straight-chain aliphatic alcohols and of hydroxyl-radical-scavenging agents during NADPH-dependent electron transfer. The iron-chelating agent desferrioxamine, which blocks the generation of hydroxyl radicals in other systems, was found to inhibit the following microsomal reactions: production of formaldehyde from either dimethyl sulphoxide or 2-methylpropan-2-ol (t-butylalcohol); generation of ethylene from 4-oxothiomethylbutyric acid; release of 14CO2 from [I-14C]benzoate; production of acetaldehyde from ethanol or butanal (butyraldehyde) from butan-1-ol. Desferrioxamine also blocked the increase in the oxidation of all these substrates produced by the addition of iron-EDTA to the microsomes. Desferrioxamine had no effect on a typical mixed-function-oxidase activity, the N-demethylation of aminopyrine, nor on the peroxidatic activity of catalase/H2O2 with ethanol. H2O2 appears to be the precursor of the oxidizing radical responsible for the oxidation of the alcohols and the other hydroxyl-radical scavengers. Chelation of microsomal iron by desferrioxamine most likely decreases the generation of hydroxyl radicals, which results in an inhibition of the oxidation of the alcohols and the hydroxyl-radical scavengers. Whereas desferrioxamine inhibited the oxidation of 2-methylpropan-2-ol, dimethyl sulphoxide, 4-oxothiomethylbutyrate and benzoate by more than 90%, the oxidation of ethanol and butanol could not be decreased by more than 45-60%. Higher concentrations of desferrioxamine were required to block the metabolism of the primary alcohols than to inhibit the metabolism of the other substrates. The desferrioxamine-insensitive rate of oxidation of ethanol was not inhibited by competitive hydroxyl-radical scavengers. These results suggest that primary alcohols may be oxidized by two pathways in microsomes, one dependent on the interaction of the alcohols with hydroxyl radicals (desferrioxamine

  11. Metabolism of capsaicinoids: evidence for aliphatic hydroxylation and its pharmacological implications. (United States)

    Surh, Y J; Ahn, S H; Kim, K C; Park, J B; Sohn, Y W; Lee, S S


    A new metabolic oxidation pathway of capsaicin (N-[(4-hydroxy-3-methoxyphenyl)-methyl]-8-methyl-(E)-6 -nonenamide), a major pungent and pharmacologically active principle of hot peppers, was investigated. Incubation of capsaicin with phenobarbital-induced rat liver postmitochondrial supernatant enriched with NADPH-generating system produced N-(4,5-dihydroxy-3-methoxybenzyl)-(E)-6 -nonenylamide and a more polar metabolite. The latter metabolite was spectrophotometrically and chromatographically identical to authentic omega-hydroxycapsaicin. This new metabolite was also detected in the urine of rabbits given capsaicin by gastric intubation. Other analogs of capsaicin, such as dihydrocapsaicin and nonivamide, also formed similar metabolites via aliphatic hydroxylation. When tested for antinociceptive activity as well as pungency, the above polar metabolites were found to be inactive while their parent compounds exhibited strong sensory effects. Capsaicin interacted irreversibly with heptic drug metabolizing enzymes, thereby inhibiting their activity as indicated by prolongation of pentobarbital sleeping time in rats. Such inhibition of drug metabolism was not observed with omega-hydroxycapsaicin. These findings suggest that metabolism of capsaicinoids via hydroxylation of their side chains plays an important role in the detoxification of these pharmacologically active substances.

  12. Coumestan inhibits radical-induced oxidation of DNA: is hydroxyl a necessary functional group? (United States)

    Xi, Gao-Lei; Liu, Zai-Qun


    Coumestan is a natural tetracycle with a C═C bond shared by a coumarin moiety and a benzofuran moiety. In addition to the function of the hydroxyl group on the antioxidant activity of coumestan, it is worth exploring the influence of the oxygen-abundant scaffold on the antioxidant activity as well. In this work, seven coumestans containing electron-withdrawing and electron-donating groups were synthesized to evaluate the abilities to trap 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(•+)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively, and to inhibit the oxidations of DNA mediated by (•)OH, Cu(2+)/glutathione (GSH), and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH), respectively. It was found that all of the coumestans used herein can quench the aforementioned radicals and can inhibit (•)OH-, Cu(2+)/GSH-, and AAPH-induced oxidations of DNA. In particular, substituent-free coumestan exhibits higher ability to quench DPPH and to inhibit AAPH-induced oxidation of DNA than Trolox. In addition, nonsubstituted coumestan shows a similar ability to inhibit (•)OH- and Cu(2+)/GSH-induced oxidations of DNA relative to that of Trolox. The antioxidant effectiveness of the coumestan can be attributed to the lactone in the coumarin moiety and, therefore, a hydroxyl group may not be a necessary functional group for coumestan to be an antioxidant.

  13. Hydroxyl radical modification of collagen type II increases its arthritogenicity and immunogenicity. (United States)

    Shahab, Uzma; Ahmad, Saheem; Moinuddin; Dixit, Kiran; Habib, Safia; Alam, Khursheed; Ali, Asif


    The oxidation of proteins by endogenously generated free radicals causes structural modifications in the molecules that lead to generation of neo-antigenic epitopes that have implications in various autoimmune disorders, including rheumatoid arthritis (RA). Collagen induced arthritis (CIA) in rodents (rats and mice) is an accepted experimental model for RA. Hydroxyl radicals were generated by the Fenton reaction. Collagen type II (CII) was modified by •OH radical (CII-OH) and analysed by ultraviolet-visible (UV-VIS), fluorescence and circular dichroism (CD) spectroscopy. The immunogenicity of native and modified CII was checked in female Lewis rats and specificity of the induced antibodies was ascertained by enzyme linked immunosorbent assay (ELISA). The extent of CIA was evaluated by visual inspection. We also estimated the oxidative and inflammatory markers in the sera of immunized rats. A slight change in the triple helical structure of CII as well as fragmentation was observed after hydroxyl radical modification. The modified CII was found to be highly arthritogenic and immunogenic as compared to the native form. The CII-OH immunized rats exhibited increased oxidative stress and inflammation as compared to the CII immunized rats in the control group. Neo-antigenic epitopes were generated on (•)OH modified CII which rendered it highly immunogenic and arthritogenic as compared to the unmodified form. Since the rodent CIA model shares many features with human RA, these results illuminate the role of free radicals in human RA.

  14. Electrochemiluminescence of palmatine being oxidized by electrogenerated hydroxyl radical and its analytical application. (United States)

    Liang, Yao-Dong; Yu, Chun-Xia; Song, Jun-Feng


    A strong electrochemiluminescence (ECL) of palmatine in NaOH medium was observed at a vaseline-impregnated graphite anode. The ECL production could be described as follows: hydroxyl radical (OH(•)) was generated via the oxidation of hydroxyl group (OH(-)) in NaOH medium, and the formed OH(•) subsequently oxidized palmatine base converted from palmatine in NaOH medium to the excited state oxypalmatine (oxypalmatine*). As the oxypalmatine* went back to its ground state, a stronger chemiluminescence was produced. Based on the ECL of palmatine, an ECL method for the determination of palmatine was proposed. An ECL signal of palmatine in NaOH solution was obtained by applying direct current of 15 mA to the vaseline-impregnated graphite anode. The ECL intensity was rectilinear with palmatine concentration in the range of 8.0 × 10(-7) to 2.0 × 10(-5) mol l(-1) and the limit of detection (signal-to-noise = 3) was 3 × 10(-7) mol l(-1) . The proposed method was applied to the determination of palmatine in pharmaceutical preparations. Copyright © 2010 John Wiley & Sons, Ltd.

  15. Making graphene holey. Gold-nanoparticle-mediated hydroxyl radical attack on reduced graphene oxide. (United States)

    Radich, James G; Kamat, Prashant V


    Graphene oxide (GO) and reduced graphene oxide (RGO) have important applications in the development of new electrode and photocatalyst architectures. Gold nanoparticles (AuNPs) have now been employed as catalyst to generate OH(•) and oxidize RGO via hydroxyl radical attack. The oxidation of RGO is marked by pores and wrinkles within the 2-D network. Nanosecond laser flash photolysis was used in conjunction with competition kinetics to elucidate the oxidative mechanism and calculate rate constants for the AuNP-catalyzed and direct reaction between RGO and OH(•). The results highlight the use of the AuNP-mediated oxidation reaction to tune the properties of RGO through the degree of oxidation and/or functional group selectivity in addition to the nanoporous and wrinkle facets. The ability of AuNPs to catalyze the photolytic decomposition of H2O2 as well as the hydroxyl radical-induced oxidation of RGO raises new issues concerning graphene stability in energy conversion and storage (photocatalysis, fuel cells, Li-ion batteries, etc.). Understanding RGO oxidation by free radicals will aid in maintaining the long-term stability of RGO-based functional composites where intimate contact with radical species is inevitable.

  16. In vitro toxicity assessment of three hydroxylated fullerenes in human skin cells. (United States)

    Saathoff, J G; Inman, A O; Xia, X R; Riviere, J E; Monteiro-Riviere, N A


    Carbon fullerenes possess unique properties and their interactions with biomolecules have widespread applications. Functionalization of fullerenes with hydroxyl groups (fullerenols) can increase the solubility and potential for cellular interaction, but the health and safety effects of varying degrees of fullerene hydroxylation in biological systems is poorly understood. Existing reports regarding the toxicity and inflammatory potential of fullerenols give conflicting conclusions. To further elucidate the potential for toxicity of fullerenols, human epidermal keratinocytes (HEK) were exposed to fullerenols (low (C60(OH)20), medium (C60(OH)24), and high (C60(OH)32)) at concentrations ranging from 0.000544-42.5 μg/ml for 24 and 48 h. A statistically significant (pfullerenes caused no cytotoxicity or inflammation up to 8.55 μg/ml. These findings suggest that extrapolation across similar NP will be dependent upon surface chemistry and concentration which may affect the degree of agglomeration and thus biological effects. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. The antimicrobial activity of gramicidin A is associated with hydroxyl radical formation.

    Directory of Open Access Journals (Sweden)

    Je-Wen Liou

    Full Text Available Gramicidin A is an antimicrobial peptide that destroys gram-positive bacteria. The bactericidal mechanism of antimicrobial peptides has been linked to membrane permeation and metabolism disruption as well as interruption of DNA and protein functions. However, the exact bacterial killing mechanism of gramicidin A is not clearly understood. In the present study, we examined the antimicrobial activity of gramicidin A on Staphylococcus aureus using biochemical and biophysical methods, including hydroxyl radical and NAD+/NADH cycling assays, atomic force microscopy, and Fourier transform infrared spectroscopy. Gramicidin A induced membrane permeabilization and changed the composition of the membrane. The morphology of Staphylococcus aureus during gramicidin A destruction was divided into four stages: pore formation, water permeability, bacterial flattening, and lysis. Changes in membrane composition included the destruction of membrane lipids, proteins, and carbohydrates. Most interestingly, we demonstrated that gramicidin A not only caused membrane permeabilization but also induced the formation of hydroxyl radicals, which are a possible end product of the transient depletion of NADH from the tricarboxylic acid cycle. The latter may be the main cause of complete Staphylococcus aureus killing. This new finding may provide insight into the underlying bactericidal mechanism of gA.

  18. Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups. (United States)

    Salmeron, M; Bluhm, H; Tatarkhanov, M; Ketteler, G; Shimizu, T K; Mugarza, A; Deng, Xingyi; Herranz, T; Yamamoto, S; Nilsson, A


    We discuss the role of the presence of dangling H-bonds from water or from surface hydroxyl species on the wetting behavior of surfaces. Using scanning tunneling and atomic force microscopies and photoelectron spectroscopy, we have examined a variety of surfaces, including mica, oxides and pure metals. We find that in all cases, the availability of free, dangling H-bonds at the surface is crucial for the subsequent growth of wetting water films. In the case of mica, electrostatic forces and H-bonding to surface O atoms determine the water orientation in the first layer and also in subsequent layers with a strong influence in its wetting characteristics. In the case of oxides like TiO2, Cu2O, SiO2 and Al2O3, surface hydroxyls form readily on defects upon exposure to water vapor and help nucleate the subsequent growth of molecular water films. On pure metals, such as Pt, Pd and Ru, the structure of the first water layer and whether or not it exhibits dangling H-bonds is again crucial. Dangling H-bonds are provided by molecules with their plane oriented vertically, or by OH groups formed by the partial dissociation of water. By tying the two H atoms of the water molecules into strong H-bonds with pre-adsorbed O on Ru can also quench the wettability of the surface.

  19. Temperature dependence of hydroxyl radical reactions with chloramine species in aqueous solution. (United States)

    Gleason, Jamie M; McKay, Garrett; Ishida, Kenneth P; Mezyk, Stephen P


    The absolute temperature-dependent kinetics for the reaction between hydroxyl radicals and the chloramine water disinfectant species monochloramine (NH2Cl), as well as dichloramine (NHCl2) and trichloramine (NCl3), have been determined using electron pulse radiolysis and transient absorption spectroscopy. These radical reaction rate constants were fast, with values of 6.06 × 108, 2.57 × 108, and 1.67 × 108 M-1 s-1 at 25 °C for NH2Cl, NHCl2, and NCl3, respectively. The corresponding temperature dependence of these reaction rate constants, measured over the range 10-40 °C, is well-described by the transformed Arrhenius equations:giving activation energies of 8.57 ± 0.58, 6.11 ± 0.40, and 5.77 ± 0.72 kJ mol-1 for these three chloramines, respectively. These data will aid water utilities in predicting hydroxyl radical partitioning and chemical contaminant removal efficiencies under real-world advanced oxidation process treatment conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.


    Directory of Open Access Journals (Sweden)

    Nuni Widiarti


    Full Text Available CuO/TS-1 catalysts have been prepared and tested in the benzene hydroxylation. TS-1 was synthesized by hydrothermalmethod, while CuO/TS-1 was prepared by impregnation method using Cu(NO2.3H2O as precursor. Catalysts werecharacterized by using X-ray diffraction (XRD, infrared spectroscopy (IR, and N2 adsorption-desorption techniques.The catalytic activity was tested in the hydroxylation reaction of benzene. The products were analyzed using gaschromatography. Catalyst characterization by XRD and IR techniques have showed that the catalyst structure was aMFI type of zeolite. XRD pattern have showed the orthorombic structure and indicated the presence of CuOaggregation. The results of the pyridine adsorption have found that the acidity of TS-1 and CuO/TS-1 were a Lewis acidand it’s increased with an increasing amount of CuO loading. The results of nitrogen adsorption analysis have showeddecreasing of surface areas of catalyst with increasing amount of CuO loading. The optimum conditions of benzenehydroxylation was observed by 1%CuO/TS-1 catalyst at 70 °C, reaction time 2 h and acetic acid as the solvent yielded27.6% of phenol with phenol selectivity was 75.5%.

  1. UVA-induced reset of hydroxyl radical ultradian rhythm improves temporal lipid production in Chlorella vulgaris. (United States)

    Balan, Ranjini; Suraishkumar, G K


    We report for the first time that the endogenous, pseudo-steady-state, specific intracellular levels of the hydroxyl radical (si-OH) oscillate in an ultradian fashion (model system: the microalga, Chlorella vulgaris), and also characterize the various rhythm parameters. The ultradian rhythm in the endogenous levels of the si-OH occurred with an approximately 6 h period in the daily cycle of light and darkness. Further, we expected that the rhythm reset to a shorter period could rapidly switch the cellular redox states that could favor lipid accumulation. We reset the endogenous rhythm through entrainment with UVA radiation, and generated two new ultradian rhythms with periods of approximately 2.97 h and 3.8 h in the light phase and dark phase, respectively. The reset increased the window of maximum lipid accumulation from 6 h to 12 h concomitant with the onset of the ultradian rhythms. Further, the saturated fatty acid content increased approximately to 80% of total lipid content, corresponding to the peak maxima of the hydroxyl radical levels in the reset rhythm. © 2014 American Institute of Chemical Engineers.

  2. Hydroxylation of phenol over MeAPO molecular sieves synthesized by vapor phase transport (United States)

    Shao, Hui; Chen, Jingjing; Chen, Xia; Leng, Yixin; Zhong, Jing


    In this study, MeAPO-25 (Me = Fe, Cu, Mn) molecular sieves were first synthesized by a vapor phase transport method using tetramethyl guanidine as the template and applied to hydroxylation of phenol. The zeolites were characterized by XRD, SEM, FT-IR, and DR UV-Vis. As a result, MeAPO-21 and MeAPO-15 were synthesized by changing the Me/Al ratio. UV-Visible diffuse reflectance study suggested incorporation of heteroatoms into the framework and FT-IR study also supported these data. Effects of heteroatoms, contents of Me in MeAPO-25, reaction temperature, phenol/H2O2 mole ratios, reaction time and concentration of catalyst on the conversion of phenol, as well as on the selectivity were studied. FeAPO-25 exhibited a high catalytic activity at the mole ratio of FeO and Al2O3 equal to 0.1 in the synthesis gel, giving the phenol conversion of 88.75% and diphenols selectivity of 66.23% at 60°C within 3 h [ n(phenol)/ n(H2O2) = 0.75, m(FeAPO-25)/ m(phenol) = 7.5%]. Experimental results indicated that the FeAPO-25 molecular sieve was a fairly promising candidate for the application in hydroxylation of phenol.

  3. In situ measurement of superoxide and hydroxyl radicals by frequency mixing detection technique. (United States)

    Hong, HyoBong; Krause, Hans Joachim; Sohn, SungWon; Baik, TaiKyong; Park, Jong Hyun; Shin, SungWoong; Park, ChiHu; Song, DaeYong


    Frequency mixing magnetic detection (FMMD) was used to detect superoxide from hypoxanthine and xanthine reaction and to detect hydroxyl radical from the Fenton reaction. FMMD was also applied to measure the reactive oxygen species (ROS) level released from microglial cells. We could assess the formation and extinction of the free radicals without a spin trap reagent. The FMMD signal amplitude scaled with the concentration of the radicals. It was verified that no signals are obtained from the substrates and reagents. Based on the observations and on previous research, we suggest that the FMMD signals originate from superoxide and hydroxyl radicals, indicating that FMMD can be used to detect O-centered radicals. Subsequent analysis of free radicals generated from living microglial cells showed that there were significant differences between the activated microglial cells and resting ones. The results of this research are promising regarding the applications of FMMD for in situ measurement of free radicals from various sources, including the cell. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Single-layer nanosheets with exceptionally high and anisotropic hydroxyl ion conductivity. (United States)

    Sun, Pengzhan; Ma, Renzhi; Bai, Xueyin; Wang, Kunlin; Zhu, Hongwei; Sasaki, Takayoshi


    When the dimensionality of layered materials is reduced to the physical limit, an ultimate two-dimensional (2D) anisotropy and/or confinement effect may bring about extraordinary physical and chemical properties. Layered double hydroxides (LDHs), bearing abundant hydroxyl groups covalently bonded within 2D host layers, have been proposed as inorganic anion conductors. However, typical hydroxyl ion conductivities for bulk or lamellar LDHs, generally up to 10 -3 S cm -1 , are considered not high enough for practical applications. We show that single-layer LDH nanosheets exhibited exceptionally high in-plane conductivities approaching 10 -1 S cm -1 , which were the highest among anion conductors and comparable to proton conductivities in commercial proton exchange membranes (for example, Nafion). The in-plane conductivities were four to five orders of magnitude higher than the cross-plane or cross-membrane values of restacked LDH nanosheets. This 2D superionic transport characteristic might have great promises in a variety of applications including alkaline fuel cells and water electrolysis.

  5. Hydroxylated chalcones with dual properties: Xanthine oxidase inhibitors and radical scavengers. (United States)

    Hofmann, Emily; Webster, Jonathan; Do, Thuy; Kline, Reid; Snider, Lindsey; Hauser, Quintin; Higginbottom, Grace; Campbell, Austin; Ma, Lili; Paula, Stefan


    In this study, we evaluated the abilities of a series of chalcones to inhibit the activity of the enzyme xanthine oxidase (XO) and to scavenge radicals. 20 mono- and polyhydroxylated chalcone derivatives were synthesized by Claisen-Schmidt condensation reactions and then tested for inhibitory potency against XO, a known generator of reactive oxygen species (ROS). In parallel, the ability of the synthesized chalcones to scavenge a stable radical was determined. Structure-activity relationship analysis in conjunction with molecular docking indicated that the most active XO inhibitors carried a minimum of three hydroxyl groups. Moreover, the most effective radical scavengers had two neighboring hydroxyl groups on at least one of the two phenyl rings. Since it has been proposed previously that XO inhibition and radical scavenging could be useful properties for reduction of ROS-levels in tissue, we determined the chalcones' effects to rescue neurons subjected to ROS-induced stress created by the addition of β-amyloid peptide. Best protection was provided by chalcones that combined good inhibitory potency with high radical scavenging ability in a single molecule, an observation that points to a potential therapeutic value of this compound class. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Hydroxyl radical modification of collagen type II increases its arthritogenicity and immunogenicity.

    Directory of Open Access Journals (Sweden)

    Uzma Shahab

    Full Text Available BACKGROUND: The oxidation of proteins by endogenously generated free radicals causes structural modifications in the molecules that lead to generation of neo-antigenic epitopes that have implications in various autoimmune disorders, including rheumatoid arthritis (RA. Collagen induced arthritis (CIA in rodents (rats and mice is an accepted experimental model for RA. METHODOLOGY/PRINCIPAL FINDINGS: Hydroxyl radicals were generated by the Fenton reaction. Collagen type II (CII was modified by •OH radical (CII-OH and analysed by ultraviolet-visible (UV-VIS, fluorescence and circular dichroism (CD spectroscopy. The immunogenicity of native and modified CII was checked in female Lewis rats and specificity of the induced antibodies was ascertained by enzyme linked immunosorbent assay (ELISA. The extent of CIA was evaluated by visual inspection. We also estimated the oxidative and inflammatory markers in the sera of immunized rats. A slight change in the triple helical structure of CII as well as fragmentation was observed after hydroxyl radical modification. The modified CII was found to be highly arthritogenic and immunogenic as compared to the native form. The CII-OH immunized rats exhibited increased oxidative stress and inflammation as compared to the CII immunized rats in the control group. CONCLUSIONS/SIGNIFICANCE: Neo-antigenic epitopes were generated on (•OH modified CII which rendered it highly immunogenic and arthritogenic as compared to the unmodified form. Since the rodent CIA model shares many features with human RA, these results illuminate the role of free radicals in human RA.

  7. Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu-Juan [School of Materials Science and Engineering, University of Science and Technology Beijing, 100083 Beijing (China); Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); Lan, Jian-Hui; Wang, Lin; Wu, Qun-Yan; Wang, Cong-Zhi; Bo, Tao [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); Chai, Zhi-Fang [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); School of Radiological & Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, 215123 Suzhou (China); Shi, Wei-Qun, E-mail: [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China)


    Highlights: • Ti{sub 3}C{sub 2}(OH){sub 2} is firstly predicted to be an effective adsorbent for uranyl ions. • The bidentate coordination is energetically more favorable. • The uranyl ion prefers to bind with the deprotonated O adsorption site. • Chemical interaction and hydrogen bonds contribute to the adsorption mechanism. • The theoretical adsorption capacity can approach 595.3 mg/g. - Abstract: In this work, hydroxylated titanium carbide Ti{sub 3}C{sub 2}(OH){sub 2}, a representative of the two-dimensional transition metal carbides, has been predicted to be an effective adsorbent for uranyl ions in aqueous environments for the first time using density functional theory simulations. The calculations revealed that the uranyl ion can strongly bind with Ti{sub 3}C{sub 2}(OH){sub 2} nanosheet in aqueous solution regardless of the presence of anionic ligands such as OH{sup −}, Cl{sup −} and NO{sub 3}{sup −}. The bidentate coordination of uranyl to the surface is energetically more favorable than other adsorption configurations, and the uranyl ion prefers to bind with the deprotonated O adsorption site rather than the protonated one on the hydroxylated surface. During the adsorption process, the chemical adsorption as well as the formation of hydrogen bonds is the dominant factor.

  8. Eugenol derivatives as potential anti-oxidants: is phenolic hydroxyl necessary to obtain an effect? (United States)

    d' Avila Farias, Marília; Oliveira, Pathise Souto; Dutra, Filipe S Pereira; Fernandes, Thiely Jacobsen; de Pereira, Claudio M P; de Oliveira, Simone Quintana; Stefanello, Francieli Moro; Lencina, Claiton Leonetti; Barschak, Alethéa Gatto


    Eugenol, obtained from clove oil (Eugenia caryophyllata), possess several biological activities. It is anti-inflammatory, analgesic, anaesthesic, antipyretic, antiplatelet, anti-anaphylactic, anticonvulsant, anti-oxidant, antibacterial, antidepressant, antifungal and antiviral. The anti-oxidant activity of eugenol have already been proven. From this perspective testing, a series of planned structural derivatives of eugenol were screened to perform structural optimization and consequent increase of the potency of these biological activities. In an attempt to increase structural variability, 16 compounds were synthesized by acylation and alkylation of the phenolic hydroxyl group. Anti-oxidant activity capacity was based on the capture of DPPH radical (2,2-diphenyl-1-picryl-hydrazyl), ABTS radical 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid), measure of TBARS (thiobarbituric acid-reactive species), total sulfhydryl and carbonyl content (eugenol derivatives final concentrations range from 50 to 200 μm). Four derivatives presented an efficient concentration to decrease 50% of the DPPH radical (EC50 ) Eugenol derivatives presenting alkyl or aryl (alkylic or arylic) groups substituting hydroxyl 1 of eugenol were effective in reducing lipid peroxidation, protein oxidative damage by carbonyl formation and increase total thiol content in cerebral cortex homogenates. In liver, the eugenol derivatives evaluated had no effect. Our results suggest that these molecules are promising anti-oxidants agents. © 2013 Royal Pharmaceutical Society.

  9. Suitability of the hydrocarbon-hydroxylating molybdenum-enzyme ethylbenzene dehydrogenase for industrial chiral alcohol production. (United States)

    Tataruch, M; Heider, J; Bryjak, J; Nowak, P; Knack, D; Czerniak, A; Liesiene, J; Szaleniec, M


    The molybdenum/iron-sulfur/heme protein ethylbenzene dehydrogenase (EbDH) was successfully applied to catalyze enantiospecific hydroxylation of alkylaromatic and alkylheterocyclic compounds. The optimization of the synthetic procedure involves use of the enzyme in a crude purification state that saves significant preparation effort and is more stable than purified EbDH without exhibiting unwanted side reactions. Moreover, immobilization of the enzyme on a crystalline cellulose support and changes in reaction conditions were introduced in order to increase the amounts of product formed (anaerobic atmosphere, electrochemical electron acceptor recycling or utilization of ferricyanide as alternative electron acceptor in high concentrations). We report here on an extension of effective enzyme activity from 4h to more than 10 days and final product yields of up to 0.4-0.5g/l, which represent a decent starting point for further optimization. Therefore, we expect that the hydrocarbon-hydroxylation capabilities of EbDH may be developed into a new process of industrial production of chiral alcohols. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. An efficient quantitation strategy for hydroxyl radical-mediated protein footprinting using Proteome Discoverer. (United States)

    Rinas, Aimee; Espino, Jessica A; Jones, Lisa M


    Hydroxyl radical protein footprinting coupled with mass spectrometry has become an invaluable technique for protein structural characterization. In this method, hydroxyl radicals react with solvent exposed amino acid side chains producing stable, covalently attached labels. Although this technique yields beneficial information, the extensive list of known oxidation products produced make the identification and quantitation process considerably complex. Currently, the methods available for analysis either involve manual analysis steps, or limit the amount of searchable modifications or the size of sequence database. This creates a bottleneck which can result in a long and arduous analysis process, which is further compounded in a complex sample. Here, we report the use of a new footprinting analysis method for both peptide and residue-level analysis, demonstrated on the GCaMP2 synthetic construct in calcium free and calcium bound states. This method utilizes a customized multi-search node workflow developed for an on-market search platform in conjunction with a quantitation platform developed using a free Excel add-in. Moreover, the method expedites the analysis process, requiring only two post-search hours to complete quantitation, regardless of the size of the experiment or the sample complexity.

  11. Metabolism of diclofenac in plants--hydroxylation is followed by glucose conjugation. (United States)

    Huber, Christian; Bartha, Bernadett; Schröder, Peter


    Pharmaceuticals from human or veterinary medication form a new class of micropollutants that poses a serious threat to our aquatic environment and its organisms. The intensively used nonsteroidal anti-inflammatory drug diclofenac is found in the environment worldwide due to its poor elimination during waste water treatment processes. In order to test phytoremediation as a tool for the removal of this drug from waste water, the uptake of the compound into plant tissues and its metabolic pathway was addressed using Hordeum vulgare (barley) and a hairy root cell culture of Armoracia rusticana (horse radish) as model species. Diclofenac is taken up by plants and undergoes rapid metabolization; already after 3h of exposure the drug and its metabolites could be detected in the plant tissues. Similar to its fate in mammalian cells the drug is activated in a phase I reaction resulting in the hydroxylated metabolite 4'OH-diclofenac which is conjugated subsequently in phase II to a glucopyranoside, a typical plant specific metabolite. After exposure to 10 and 100 μM diclofenac a concentration dependent formation of the hydroxylated metabolite was observed, while the formation of the phase II metabolite OH-diclofenac glucopyranoside was not positively affected by the higher concentration. To our knowledge this is the first time these two human painkiller metabolites are shown to occur in plant tissues. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Structural and Functional Properties Changes of β-Conglycinin Exposed to Hydroxyl Radical-Generating Systems

    Directory of Open Access Journals (Sweden)

    Jing Xu


    Full Text Available The objective of the present study was to examine the structural and functional changes of β-conglycinin exposed to oxidizing radicals produced by FeCl3/H2O2/ascorbic acid hydroxyl radical-generating system (HRGS for 3 h at room temperature. Increasing H2O2 concentrations resulted in a loss of histidine residues, lysine residues, and available lysine, which was accompanied by the formation of protein carbonyls and disulphide bonds (p < 0.05. Changes in secondary structure, surface hydrophobicity, and intrinsic fluorescence indicated that hydroxyl radicals had induced protein unfolding and conformational alterations. Results from SDS-PAGE implied that a small amount of protein cross-linkages produced by oxidative incubation. The emulsifying properties of β-conglycinin were gradually improved with the increasing extent of oxidation. The structural changes above contributed to the reduction of potential allergenicity of β-conglycinin, as verified by specific ELISA analysis. These results suggest that moderate oxidation could partially improve the protein functional properties and reduced the potential allergy of protein, providing guidance for effective use of moderately oxidized soy protein in the industry.

  13. Antitumor potential of conjugable valinomycins bearing hydroxyl sites: in vitro studies. (United States)

    Iacobazzi, Rosa M; Annese, Cosimo; Azzariti, Amalia; D'Accolti, Lucia; Franco, Massimo; Fusco, Caterina; La Piana, Gianluigi; Laquintana, Valentino; Denora, Nunzio


    Following our pioneering studies on the direct and efficient introduction of derivatizable hydroxyl handles into the valinomycin (VLM, 1) structure, a K(+)-ionophore with potent antitumor activity, the ensuing conjugable analogues (HyVLMs 2, 3, and 4) have herein been compared to the parent macrocycle for their potential antiproliferative effects on a panel of cancer cell lines, namely, human MCF-7, A2780, and HepG2, as well as rat C6 cells. On the basis of IC50 values, we find that hydroxyl analogues 3 and 4 are only moderately less active than 1, while analogue 2 experiences a heavily diminished activity. Cytofluorimetric analyses of MCF-7 cells treated with HyVLMs suggest that the latter depolarize mitochondria, thus retaining the typical VLM behavior. It is likely that C6 cells, for which the exceptionally potent cytotoxicity of VLM has never reported previously, follow the same fate, as evidenced by alteration of mitochondrial morphology upon incubation with each ionophore.

  14. Openness initiative

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, S.S. [Los Alamos National Lab., NM (United States)


    Although antinuclear campaigns seem to be effective, public communication and education efforts on low-level radioactive waste have mixed results. Attempts at public information programs on low-level radioactive waste still focus on influencing public opinion. A question then is: {open_quotes}Is it preferable to have a program focus on public education that will empower individuals to make informed decisions rather than trying to influence them in their decisions?{close_quotes} To address this question, a case study with both quantitative and qualitative data will be used. The Ohio Low-Level Radioactive Waste Education Program has a goal to provide people with information they want/need to make their own decisions. The program initiated its efforts by conducting a statewide survey to determine information needed by people and where they turned for that information. This presentation reports data from the survey and then explores the program development process in which programs were designed and presented using the information. Pre and post data from the programs reveal attitude and knowledge shifts.

  15. Well-Defined Bilayered Molecular Cobrushes with Internal Polyethylene Blocks and ω-Hydroxyl-Functionalized Polyethylene Homobrushes

    KAUST Repository

    Zhang, Hefeng


    Novel well-defined bilayered molecular cobrushes with internal polyethylene blocks, P(PEcore-b-PScorona) (PE: polyethylene; PS: polystyrene), and ω-hydroxyl-functionalized polyethylene homobrushes, P(PE-OH), were synthesized through the macromonomer strategy. Two main steps were involved in the synthesis of the P(PEcore-b-PScorona) bilayered cobrushes: (i) formation of norbornyl-terminated macromonomer (Nor-PE-b-PS) by esterification of PS-b-PE-OH (combination of anionic polymerization, hydroboration, and polyhomologation) with 5-norbornene-2-carboxylic acid and (ii) ring-opening metathesis polymerization (ROMP) of Nor-PE-b-PS. The synthesis of P(PE-OH) was achieved by (i) hydroboration of tert-butyldimethylsilyl-protected allyl alcohol, followed by polyhomologation of dimethylsulfoxoniun methylide with the formed tri[3-(tert-butyldimethylsilyloxyl)propyl]borane initiator, oxidation/hydrolysis, and esterification of the TBDMS-O-PE-OH with 5-norbornene-2-carboxylic acid to afford the macromonomer TBDMS-O-PE-Nor, and (ii) ROMP of TBDMS-O-PE-Nor, followed by deprotection. Nuclear magnetic resonance spectroscopy (1H and 13C NMR) and high temperature gel permeation chromatography (HT-GPC) were used to characterize all macromonomers/molecular brushes and differential scanning calorimetry (DSC) to study the thermal properties. The molecular brush P(PE-b-PS) showed lower melting point (Tm) and better solubility in toluene than the corresponding macromonomer PS-b-PE-Nor. In the case of homobrushes, the thermal properties were strongly affected by the presence of the PE end-groups. © 2016 American Chemical Society.

  16. Role of hydroxylation modification on the structure and property of reduced graphene oxide/TiO{sub 2} hybrids

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Shiyi [College of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Liu, Tiangui, E-mail: [College of Physics and Microelectronics Science, Hunan University, Changsha 410082 (China); Tsang, Yuenhong [Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, 999077 (China); Chen, Chuansheng, E-mail: [College of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China)


    Graphical abstract: The structure model and enhancement mechanism of hydroxylation treatment on adsorbability and photocatalytic activity. - Highlights: • Highly-hydroxylated TiO{sub 2}/rGO hybrids can be obtained by UV pre-excitation and microwave method. • Surface hydroxylation induces many defects (Ti{sup 3+}, O vacancy and Ti-OH) and changes color into yellow. • Hydroxylation expands the light absorption up to about 600 nm and benefits to adsorb organic dyes. • ESR reveals the self-accumulation of hydroxyl radicals under the irradiation of UV and visible light. • The photoinduced defects and rGO/TiO{sub 2}@OH-TiO{sub 2} heterojunctions enable the excellent applicability. - Abstract: To extend the spectra response of TiO{sub 2} and enhance its photocatalytic activity, surface modification and catalyst supporter have attracted great attention. In this report, a simple and versatile approach has been developed to hydroxylate the reduced graphene oxide/TiO{sub 2} hybrids (OH-rGO/TiO{sub 2}) by UV-microwave method, and the enhanced mechanisms of hydroxylation were analyzed in details. Experimental results show that TiO{sub 2} nanocrystals@OH-TiO{sub 2} heterojunctions formed on rGO sheets in situ by UV/H{sub 2}O{sub 2} process. Hydroxylation not only can induce many surface defects (Ti{sup 3+}, O vacancy and Ti-OH) on the surface of TiO{sub 2}, but also change the color into yellow and strengthen the interaction between rGO and TiO{sub 2}. OH-rGO/TiO{sub 2} hybrids showed excellent durability for high-concentration dyes, and exhibited strong adsorbability and photocatalytic activity. These enhancements are attributed to the excellent property of rGO and surface defects of TiO{sub 2} induced by hydroxylation, which expand the light absorption up to 600 nm, benefit to the self-dispersion of hybrids, and improve the adsorption dynamic and charge transfer with lower carrier’s recombination.

  17. CYP106A2-A versatile biocatalyst with high potential for biotechnological production of selectively hydroxylated steroid and terpenoid compounds. (United States)

    Schmitz, Daniela; Janocha, Simon; Kiss, Flora Marta; Bernhardt, Rita


    CYP106A2 from Bacillus megaterium ATCC13368, was identified in the 1970s as one of the first bacterial steroid hydroxylases responsible for the conversion of progesterone to 15β-hydroxyprogesterone. Later on it has been proven to be a potent hydroxylase of numerous 3-oxo-Δ 4 as well as 3-hydroxy-Δ 5 -steroids and has recently also been characterized as a regioselective allylic bacterial diterpene hydroxylase. The main hydroxylation position of CYP106A2 is thought to be influenced by the functional groups at C3 position in the steroid core leading to a favored 15β-hydroxylation of 3-oxo-Δ 4 -steroids and 7β-hydroxylation of 3-hydroxy-Δ 5 -steroids. However, in some cases the hydroxylation is not strictly selective, resulting in the formation of undesired side-products. To overcome the unspecific hydroxylations or, on the contrary, to gain more of these products in case they are of industrial interest, rational protein design and directed evolution have been successfully performed to shift the stereoselectivity of hydroxylation by CYP106A2. The subsequently obtained hydroxylated steroid and terpene derivatives are especially useful as drug metabolites and drug precursors for the pharmaceutical industry, due to their diverse biological properties and hardship of their chemical synthesis. As a soluble prokaryotic P450 with broad substrate spectrum and hydroxylating capacity, CYP106A2 is an outstanding candidate to establish bioconversion processes. It has been expressed with respectable yields in Escherichia coli and Bacillus megaterium and was applied for the preparative hydroxylation of several steroids and terpenes. Recently, the application of the enzyme was assessed under process conditions as well, depicting a successfully optimized process development and getting us closer to industrial scale process requirements and a future large scale application. This article is part of a Special Issue entitled: Cytochrome P450 biodiversity and biotechnology, edited

  18. The possible role of hydroxylation in the detoxification of atrazine in mature vetiver (Chrysopogon zizanioides Nash) grown in hydroponics. (United States)

    Marcacci, Sylvie; Raventon, Muriel; Ravanel, Patrick; Schwitzguébel, Jean-Paul


    The resistance mechanism of vetiver (Chrysopogon zizanioides) to atrazine was investigated to evaluate its potential for phytoremediation of environment contaminated with the herbicide. Plants known to metabolise atrazine rely on hydroxylation mediated by benzoxazinones, conjugation catalyzed by glutathione-S-transferases and dealkylation probably mediated by cytochromes P450. All three possibilities were explored in mature vetiver grown in hydroponics during this research project. Here we report on the chemical role of benzoxazinones in the transformation of atrazine. Fresh vetiver roots and leaves were cut to extract and study their content in benzoxazinones known to hydroxylate atrazine, such as 2,4-dihydroxy-2H-1,4-benzoxazin-3(4H)-one (DIBOA), 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (DIMBOA) and their mono- and di-glucosylated forms. Identification of benzoxazinones was performed by thin layer chromatography (TLC) and comparison of retention factors (Rf) and UV spectra with standards: although some products exhibited the same Rf as standards, UV spectra were different. Furthermore, in vitro hydroxylation of atrazine could not be detected in the presence of vetiver extracts. Finally, vetiver organs exposed to [14C]-atrazine did not produce any significant amount of hydroxylated products, such as hydroxyatrazine (HATR), hydroxy-deethylatrazine (HDEA), and hydroxy-deisopropylatrazine (HDIA). Altogether, these metabolic features suggest that hydroxylation was not a major metabolic pathway of atrazine in vetiver.

  19. Impact of Ti Incorporation on Hydroxylation and Wetting of Fe 3 O 4

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A.; Pearce, Carolyn I.; Droubay, Timothy C.; Shutthanandan, Vaithiyalingam; Shavorskiy, Andrey [Chemical; Bluhm, Hendrik [Chemical; Rosso, Kevin M.


    Understanding the interaction of water with compositionally tuned metal oxides is central to exploiting their unique catalytic and magnetic properties. However, processes such as hydroxylation, wetting, and resulting changes in electronic structure at ambient conditions are challenging to probe in situ. Here, we examine the hydroxylation and wetting of Fe(3-x)TixO4 epitaxial films directly using ambient pressure X-ray photoelectron spectroscopy under controlled relative humidity. Fe2+ formation promoted by Ti4+ substitution for Fe3+ increases with hydroxylation, commensurate with a decrease in the surface work function or change in the surface dipole. The incorporation of small amounts of Ti (x=0.25) as a bulk dopant dramatically impacts hydroxylation, in part due to surface segregation, leading to coverages closer to that of TiO2 than Fe3O4. However, the Fe(3-x)TixO4 compositional series shows a similar affinity for water physisorption, which begins at notably lower relative humidity than on TiO2. The findings suggest that relative humidity rather than surface hydroxyl density controls wettability. Studies of this kind directly relate to rational design of doped magnetite into more active catalysts for UV/Fenton degradation, the adsorption of contaminants, and the development of spin filters.

  20. Energy balance of the metropolitan zone of the valley of Mexico, methodology and the entailment energy-air quality; Balance de energia de la zona metropolitana del valle de Mexico metodologia y la vinculacion energia - calidad del aire

    Energy Technology Data Exchange (ETDEWEB)

    Bazan Navarrete, Gerardo [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)


    The present document raises a methodology for the elaboration of the Energy Balance of the Metropolitan Zone of the Valley of Mexico (ZMVM), in order to unify criteria and to facilitate the work of entities and investigators, mainly of those that require the entailment of energy and environment. The applied methodology, the consolidated format and the caloric unity facilitates the insertion of the Energy Balance of the ZMVM within the National Balance of Energy. The regional balances of energy have the intention of knowing the energy consumption patterns in the ZMVM and the indexes of energy intensity by sector. They establish the relationship of the indexes of energy intensity with the local and global air quality of the region, performing studies of incidence with the main polluting agents and with the greenhouse effect gases. [Spanish] El presente documento plantea una metodologia para la elaboracion del Balance de Energia de la Zona Metropolitana del Valle de Mexico (ZMVM), con el proposito de unificar criterios y facilitar el trabajo de organismos e investigadores, sobre todo de aquellos que requieren vincular energia y medio ambiente. La metodologia aplicad, el formato consolidado y la unidad calorica facilitan la insercion del Balance de Energia de la ZMVM dentro del Balance Nacional de Energia. Los balances regionales de energia tienen el proposito de conocer los patrones de consumo de energia en la ZMVM y los indices de intensidad energetica por sector. Establecen la relacion de los indices de intensidad energetica con la calidad del aire local y global de la region, realizando estudios de incidencia con los principales contaminantes y con los gases de efecto invernadero.

  1. Microdrill Initiative - Initial Market Evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Spears & Associates, Inc


    The U.S. Department of Energy (DOE) is launching a major research and development initiative to create a small, fast, inexpensive and environmentally friendly rig for drilling 5000 feet boreholes to investigate potential oil and gas reservoirs. DOE wishes to get input from petroleum industry operators, service companies and equipment suppliers on the operation and application of this coiled-tubing-based drilling unit. To that end, DOE has asked Spears & Associates, Inc. (SAI) to prepare a special state-of-the-market report and assist during a DOE-sponsored project-scoping workshop in Albuquerque near the end of April 2003. The scope of the project is four-fold: (1) Evaluate the history, status and future of demand for very small bore-hole drilling; (2) Measure the market for coiled tubing drilling and describe the state-of-the-art; (3) Identify companies and individuals who should have an interest in micro drilling and invite them to the DOE workshop; and (4) Participate in 3 concurrent workshop sessions, record and evaluate participant comments and report workshop conclusions.

  2. Improved brain MRI indices in the acute brain stem infarct sites treated with hydroxyl radical scavengers, Edaravone and hydrogen, as compared to Edaravone alone. A non-controlled study. (United States)

    Ono, Hirohisa; Nishijima, Yoji; Adachi, Naoto; Tachibana, Shigekuni; Chitoku, Shiroh; Mukaihara, Shigeo; Sakamoto, Masaki; Kudo, Yohei; Nakazawa, Jun; Kaneko, Kumi; Nawashiro, Hiroshi


    In acute stage of cerebral infarction, MRI indices (rDWI & rADC) deteriorate during the first 3-7 days after the ictus and then gradually normalize in approximately 10 days (pseudonormalization time), although the tissue is already infarcted. Since effective treatments improve these indices significantly and in less than the natural pseudonormalization time, a combined analysis of these changes provides an opportunity for objective evaluation on the effectiveness of various treatments for cerebral infarction. Hydroxyl radicals are highly destructive to the tissue and aggravate cerebral infarction. We treated brainstem infarction patients in acute stage with hydroxyl radical scavengers (Edaravone and hydrogen) by intravenous administration and evaluated the effects of the treatment by a serial observation and analysis of these MRI indices. The effects of the treatment were evaluated and compared in two groups, an Edaravone alone group and a combined group with Edaravone and hydrogen, in order to assess beneficial effects of addition of hydrogen. The patients were divided in Edaravone only group (E group. 26 patients) and combined treatment group with Edaravone and hydrogen enriched saline (EH group. 8 patients). The extent of the initial hump of rDWI, the initial dip of rADC and pseudo-normalization time were determined in each patient serially and averages of these data were compared in these two groups and also with the natural course in the literatures. The initial hump of rDWI reached 2.0 in the E group which was better than 2.5 of the natural course but was not as good as 1.5 of the EH group. The initial dip of rADC was 0.6 in the E group which was close to the natural course but worse than 0.8 of the EH group. Pseudonormalization time of rDWI and rADC was 9 days only in EH group but longer in other groups. Addition of hydrogen caused no side effects. Administration of hydroxyl radical scavengers in acute stage of brainstem infarction improved MRI indices

  3. Improved brain MRI indices in the acute brain stem infarct sites treated with hydroxyl radical scavengers, Edaravone and hydrogen, as compared to Edaravone alone. A non-controlled study

    Directory of Open Access Journals (Sweden)

    Ono Hirohisa


    Full Text Available Abstract Background In acute stage of cerebral infarction, MRI indices (rDWI & rADC deteriorate during the first 3-7 days after the ictus and then gradually normalize in approximately 10 days (pseudonormalization time, although the tissue is already infarcted. Since effective treatments improve these indices significantly and in less than the natural pseudonormalization time, a combined analysis of these changes provides an opportunity for objective evaluation on the effectiveness of various treatments for cerebral infarction. Hydroxyl radicals are highly destructive to the tissue and aggravate cerebral infarction. We treated brainstem infarction patients in acute stage with hydroxyl radical scavengers (Edaravone and hydrogen by intravenous administration and evaluated the effects of the treatment by a serial observation and analysis of these MRI indices. The effects of the treatment were evaluated and compared in two groups, an Edaravone alone group and a combined group with Edaravone and hydrogen, in order to assess beneficial effects of addition of hydrogen. Methods The patients were divided in Edaravone only group (E group. 26 patients and combined treatment group with Edaravone and hydrogen enriched saline (EH group. 8 patients. The extent of the initial hump of rDWI, the initial dip of rADC and pseudo-normalization time were determined in each patient serially and averages of these data were compared in these two groups and also with the natural course in the literatures. Results The initial hump of rDWI reached 2.0 in the E group which was better than 2.5 of the natural course but was not as good as 1.5 of the EH group. The initial dip of rADC was 0.6 in the E group which was close to the natural course but worse than 0.8 of the EH group. Pseudonormalization time of rDWI and rADC was 9 days only in EH group but longer in other groups. Addition of hydrogen caused no side effects. Conclusions Administration of hydroxyl radical scavengers in

  4. Pristine and thermally-rearranged gas separation membranes from novel o-hydroxyl-functionalized spirobifluorene-based polyimides

    KAUST Repository

    Ma, Xiaohua


    A novel o-hydroxyl-functionalized spirobifluorene-based diamine monomer, 2,2′-dihydroxyl-9,9′-spiro-bifluorene- 3,3′-diamine (HSBF), was successfully prepared by a universal synthetic method. Two o-hydroxyl-containing polyimides, denoted as 6FDA-HSBF and SPDA-HSBF, were synthesized and characterized. The BET surface areas of 6FDA-HSBF and SPDA-HSBF are 70 and 464 m2 g-1, respectively. To date, SPDA-HSBF exhibits the highest CO2 permeability (568 Barrer) among all hydroxyl-containing polyimides. The HSBF-based polyimides exhibited higher CO2/CH4 selectivity than their spirobifluorene (SBF) analogues (42 for 6FDA-HSBF vs. 27 for 6FDA-SBF) due to an increase in their diffusivity selectivity. Polybenzoxazole (PBO) membranes obtained from HSBF-based polyimide precursors by thermal rearrangement showed enhanced permeability but at the cost of significantly decreased selectivity.

  5. Nanocomposites of ferroelectric polymers with surface-hydroxylated BaTiO 3 nanoparticles for energy storage applications

    KAUST Repository

    Almadhoun, Mahmoud Nassar Mahmoud


    A facile surface hydroxylation treatment using hydrogen peroxide to modify the surface of BaTiO 3 nanofillers dispersed in a ferroelectric copolymer host has been investigated. We demonstrate that the surface functionalization of the BaTiO 3 nanofillers (<100 nm) with hydroxyl groups results in as much as two orders of magnitude reduction in the leakage current of nanocomposite thin-film capacitors. This reduction is observed concurrently with the enhancement of the effective permittivity and breakdown strength of the thin-film nanocomposites. Surface modified BaTiO 3 particles display better dispersion within the polymer matrix, resulting in enhanced relative permittivity and reduced dielectric loss. The dielectric behavior of the nanocomposite films containing up to 30 vol.% BaTiO 3 agreed well with the Bruggeman model. These results demonstrate the potential of facile surface hydroxylation of nanoparticles towards the fabrication of higher energy-density nanocomposites. © 2012 The Royal Society of Chemistry.

  6. Metabolic network capacity of Escherichia coli for Krebs cycle-dependent proline hydroxylation. (United States)

    Theodosiou, Eleni; Frick, Oliver; Bühler, Bruno; Schmid, Andreas


    Understanding the metabolism of the microbial host is essential for the development and optimization of whole-cell based biocatalytic processes, as it dictates production efficiency. This is especially true for redox biocatalysis where metabolically active cells are employed because of the cofactor/cosubstrate regenerative capacity endogenous in the host. Recombinant Escherichia coli was used for overproducing proline-4-hydroxylase (P4H), a dioxygenase catalyzing the hydroxylation of free L-proline into trans-4-hydroxy-L-proline with a-ketoglutarate (a-KG) as cosubstrate. In this whole-cell biocatalyst, central carbon metabolism provides the required cosubstrate a-KG, coupling P4H biocatalytic performance directly to carbon metabolism and metabolic activity. By applying both experimental and computational biology tools, such as metabolic engineering and (13)C-metabolic flux analysis ((13)C-MFA), we investigated and quantitatively described the physiological, metabolic, and bioenergetic response of the whole-cell biocatalyst to the targeted bioconversion and identified possible metabolic bottlenecks for further rational pathway engineering. A proline degradation-deficient E. coli strain was constructed by deleting the putA gene encoding proline dehydrogenase. Whole-cell biotransformations with this mutant strain led not only to quantitative proline hydroxylation but also to a doubling of the specific trans-4-L-hydroxyproline (hyp) formation rate, compared to the wild type. Analysis of carbon flux through central metabolism of the mutant strain revealed that the increased a-KG demand for P4H activity did not enhance the a-KG generating flux, indicating a tightly regulated TCA cycle operation under the conditions studied. In the wild type strain, P4H synthesis and catalysis caused a reduction in biomass yield. Interestingly, the ΔputA strain additionally compensated the associated ATP and NADH loss by reducing maintenance energy demands at comparably low glucose

  7. [Influence of sodium nitrite exposure on sulfhemoglobin and hydroxyl radicals in mice]. (United States)

    Zhang, Z Q; Lin, L; Zhang, C Z


    Objective: To investigate the influence of sodium nitrite exposure on sulfhemoglobin and hydroxyl radicals in mice. Methods: A total of 60 mice were randomly divided into low-, middle-, and high-dose groups (the concentrations of sodium nitrite were 0.055 mg/ml, 0.110 mg/ml, and 0.220 mg/ml, respectively) and control group (treated with distilled water) , with 15 mice in each group (male/female ratio=1: 1) . A free-drink model was applied and the duration of exposure was 2 weeks. The body weight of all mice was recorded before exposure and at weeks 1 and 2 of exposure. At the end of exposure, the mice were treated with intraperitoneally injected sodium salicylate to capture the hydroxyl radicals and produce 2, 5-dihydroxybenzoic acid and 2, 3-dihydroxybenzoic acid, and high-performance liquid chromatography was used to measure their content. Spectrophotometry was used to measure the relative content of sulfhemoglobin. Results: At week 2 of exposure, the low-, middle-, and high-dose groups had significantly lower body weight than the control group (22.8±2.8 g/21.6±2.8 g/21.2±3.0 g vs 25.6±2.2 g, Pgroups had a significantly higher total content of hydroxyl radicals than the control group[ (0.015 3±0.006 5) μg/ml, (0.016 4±0.017 2) μg/ml, and (0.062 7±0.091 0) μg/ml vs (0.009 ±0.007 3) μg/ml, Pgroups, and the middle- and high-dose groups had a significant increase in the relative content of sulfhemoglobin compared with the control group (2.22%±0.44%/2.80%±0.69% vs 1.76%±0.60%, Phydroxyl radicals was positively correlated with the relative content of sulfhemoglobin (r=0.837, Phydroxyl radicals in blood, and there is a positive correlation between them.

  8. Experiments and simulations of NOx formation in the combustion of hydroxylated fuels

    KAUST Repository

    Bohon, Myles


    This work investigates the influence of molecular structure in hydroxylated fuels (i.e. fuels with one or more hydroxyl groups), such as alcohols and polyols, on NOx formation. The fuels studied are three lower alcohols (methanol, ethanol, and n-propanol), two diols (1,2-ethanediol and 1,2-propanediol), and one triol (1,2,3-propanetriol); all of which are liquids at room temperature and span a wide range of thermophysical properties. Experimental stack emissions measurements of NO/NO2, CO, and CO2 and flame temperature profiles utilizing a rake of thermocouples were obtained in globally lean, swirling, liquid atomized spray flames inside a refractory-lined combustion chamber as a function of the atomizing air flow rate and swirl number. These experiments show significantly lower NOx formation with increasing fuel oxygen content despite similarities in the flame temperature profiles. By controlling the temperature profiles, the contribution to NOx formation through the thermal mechanism were matched, and variations in the contribution through non-thermal NOx formation pathways are observed. Simulations in a perfectly stirred reactor, at conditions representative of those measured within the combustion region, were conducted as a function of temperature and equivalence ratio. The simulations employed a detailed high temperature chemical kinetic model for NOx formation from hydroxylated fuels developed based on recent alcohol combustion models and extended to include polyol combustion chemistry. These simulations provide a qualitative comparison to the range of temperatures and equivalence ratios observed in complex swirling flows and provide insight into the influence of variations in the fuel decomposition pathways on NOx formation. It is observed that increasing the fuel bound oxygen concentration ultimately reduces the formation of NOx by increasing the proportion of fuel oxidized through formaldehyde, as opposed to acetylene or acetaldehyde. The subsequent

  9. Structural and enzymatic parameters that determine alkyl dehydrogenation/hydroxylation of capsaicinoids by cytochrome p450 enzymes. (United States)

    Reilly, Christopher A; Yost, Garold S


    Previous studies on the metabolism of capsaicinoids, natural products isolated from chili peppers, demonstrated the production of unique macrocyclic, alkyl dehydrogenated, omega-, and omega-1-hydroxylated products. This study investigated the structural and enzymatic parameters that direct selective alkyl dehydrogenation and hydroxylation of capsaicinoids, using a variety of structurally related capsaicinoid analogs and cytochrome P450 (P450) enzymes. CYP2C9 preferentially catalyzed alkyl dehydrogenation, whereas CYP2E1 and 3A4 catalyzed omega- and omega-1-hydroxylation, respectively. Analysis of incubations containing various P450s and structural variants of capsaicin by liquid chromatography-tandem mass spectrometry demonstrated similarities in the rate of capsaicinoid metabolism, but marked differences in the metabolite profiles. Production of macrocyclic and omega-1-hydroxylated metabolites from the various capsaicinoids was dependent on the structure of the alkyl terminus and P450 enzyme. A tertiary carbon at the omega-1 position, coupled to an adjacent unsaturated bond at the omega-2,3 position, enhanced the formation of the macrocyclic and dehydrogenated metabolites and were requisite structural features for omega-1-hydroxylated product formation. Conversely, substrates lacking these structural features were efficiently oxidized to the omega-hydroxylated metabolite. These data were consistent with our hypothesis that metabolism of the alkyl portion of capsaicinoids was governed, in part, by the stability and propensity to form an intermediate radical and a carbocation, and a direct interaction between the alkyl terminus and the heme of many P450 enzymes. These results provided valuable insights into potential mechanisms by which P450s metabolize capsaicinoids and highlight critical chemical features that may also govern the metabolism of structurally related compounds including fatty acids, monoter-penes, and isoprenoids.

  10. New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Siyu [Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016 (China); Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Ren, Honglei; Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)


    The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (t{sub d,E}) and hydroxyl-radical oxidation half-lives (t{sub ·OH,E}) in sunlit surface waters. The t{sub d,E} values range from 0.56 min to 28.8 min at 45° N latitude, whereas t{sub ·OH,E} ranges from 3.24 h to 33.6 h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. - Highlights: • It is first reported on hydroxyl-radical oxidation of 6 fluoroquinolone antibiotics. • Methods were developed to assess photolysis and oxidation fate in surface waters. • The neutral form reacted faster with hydroxyl radical than protonated forms. • The main oxidation intermediates and transformation pathways were clarified. • The antibacterial activity changes depend on dominant photolysis pathways.

  11. Elucidation of the substitution pattern of 9,10-anthraquinones through the chemical shifts of peri-hydroxyl protons

    DEFF Research Database (Denmark)

    Schripsema, Jan; Danigno, Denise


    In 9,10-anthraquinones the chemical shift of a peri-hydroxyl proton is affected by the substituents in the other benzenoid ring. These effects are additive. They are useful for the determination of substitution patterns and have been used to revise the structures of six previously reported...... anthraquinones containing methoxyl, hydroxyl, methylenedioxy and beta-methyl substituents. Because the chemical shifts of the other protons are hardly affected by substitutions in the other ring, the characteristic chemical shifts for a wide variety of substitution patterns could be derived....

  12. Nucleophilic Hydroxylation in Water Media Promoted by a Hexa-Ethylene Glycol-Bridged Dicationic Ionic Liquid. (United States)

    Jadhav, Vinod H; Kim, Jin Gwan; Jeong, Hyeon Jin; Kim, Dong Wook


    Hexaethylene glycol bis(3-hexaethylene glycol imidazolium) dimesylate ionic liquid (hexaEG-DHIM) was designed and prepared as a highly efficient promoter for the nucleophilic hydroxylation of alkyl halides to the corresponding alcohol products in neat water media. It was observed that hexaEG-DHIM promoter enhanced the nucleophilicity of water significantly in the reaction. In addition, the hexaEG-DHIM could be reused several times without loss of activity. Moreover, the hydroxylation reactions of base-sensitive and/or polar alkyl halide substrates proceeded highly chemoselectively in excellent yields.

  13. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng


    Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing

  14. Methemoglobinemia Hemotoxicity of Some Antimalarial 8-Aminoquinoline Analogues and Their Hydroxylated Derivatives: Density Functional Theory Computation of Ionization Potentials. (United States)

    Ding, Yuanqing; Liu, Haining; Tekwani, Babu L; Nanayakkara, N P Dhammika; Khan, Ikhlas A; Walker, Larry A; Doerksen, Robert J


    The administration of primaquine (PQ), an essential drug for the treatment and radical cure of malaria, can lead to methemoglobin formation and life-threatening hemolysis for glucose-6-phosphate dehydrogenase deficient patients. The ionization potential (IP, a quantitative measure of the ability to lose an electron) of the metabolites generated by antimalarial 8-aminoquinoline (8-AQ) drugs like PQ has been believed to be correlated in part to this methemoglobinemia hemotoxicity: the lower the IP of an 8-AQ derivative, the higher the concentration of methemoglobin generated. In this work, demethoxylated primaquine (AQ02) was employed as a model, by intensive computation at the B3LYP-SCRF(PCM)/6-311++G**//B3LYP/6-31G** level in water, to study the effects of hydroxylation at various positions on the ionization potential. Compared to the parent AQ02, the IPs of AQ02's metabolites hydroxylated at N1', C5, and C7 were lower by 61, 30, and 19 kJ/mol, respectively, while differences in the IP relative to PQ were small for hydroxylation at all other positions. The C6 position, at which the IP of the hydroxylated metabolite was greater than that of AQ02, by 2 kJ/mol, was found to be unique. Several literature and proposed 8-AQ analogues were studied to evaluate substituent effects on their potential to generate methemoglobin, with the finding that hydroxylations at N1' and C5 contribute the most to the potential hemotoxicity of PQ-based antimalarials, whereas hydroxylation at C7 has little effect. Phenoxylation at C5 in PQ-based 8-AQs can block the hydroxylation at C5 and reduce the potential for methemoglobin generation, while -CF3 and chlorines attached to the phenolic ring can further reduce the risk. The H-shift at N1' during the cationization of hydroxylated metabolites of 8-AQs sharply decreased their IPs, but this effect can be significantly reduced by the introduction of an electron-withdrawing group to the quinoline core. The results and this approach may be

  15. Hydroxylated Fluorescent Dyes for Live‐Cell Labeling: Synthesis, Spectra and Super‐Resolution STED† (United States)

    Kolmakov, Kirill; Sokolov, Viktor V.; Shojaei, Heydar; Sidenstein, Sven C.; Kamin, Dirk; Matthias, Jessica; Vlijm, Rifka; Engelhardt, Johann


    Abstract Hydroxylated rhodamines, carbopyronines, silico‐ and germanorhodamines with absorption maxima in the range of 530–640 nm were prepared and applied in specific labeling of living cells. The direct and high‐yielding entry to germa‐ and silaxanthones tolerates the presence of protected heteroatoms and may be considered for the syntheses of various sila‐ and germafluoresceins, as well as ‐rhodols. Application in stimulated emission depletion (STED) fluorescence microscopy revealed a resolution of 50–75 nm in one‐ and two‐color imaging of vimentin‐HaloTag fused protein and native tubulin. The established structure–property relationships allow for prediction of the spectral properties and the positions of spirolactone/zwitterion equilibria for the new analogues of rhodamines, carbo‐, silico‐, and germanorhodamines using simple additive schemes. PMID:28370443

  16. Rates of production of hydroxyl radicals and singlet oxygen from irradiated compost. (United States)

    Coelho, Christian; Cavani, Luciano; ter Halle, Alexandra; Guyot, Ghislain; Ciavatta, Claudio; Richard, Claire


    The use of organic matter from compost to promote the catalytic photodegradation of micropollutants by solar light appears to be environmentally promising. However, quantitative evaluation of the photodegradation potential of the compost is needed. Our goal was to measure the formation rate of hydroxyl radicals and singlet oxygen, two strongly oxidant species, from irradiated compost organic matter. These two reactive species were photogenerated in all of our extracts regardless of the origin of the compost or the extraction procedure; however, their formation rates increased with composting time. Two herbicides and a fungicide were successfully photodegraded when irradiated with simulated or natural solar light in the presence of the compost organic matter or compost suspensions. For reasons of simplification and ease, the use of the latter is recommended in practice. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Hydroxylated graphene-based flexible carbon film with ultrahigh electrical and thermal conductivity (United States)

    Ding, Jiheng; Rahman, Obaid ur; Zhao, Hongran; Peng, Wanjun; Dou, Huimin; Chen, Hao; Yu, Haibin


    Graphene-based films are widely used in the electronics industry. Here, surface hydroxylated graphene sheets (HGS) have been synthesized from natural graphite (NG) by a rapid and efficient molten hydroxide-assisted exfoliation technique. This method enables preparation of aqueous dispersible graphene sheets with a high dispersed concentration (˜10.0 mg ml-1) and an extraordinary production yield (˜100%). The HGS dispersion was processed into graphene flexible film (HGCF) through fast filtration, annealing treatment and mechanical compression. The HGS endows graphene flexible film with a high electrical conductivity of 11.5 × 104 S m-1 and a superior thermal conductivity of 1842 W m-1 K-1. Simultaneously, the superflexible HGCF could endure 3000 repeated cycles of bending or folding. As a result, this graphene flexible film is expected to be integrated into electronic packaging and high-power electronics applications.

  18. The Creation and Physiological Relevance of Divergent Hydroxylation Patterns in the Flavonoid Pathway

    Directory of Open Access Journals (Sweden)

    Heidi Halbwirth


    Full Text Available Flavonoids and biochemically-related chalcones are important secondary metabolites, which are ubiquitously present in plants and therefore also in human food. They fulfill a broad range of physiological functions in planta and there are numerous reports about their physiological relevance for humans. Flavonoids have in common a basic C6-C3-C6 skeleton structure consisting of two aromatic rings (A and B and a heterocyclic ring (C containing one oxygen atom, whereas chalcones, as the intermediates in the formation of flavonoids, have not yet established the heterocyclic C-ring. Flavonoids are grouped into eight different classes, according to the oxidative status of the C-ring. The large number of divergent chalcones and flavonoid structures is from the extensive modification of the basic molecules. The hydroxylation pattern influences physiological properties such as light absorption and antioxidative activity, which is the base for many beneficial health effects of flavonoids. In some cases antiinfective properties are also effected.

  19. Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide with Epoxide and Hydroxyl Groups (United States)

    Nancy Anna Anasthasiya, A.; Khaneja, Mamta; Jeyaprakash, B. G.


    Ammonia adsorption on graphene (G) and graphene oxide (GO) was investigated through density functional theory calculations. In the GO system, the obtained binding energy, band gap, charge transfer and electronic structure revealed that the epoxide (GO-O) and hydroxyl groups (GO-OH) in GO enhance the NH3 adsorption, which leads to the chemisorption of NH3 on GO. The dissociation of NH3 to NH2 and formation of OH was also observed when the O and H atoms were separated at 0.985 Å, 1.019 Å, 1.035 Å, and 1.044 Å for various GO systems. The maximum charge transfer value was found to be 0.054 |e| with the binding energy of 1.143 eV for GO with a single epoxide (GO-1O) group. The charge transfer from NH3 to G or GO and the bond formation in this study agree with the reported experimental results.

  20. Genomic organization and splicing variants of a peptidylglycine alpha-hydroxylating monooxygenase from sea anemones

    DEFF Research Database (Denmark)

    Williamson, M; Hauser, F; Grimmelikhuijzen, C J


    of primitive nervous systems. In mammals, peptide amidation is catalyzed by two enzymes, peptidylglycine alpha-hydroxylating monooxygenase (PHM) and peptidyl-alpha-hydroxyglycine alpha-amidating lyase (PAL) that act sequentially. These two activities are contained within one bifunctional enzyme......, peptidylglycine alpha-amidating monooxygenase (PAM), which is coded for by a single gene. In a previous paper (F. Hauser et al., Biochem. Biophys. Res. Commun. 241, 509-512, 1997) we have cloned the first known cnidarian PHM from the sea anemone Calliactis parasitica. In the present paper we have determined...... the structure of its gene (CP1). CP1 is >12 kb in size and contains 15 exons and 14 introns. The last coding exon (exon 15) contains a stop codon, leaving no room for PAL and, thereby, for a bifunctional PAM enzyme as in mammals. Furthermore, we found a CP1 splicing variant (CP1-B) that contains exon-9 instead...

  1. Synthesis and antinociceptive behaviors of new methyl and hydroxyl derivatives of phencyclidine. (United States)

    Ahmadi, A; Kermani, M; Naderi, N; Hajikhani, R; Rezaee, N M; Javadi, M; Niknafs, B N


    Phencyclidine (I) and its derivatives show such pharmacological behaviors as analgesic, anticonsulvant, anti-anxiety and antidepressant, while interacting with central nervous system. In this study, new methyl and hydroxyl derivatives of PCP were synthesized and their antinociceptive behaviors in animals were examined by measuring the number of writhing in a writhing test of visceral pain and the pain scores in Formalin test. Compared to control and PCP groups, findings in experimental groups indicated the new synthesized analogues (compounds II, III and V, 10 mg/kg) of PCP were able to produce more analgesic effects in formalin and writhing tests, especially for compound V. It was concluded that the new synthesized derivatives of PCP could substantially and respectively diminish acute and chronic pains.

  2. The Creation and Physiological Relevance of Divergent Hydroxylation Patterns in the Flavonoid Pathway (United States)

    Halbwirth, Heidi


    Flavonoids and biochemically-related chalcones are important secondary metabolites, which are ubiquitously present in plants and therefore also in human food. They fulfill a broad range of physiological functions in planta and there are numerous reports about their physiological relevance for humans. Flavonoids have in common a basic C6-C3-C6 skeleton structure consisting of two aromatic rings (A and B) and a heterocyclic ring (C) containing one oxygen atom, whereas chalcones, as the intermediates in the formation of flavonoids, have not yet established the heterocyclic C-ring. Flavonoids are grouped into eight different classes, according to the oxidative status of the C-ring. The large number of divergent chalcones and flavonoid structures is from the extensive modification of the basic molecules. The hydroxylation pattern influences physiological properties such as light absorption and antioxidative activity, which is the base for many beneficial health effects of flavonoids. In some cases antiinfective properties are also effected. PMID:20386656

  3. Haber Process Made Efficient by Hydroxylated Graphene: Ab Initio Thermochemistry and Reactive Molecular Dynamics. (United States)

    Chaban, Vitaly V; Prezhdo, Oleg V


    The Haber-Bosch process is the main industrial method for producing ammonia from diatomic nitrogen and hydrogen. We use a combination of ab initio thermochemical analysis and reactive molecular dynamics to demonstrate that a significant increase in the ammonia production yield can be achieved using hydroxylated graphene and related species. Exploiting the polarity difference between N2/H2 and NH3, as well as the universal proton acceptor behavior of NH3, we demonstrate a strong shift of the equilibrium of the Haber-Bosch process toward ammonia (ca. 50 kJ mol(-1) enthalpy gain and ca. 60-70 kJ mol(-1) free energy gain). The modified process is of significant importance to the chemical industry.

  4. Synthesis of two new hydroxylated derivatives of spironolactone by microbial transformation. (United States)

    Mei, Jianfeng; Wang, Luoyi; Wang, Siyuan; Zhan, Jixun


    Spironolactone is a medicinally important molecule that is clinically used in the treatment and management of many diseases such as oedema and ascites in cirrhosis of the liver, malignant ascites, nephrotic syndrome, chronic lung disease, resistant hypertension, congestive heart failure, and primary hyperaldosteronism. Microbial transformations of spironolactone by Cunninghamella elegans ATCC 9245 was carried out. Two new hydroxylated derivatives, 12β-hydroxy-spironolactone and 2α-hydroxy-spironolactone, were synthesized. Their structures were characterized on the basis of the spectroscopic data. The substrate can be efficiently converted into the products within 72 h after its addition to the fermentation broth of C. elegans ATCC 9245. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Hydroxylation of a hederagenin derived saponin by a Xylareaceous fungus found in fruits of Sapindus saponaria

    Energy Technology Data Exchange (ETDEWEB)

    Murgu, Michael; Santos, Luiz F. Arruda; Souza, Gezimar D. de; Daolio, Cristina; Ferreira, Antonio Gilberto; Rodrigues-Filho, Edson [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil). Dept. de Quimica; Schneider, Bernd [Max Planck Institute for Chemical Ecology, Beutenberg Campus, Jena (Germany)


    During our screening of tropical plants for endophyte microorganisms, a Xylareaceous fungus was found living on the internal part of Sapindus saponaria fruits. The fruits of S. saponaria accumulate great amounts of triterpenoidal and sesquiterpenoidal saponins. The saponin 3-O-({beta}-D-xylopyranosyl)-(1{yields}3)-{alpha}-L -rhamnopyranosyl-(1{yields}2)-{alpha}-L-arabinopyranosyl-hederagenin was isolated using chromatographic methods, after alkaline hydrolysis of the crude extract obtained from S. saponaria fruits and added to the culture medium used to grows the fungus. A new saponin was isolated from this experiment by preparative scale HPLC and characterized as a 22{alpha}-hydroxy derivative. The structure of this hydroxylated saponin was elucidated based on interpretation of MS/MS data and NMR spectra. (author)

  6. Substitution effect on a hydroxylated chalcone: Conformational, topological and theoretical studies (United States)

    Custodio, Jean M. F.; Vaz, Wesley F.; de Andrade, Fabiano M.; Camargo, Ademir J.; Oliveira, Guilherme R.; Napolitano, Hamilton B.


    The effect of substituents on two hydroxylated chalcones was studied in this work. The first chalcone, with a dimethylamine group (HY-DAC) and the second, with three methoxy groups (HY-TRI) were synthesized and crystallized from ethanol on centrosymmetric space group P21/c. The geometric parameters and supramolecular arrangement for both structures obtained from single crystal X-ray diffraction data were analyzed. The intermolecular interactions were investigated by Hirshfeld surfaces with their respective 2D plot for quantification of each type of contact. Additionally, the observed interactions were characterized by QTAIM analysis, and DFT calculations were applied for theoretical vibrational spectra, localization and quantification of frontier orbitals and potential electrostatic map. The flatness of both structures was affected by the substituents, which led to different monoclinic crystalline packing. The calculated harmonic vibrational frequencies and homo-lumo gap confirmed the stability of the structures, while intermolecular interactions were confirmed by potential electrostatic map and QTAIM analysis.

  7. Self-Cyclizing Antioxidants to Prevent DNA Damage Caused by Hydroxyl Radical. (United States)

    AbdulSalam, Safnas F; Gurjar, Purujit N; Zhu, Haizhou; Liu, Jing; Johnson, Emma S; Kadekaro, Ana Luisa; Landero-Figueroa, Julio; Merino, Edward J


    Antioxidant therapy is a promising treatment strategy for protecting DNA from the damage caused by reactive oxygen species (ROS). Here, we report new self-cyclizing antioxidant reagents that are selective for the hydroxyl radical. Our mechanistic investigation revealed that the reagents react with three equivalents of oxidant in a cascade reaction to form a bicyclic final product. Among the reagents synthesized, 1 c showed favorable properties in vitro and in cellular studies. Using As2 O3 , which triggers ROS production, we showed that 1 c prevents formation of the guanine oxidation product 2,2,4-triamino-2H-oxazol-5-one-2'-deoxyribonucleoside and lowers cellular levels of reactive oxygen. The described self-cyclizing antioxidants are efficient, flexible, and tunable reagents with the potential to limit toxic oxidative stress. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.


    Energy Technology Data Exchange (ETDEWEB)

    Al-Marzouk, A. A.; Araya, E. D. [Physics Department, Western Illinois University, 1 University Circle, Macomb, IL 61455 (United States); Hofner, P. [Physics Department, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801 (United States); Kurtz, S. [Centro de Radioastronomia y Astrofisica, Universidad Nacional Autonoma de Mexico, Apdo. Postal 3-72, 58090, Morelia, Michoacan (Mexico); Linz, H. [Max-Planck-Institut fuer Astronomie, Koenigstuhl 17, D-69117 Heidelberg (Germany); Olmi, L. [INAF, Osservatorio Astrofisico di Arcetri, Largo E. Fermi 5, I-50125 Firenze (Italy)


    We report the discovery of 6.035 GHz hydroxyl (OH) maser flares toward the massive star-forming region IRAS 18566+0408 (G37.55+0.20), which is the only region known to show periodic formaldehyde (4.8 GHz H{sub 2}CO) and methanol (6.7 GHz CH{sub 3}OH) maser flares. The observations were conducted between 2008 October and 2010 January with the 305 m Arecibo Telescope in Puerto Rico. We detected two flare events, one in 2009 March and one in 2009 September to November. The OH maser flares are not simultaneous with the H{sub 2}CO flares, but may be correlated with CH{sub 3}OH flares from a component at corresponding velocities. A possible correlated variability of OH and CH{sub 3}OH masers in IRAS 18566+0408 is consistent with a common excitation mechanism (IR pumping) as predicted by theory.

  9. Photo-oxidation of PAHs with calcium peroxide as a source of the hydroxyl radicals

    Directory of Open Access Journals (Sweden)

    Kozak Jolanta


    Full Text Available The efficiency of the removal of selected PAHs from the pretreated coking wastewater with usage of CaO2, Fenton reagent (FeSO4 and UV rays are presented in this article. The investigations were carried out using coking wastewater originating from biological, industrial wastewater treatment plant. At the beginning of the experiment, the calcium peroxide (CaO2 powder as a source of hydroxyl radicals (OH• and Fenton reagent were added to the samples of wastewater. Then, the samples were exposed to UV rays for 360 s. The process was carried out at pH 3.5-3.8. After photo-oxidation process a decrease in the PAHs concentration was observed. The removal efficiency of selected hydrocarbons was in the ranged of 89-98%. The effectiveness of PAHs degradation was directly proportional to the calcium peroxide dose.

  10. Bactericidal effect of colistin on planktonic Pseudomonas aeruginosa is independent of hydroxyl radical formation

    DEFF Research Database (Denmark)

    Brochmann, Rikke Prejh; Toft, Anders; Ciofu, Oana


    The bactericidal effect of several major types of antibiotics has recently been demonstrated to be dependent on the formation of toxic amounts of hydroxyl radicals (OH·) resulting from oxidative stress in metabolically active cells. Since killing by the antimicrobial peptide colistin does...... not require bacterial metabolic activity, we tested whether the bactericidal effect of colistin depends on the formation of OH·. In Pseudomonas aeruginosa cultures, OH-mediated killing by ciprofloxacin was demonstrated by decreased bacterial survival and induction of 3'-(p-hydroxyphenyl) fluorescein (HPF......) fluorescence. OH·-mediated killing by ciprofloxacin was further confirmed by rescue of cells and reduction of HPF fluorescence due to prevention of OH· accumulation by scavenging with thiourea, by chelating with dipyridyl, by decreasing metabolism as well as by anoxic growth. In contrast, no formation of OH...

  11. Silymarin inhibits cisplatin-mediated apoptosis via inhibition of hydrogen peroxide and hydroxyl radical generation

    Directory of Open Access Journals (Sweden)

    Angkana Tantituvanont


    Full Text Available Cisplatin mediated nephrotoxicity has been continuously reported and recognized as a major obstacle for cisplatinbased chemotherapy. The present study aimed to demonstrate the potential use of silymarin, an extract from the seed of Silybum marianum L., as a combination therapy with cisplatin. Previous studies indicated that cisplatin-mediated toxicity was primarily caused by cellular oxidative stress. This study found that pretreatment with silymarin significantly attenuated oxidative stress induced by cisplatin in human renal epithelial cells (HK2-cells and protected against cisplatin-mediated apoptosis. Moreover, the present study demonstrated that silymarin could attenuate hydrogen peroxide and hydroxyl radical generated by cisplatin while having minimal effect on superoxide anion level. In summary, these observation showed significant impact of silymarin in the inhibition of cisplatin-mediated renal cell death in vitro and could be beneficial for the development of this compound as a combination therapy in patients before receiving cisplatin.

  12. Comparison of Polyurethanes with Polyhydroxyurethanes: Effect of the Hydroxyl Group on Structure-Property Relationships (United States)

    Leitsch, Emily K.; Lombardo, Vince M.; Scheidt, Karl A.; Torkelson, John M.


    Polyurethanes (PUs) are commonly synthesized by rapid step-growth polymerization through the reaction of a multifunctional alcohol with a polyisocyanate. PUs can be prepared at ambient conditions utilizing a variety of starting material molecular weights and backbones, resulting in highly tunable thermal and physical properties. The urethane linkages as well as the nanophase separated morphology attainable in PU materials lead to desirable properties including elastomeric character and adhesion. The isocyanate-based monomers used in the synthesis of traditional PUs have come under increasing regulatory pressure and thus inspired the investigation of alternative routes for the formation of PU materials. We examine an alternative route to synthesize PU- the reaction of five-membered cyclic carbonate with amines. This reaction results in the formation of a urethane linkage with an adjacent alcohol group. The effects of this hydroxyl group on the thermal and mechanical properties of the resulting polymer are investigated and compared with an analogous traditional PU system.

  13. Cupric ion reducing antioxidant capacity assay for antioxidants in human serum and for hydroxyl radical scavengers. (United States)

    Apak, Reşat; Güçlü, Kubilay; Ozyürek, Mustafa; Bektaşoğlu, Burcu; Bener, Mustafa


    , for which the FRAP (ferric reducing antioxidant potency) test is basically nonresponsive. The additivity of absorbances of all the tested antioxidants confirmed that antioxidants in the CUPRAC test do not chemically interact among each other so as to cause an intensification or quenching of the theoretically expected absorbance, and that a total antioxidant capacity (TAC) assay of serum is possible. As a distinct advantage over other electron-transfer based assays (e.g., Folin, FRAP, ABTS, DPPH), CUPRAC is superior in regard to its realistic pH close to the physiological pH, favorable redox potential, accessibility and stability of reagents, and applicability to lipophilic antioxidants as well as hydrophilic ones. The CUPRAC procedure can also assay hydroxyl radicals, being the most reactive oxygen species (ROS). As a more convenient, efficient, and less costly alternative to HPLC/electrochemical detection techniques and to the nonspecific, low-yield TBARS test, we use p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of [Fe(II)+EDTA] with hydrogen peroxide. The produced hydroxyl radicals attack both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2 h. The CUPRAC absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreases in the presence of (.)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. The developed method is less lengthy, more specific, and of a higher yield than the classical TBARS assay.

  14. Hydroxylated polychlorinated biphenyl detection based on a genetically engineered bioluminescent whole-cell sensing system. (United States)

    Turner, Kendrick; Xu, Shifen; Pasini, Patrizia; Deo, Sapna; Bachas, Leonidas; Daunert, Sylvia


    The metabolites of polychlorinated biphenyls (PCBs), such as hydroxylated PCBs (OH-PCBs), have been identified as environmental contaminants. Various studies have shown that some OH-PCBs can potentially contribute to health problems. Detection of these compounds in environmental and biological samples could provide useful information about their levels and lead to a better understanding of their apparent toxicity. To that end, we have developed a whole-cell sensing system for the detection of OH-PCBs by taking advantage of the recognition of a group of related compounds, i.e., hydroxylated biphenyls, by the product of the hbpR gene in the hbp operon from Pseudomonas azelaica strain HBP1. By fusing the luxAB genes, encoding the reporter protein bacterial luciferase, to the hbp regulator-promoter sequence, a whole-cell sensing system was developed. Here, we describe the optimization and application of this whole-cell sensing system for the detection of a model compound, 2-hydroxy-3',4'-dichlorobiphenyl. A detection limit of 1 x 10(-8) M was achieved using this system. The detection of a broad range of individual OH-PCBs as well as an OH-PCB mixture was investigated. The system can detect OH-PCBs in whole serum samples in a trace amount, which is comparable to the detection of these analytes in medium alone. We envision that the method developed can potentially be employed as a rapid and sensitive way to monitor OH-PCBs for toxicological study in the laboratory, as well as a useful tool to evaluate the presence of bioavailable OH-PCBs in natural environments.

  15. Hydroxyl functionalized polytriazole-co-polyoxadiazole as substrates for forward osmosis membranes. (United States)

    Duong, Phuoc H H; Chisca, Stefan; Hong, Pei-Ying; Cheng, Hong; Nunes, Suzana P; Chung, Tai-Shung


    Hydroxyl functionalized polytriazole-co-polyoxadiazole (PTA-POD) copolymers have been synthesized and cast as promising highly thermally stable, chemically resistant, and antiorganic/biological fouling porous substrates for the fabrication of thin-film composite (TFC) forward osmosis (FO) membranes. The roles of PTA/POD ratios in the membrane substrates, TFC layers, and FO membrane performance have been investigated. This study demonstrates that the substrate fabricated from the copolymer containing 40 mol % PTA is optimal for the TFC membranes. Compared to the POD-TFC membrane, the 40 mol % PTA-TFC membrane exhibits a remarkable decrease in structural parameter (S) of more than 3.3 times. In addition, the 40 mol % PTA-TFC membrane is characterized by high water fluxes of 24.9 LMH and 47.2 LMH using 1 M NaCl as the draw solution and DI water as the feed under FO and pressure retarded osmosis (PRO) modes, respectively. Compared to a polysulfone (PSU) supported TFC-FO membrane under similar fabrication conditions, the 40% mol PTA-TFC membrane shows better FO performance and enhanced antifouling properties on the support (lower protein binding propensity and improved bacterial inhibition). Moreover, the performance of the 40 mol % PTA supported TFC-FO membrane can be improved to 37.5 LMH (FO mode)/78.4 LMH (PRO mode) and potentially higher by optimizing the support morphology, the TFC formation, and the post-treatment process. Hence, the use of newly developed hydroxyl functionalized polytriazole-co-polyoxadiazole copolymers may open up a new class of material for FO processes.

  16. Hydroxyl functionalized polytriazole-co-polyoxadiazole as substrates for forward osmosis membranes

    KAUST Repository

    Phuoc, Duong


    Hydroxyl functionalized polytriazole-co-polyoxadiazole (PTA-POD) copolymers have been synthesized and cast as promising highly thermally stable, chemically resistant, and antiorganic/biological fouling porous substrates for the fabrication of thin-film composite (TFC) forward osmosis (FO) membranes. The roles of PTA/POD ratios in the membrane substrates, TFC layers, and FO membrane performance have been investigated. This study demonstrates that the substrate fabricated from the copolymer containing 40 mol % PTA is optimal for the TFC membranes. Compared to the POD-TFC membrane, the 40 mol % PTA-TFC membrane exhibits a remarkable decrease in structural parameter (S) of more than 3.3 times. In addition, the 40 mol % PTA-TFC membrane is characterized by high water fluxes of 24.9 LMH and 47.2 LMH using 1 M NaCl as the draw solution and DI water as the feed under FO and pressure retarded osmosis (PRO) modes, respectively. Compared to a polysulfone (PSU) supported TFC-FO membrane under similar fabrication conditions, the 40% mol PTA-TFC membrane shows better FO performance and enhanced antifouling properties on the support (lower protein binding propensity and improved bacterial inhibition). Moreover, the performance of the 40 mol % PTA supported TFC-FO membrane can be improved to 37.5 LMH (FO mode)/78.4 LMH (PRO mode) and potentially higher by optimizing the support morphology, the TFC formation, and the post-treatment process. Hence, the use of newly developed hydroxyl functionalized polytriazole-co-polyoxadiazole copolymers may open up a new class of material for FO processes.

  17. Rapid estimation of activation enthalpies for cytochrome-P450-mediated hydroxylations. (United States)

    Mayeno, Arthur N; Robinson, Jonathan L; Reisfeld, Brad


    Cytochrome P450 (CYP) enzymes play a critical role in detoxication and bioactivation of xenobiotics; thus, the ability to predict the biotransformation rates and regioselectivity of CYP enzymes toward substrates is an important goal in toxicology and pharmacology. Here, we present the use of the semiempirical quantum chemistry method SAM1 to rapidly estimate relative activation enthalpies (ΔH(‡)) for the hydroxylation of aliphatic carbon centers of various substrates. The ΔH(‡) were determined via a reaction path calculation, in the reverse direction (RRP), using the iron-hydroxo-porphine intermediate and the substrate radical. The SAM1 ΔH(‡) were calculated via unrestricted Hartree-Fock (UHF) and configuration interaction (CI) formalisms for both the doublet and quartet spin states. The SAM1 RRP ΔH(‡), after subtracting a correction factor, were compared with density functional theory (DFT) B3LYP activation energies for two sets of substrates and showed R(2) ranging from 0.69 to 0.89, and mean absolute differences ranging from 1.2 ± 1.0 to 1.7 ± 1.5 kcal/mol. SAM1 UHF and CI RRP calculation times were, on average, more than 200 times faster than those for the corresponding forward reaction path DFT calculations. Certain key transition-state (TS) geometry measurements, such as the forming O···H bond length, showed good correlation with the DFT values. These results suggest that the SAM1 RRP approach can be used to rapidly estimate the DFT activation energy and some key TS geometry measurements and can potentially be applied to estimate substrate hydroxylation rates and regioselectivity by CYP enzymes. Copyright © 2010 Wiley Periodicals, Inc.

  18. Synthesis of Silver Nanoparticles Using Hydroxyl Functionalized Ionic Liquids and Their Antimicrobial Activity

    Directory of Open Access Journals (Sweden)

    Young Key Shim


    Full Text Available We report a new one phase method for the synthesis of uniform monodisperse crystalline Ag nanoparticles in aqueous systems that has been developed by using newly synthesized mono and dihydroxylated ionic liquids and cationic surfactants based on 1,3-disubstituted imidazolium cations and halogens anions. The hydroxyl functionalized ionic liquids (HFILs and hydroxyl functionalized cationic surfactants (HFCSs also simultaneously acts both as the reductant and protective agent. By changing the carbon chain length, alcohol structure and anion of the 1,3-imidazolium based HFILs and HFCSs the particle size, uniform and dispersibility of nanoparticles in aqueous solvents could be controlled. Transmission electron microscopy (TEM, electron diffraction, UV-Vis and NMR, were used for characterization of HFILs, HFCSs and silver nanoparticles. TEM studies on the solution showed representative spherical silver nanoparticles with average sizes 2-8 nm, particularly 2.2 nm and 4.5 nm in size range and reasonable narrow particle size distributions (SD-standard distribution 0.2 nm and 0.5 nm respectively. The all metal nanoparticles are single crystals with face centered cubic (fcc structure. The silver nanoparticles surface of plasmon resonance band (λmax around 420 nm broadened and little moved to the long wavelength region that indicating the formation of silver nanoparticles dispersion with broad absorption around infrared (IR region. Silver complexes of these HFILs as well as different silver nanoparticles dispersions have been tested in vitro against several gram positive and gram negative bacteria and fungus. The silver nanoparticles providing environmentally friendly and high antimicrobial activity agents.

  19. Conformational influence of the ribose 2'-hydroxyl group: crystal structures of DNA-RNA chimeric duplexes (United States)

    Egli, M.; Usman, N.; Rich, A.


    We have crystallized three double-helical DNA-RNA chimeric duplexes and determined their structures by X-ray crystallography at resolutions between 2 and 2.25 A. The two self-complementary duplexes [r(G)d(CGTATACGC)]2 and [d(GCGT)r(A)d(TACGC)]2, as well as the Okazaki fragment d(GGGTATACGC).r(GCG)d(TATACCC), were found to adopt A-type conformations. The crystal structures are non-isomorphous, and the crystallographic environments for the three chimeras are different. A number of intramolecular interactions of the ribose 2'-hydroxyl groups contribute to the stabilization of the A-conformation. Hydrogen bonds between 2'-hydroxyls and 5'-oxygens or phosphate oxygens, in addition to the previously observed hydrogen bonds to 1'-oxygens of adjacent riboses and deoxyriboses, are observed in the DNA-RNA chimeric duplexes. The crystalline chimeric duplexes do not show a transition between the DNA A- and B-conformations. CD spectra suggest that the Okazaki fragment assumes an A-conformation in solution as well. In this molecule the three RNA residues may therefore lock the complete decamer in the A-conformation. Crystals of an all-DNA strand with the same sequence as the self-complementary chimeras show a morphology which is different from those of the chimera crystals. Moreover, the oligonucleotide does not match any of the sequence characteristics of DNAs usually adopting the A-conformation in the crystalline state (e.g., octamers with short alternating stretches of purines and pyrimidines). In DNA-RNA chimeric duplexes, it is therefore possible that a single RNA residue can drive the conformational equilibrium toward the A-conformation.

  20. Cytotoxic effects of hydroxylated fullerenes on isolated rat hepatocytes via mitochondrial dysfunction. (United States)

    Nakagawa, Yoshio; Suzuki, Toshinari; Ishii, Hidemi; Nakae, Dai; Ogata, Akio


    The cytotoxic effects of hydroxylated fullerenes, also termed fullerenols or fullerols [C(60)(OH)( n )], which are known nanomaterials and water-soluble fullerene derivatives, were studied in freshly isolated rat hepatocytes. The exposure of hepatocytes to C(60)(OH)(24) caused not only concentration (0-0.25 mM)- and time (0-3 h)-dependent cell death accompanied by the formation of cell blebs, loss of cellular ATP, reduced glutathione (GSH), and protein thiol levels, but also the accumulation of glutathione disulfide and malondialdehyde, indicating lipid peroxidation. Of the other analogues examined, the cytotoxic effects of C(60)(OH)(12) and fullerene C(60) at a concentration of 0.125 mM were less than those of C(60)(OH)(24). The loss of mitochondrial membrane potential and generation of oxygen radical species in hepatocytes incubated with C(60)(OH)(24) were greater than those with C(60)(OH)(12) and fullerene C(60). In the oxygen consumption of mitochondria isolated from rat liver, the ratios of state-3/state-4 respiration were more markedly decreased by C(60)(OH)(24) and C(60)(OH)(12) compared with C(60). In addition, C(60)(OH)(24) and C(60)(OH)(12) resulted in the induction of the mitochondrial permeability transition (MPT), and the effects of C(60)(OH)(12) were less than those of C(60)(OH)(24). Taken collectively, these results indicate that (a) mitochondria are target organelles for fullerenols, which elicit cytotoxicity through mitochondrial failure related to the induction of the MPT, mitochondrial depolarization, and inhibition of ATP synthesis in the early stage and subsequently oxidation of GSH and protein thiols, and lipid peroxidation through oxidative stress at a later stage; and (b) the toxic effects of fullerenols may depend on the number of hydroxyl groups participating in fullerene in rat hepatocytes.

  1. Protective Effect against Hydroxyl-induced DNA Damage and Antioxidant Activity of Citri reticulatae Pericarpium

    Directory of Open Access Journals (Sweden)

    Dongfeng Chen


    Full Text Available Purpose: As a typical Chinese herbal medicine, Citri reticulatae pericarpium (CRP possesses various pharmacological effects involved in antioxidant ability. However, its antioxidant effects have not been reported yet. The objective of this work was to investigate its antioxidant ability, then further discuss the antioxidant mechanism. Methods: CRP was extracted by ethanol to obtain ethanol extract of Citri reticulatae pericarpium (ECRP. ECRP was then measured by various antioxidant methods, including DNA damage assay, DPPH assay, ABTS assay, Fe3+-reducing assay and Cu2+-reducing assay. Finally, the content of total flavonoids was analyzed by spectrophotometric method. Results: Our results revealed that ECRP could effectively protect against hydroxyl-induced DNA damage (IC50 944.47±147.74 μg/mL. In addition, it could also scavenge DPPH· radical (IC50349.67±1.91 μg/mL and ABTS+• radical (IC5011.33±0.10 μg/mL, reduce Fe3+ (IC50 140.95±2.15 μg/mL and Cu2+ (IC50 70.46±1.77 μg/mL. Chemical analysis demonstrated that the content of total flavonoids in ECRP was 198.29±12.24 mg quercetin/g. Conclusion: Citri reticulatae pericarpium can effectively protect against hydroxyl-induced DNA damage. One mechanism of protective effect may be radical-scavenging which is via donating hydrogen atom (H·, donating electron (e. Its antioxidant ability can be mainly attributed to the flavonoids, especially hesperidin and narirutin.

  2. Immunotoxicology of titanium dioxide and hydroxylated fullerenes engineered nanoparticles in fish models (United States)

    Jovanovic, Boris


    Nanoparticles have the potential to cause adverse effects on the fish health, but the understanding of the underlying mechanisms is limited. Major task of this dissertation was to connect gaps in current knowledge with a comprehensive sequence of molecular, cellular and organismal responses toward environmentally relevant concentrations of engineered nanoparticles (titanium dioxide -- TiO2 and hydroxylated fullerenes), outlining the interaction with the innate immune system of fish. The research was divided into following steps: 1) create cDNA libraries for the species of fathead minnow (Pimephales promelas); 2) evaluate whether, and how can nanoparticles modulate neutrophil function in P. promelas; 3) determine the changes in expression of standard biomarker genes as a result of nanoparticle treatment; 4) expose the P. promelas to nanoparticles and appraise their survival rate in a bacterial challenge study; 5) assess the impact of nanoparticles on neuro-immunological interface during the early embryogenesis of zebrafish (Danio rerio). It was hypothesized that engineered nanoparticles can cause measurable changes in fish transcriptome, immune response, and disease resistance. The results of this dissertation are: 1) application of environmentally relevant concentration of nanoparticles changed function of fish neutrophils; 2) fish exposed to nano-TiO2 had significantly increased expression of interleukin 11, macrophage stimulating factor 1, and neutrophil cytosolic factor 2, while expression of interleukin 11 and myeloperoxidase was significantly increased and expression of elastase 2 was significantly decreased in fish exposed to hydroxylated fullerenes; 3) exposure to environmental estimated concentration of nano-TiO2 significantly increased fish mortality during Aeromonas hydrophila challenge. Analysis of nano-TiO 2 distribution in fish organism outlined that the nano-TiO2 is concentrating in the fish kidney and spleen; 4) during the early embryogenesis of D

  3. Hydroxylated polychlorinated biphenyls decrease circulating steroids in female polar bears (Ursus maritimus). (United States)

    Gustavson, Lisa; Ciesielski, Tomasz M; Bytingsvik, Jenny; Styrishave, Bjarne; Hansen, Martin; Lie, Elisabeth; Aars, Jon; Jenssen, Bjørn M


    As a top predator in the Arctic food chain, polar bears (Ursus maritimus) are exposed to high levels of persistent organic pollutants (POPs). Because several of these compounds have been reported to alter endocrine pathways, such as the steroidogenesis, potential disruption of the sex steroid synthesis by POPs may cause implications for reproduction by interfering with ovulation, implantation and fertility. Blood samples were collected from 15 female polar bears in Svalbard (Norway) in April 2008. The concentrations of nine circulating steroid hormones; dehydroepiandrosterone (DHEA), androstenedione (AN), testosterone (TS), dihydrotestosterone (DHT), estrone (E1), 17α-estradiol (αE2), 17β-estradiol (βE2), pregnenolone (PRE) and progesterone (PRO) were determined. The aim of the study was to investigate associations among circulating levels of specific POP compounds and POP-metabolites (hydroxylated PCBs [OH-PCBs] and hydroxylated PBDEs [OH-PBDEs]), steroid hormones, biological and capture variables in female polar bears. Inverse correlations were found between circulating levels of PRE and AN, and circulating levels of OH-PCBs. There were no significant relationships between the steroid concentrations and other analyzed POPs or the variables capture date and capture location (latitude and longitude), lipid content, condition and body mass. Although statistical associations do not necessarily represent direct cause-effect relationships, the present study indicate that OH-PCBs may affect the circulating levels of AN and PRE in female polar bears and that OH-PCBs thus may interfere with the steroid homeostasis. Increase in PRO and a decrease in AN concentrations suggest that the enzyme CYP17 may be a potential target for OH-PCBs. In combination with natural stressors, ongoing climate change and contaminant exposure, it is possible that OH-PCBs may disturb the reproductive potential of polar bears. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. Human Liver Microsomal Cytochrome P450 3A Enzymes Involved in Thalidomide 5-Hydroxylation and Formation of a Glutathione Conjugate (United States)

    Chowdhury, Goutam; Murayama, Norie; Okada, Yusuke; Uno, Yasuhiro; Shimizu, Makiko; Shibata, Norio; Guengerich, F. Peter; Yamazaki, Hiroshi


    (R)-Thalidomide was oxidized to 5-hydroxythalidomide and 5’-hydroxythalidomide by NADPH-fortified liver microsomes from humans and monkeys. (R)-Thalidomide was hydroxylated more efficiently than (S)-thalidomide. Recombinant human P450s 3A4, 3A5, and 3A7 and monkey P450s 3A8 and 3A5 (co-expressed with NADPH-P450 reductase in bacterial membranes) also catalyzed (R)-thalidomide 5-hydroxylation. Purified human P450s 2C19, 3A4, and 3A5 mediated (R)-thalidomide 5-hydroxylation at similar rates in reconstituted systems. P450 2C19 showed a rather non-saturable substrate-velocity curve; however, P450s 3A4 and 3A5 showed sigmoidal curves. P450 also oxidized 5-hydroxythalidomide to an epoxide or dihydroxy compound. Liquid chromatography-mass spectrometry analysis revealed formation of a glutathione conjugate from (R)- and (S)-5-hydroxythalidomide, catalyzed by liver microsomal P450s 3A4 and 3A5 in the presence of glutathione (assigned as a conjugate of 5-hydroxythalidomide formed on the phenyl ring). These results indicate that human P450s 3A4 and 3A5 mediate thalidomide 5-hydroxylation and further oxidation leading to a glutathione conjugate, which may be of relevance in the pharmacological and toxicological actions of thalidomide. PMID:20443640

  5. Preparation and characterization of protein loaded microspheres based on a hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid)

    NARCIS (Netherlands)

    Ghassemi, A.H.|info:eu-repo/dai/nl/314132945; van Steenbergen, M.J.|info:eu-repo/dai/nl/304839302; Talsma, H.|info:eu-repo/dai/nl/08138212X; van Nostrum, C.F.|info:eu-repo/dai/nl/134498690; Jiskoot, W.|info:eu-repo/dai/nl/084557397; Crommelin, D.J.A.|info:eu-repo/dai/nl/074578804; Hennink, W.E.|info:eu-repo/dai/nl/070880409


    The purpose of this study was to investigate the suitability of a novel hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid) (PLHMGA), as controlled release system for pharmaceutical proteins. Dextran Blue (as a macromolecular model compound) and lysozyme-loaded PLHMGA and

  6. Placental transfer of a hydroxylated polychlorinated biphenyl and effects on fetal and maternal thyroid hormone homeostasis in the rat

    NARCIS (Netherlands)

    Meerts, I.A.T.M.; Assin, Y.; Cenijn, P.H.; Berg, van den J.J.J.; Weijers, B.M.; Bergman, A.; Koeman, J.H.; Brouwer, A.


    Earlier studies at our laboratory indicated that several hydroxylated polychlorinated biphenyls (OH-PCBs) detected in human blood could specifically inhibit thyroxine (T4) transport by competitive binding to the thyroid hormone transport protein transthyretin (TTR) in vitro. In the present study we


    In this study, a new analytical technique was developed for the identification and quantification of multi-functional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) ...

  8. Hydroxyl-Directed Cross-Coupling: A Scalable Synthesis of Debromohamigeran E and Other Targets of Interest. (United States)

    Blaisdell, Thomas P; Morken, James P


    A hydroxyl functional group positioned β to a pinacol boronate can serve to direct palladium-catalyzed cross-coupling reactions. This feature can be used to control the reaction site in multiply borylated substrates and can activate boronates for reaction that would otherwise be unreactive.

  9. Hydroxylation of Benzene via C-H Activation Using Bimetallic CuAg@g-C3N4 (United States)

    A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light.

  10. An Efficient Synthesis of Phenols via Oxidative Hydroxylation of Arylboronic Acids Using (NH42S2O8

    Directory of Open Access Journals (Sweden)

    Claudia A. Contreras-Celedón


    Full Text Available A mild and efficient method for the ipso-hydroxylation of arylboronic acids to the corresponding phenols was developed using (NH42S2O8 as an oxidizing agent. The reactions were performed under metal-, ligand-, and base-free conditions.

  11. [Effect of hydroxylated pyrimidine derivatives on activities of thiamine-dependent enzymes and some parameters of lipid metabolism in mice]. (United States)

    Oparin, D A; Gorenshteĭn, B I; Karaedova, L M; Naruta, E E; Zabrodskaia, S V; Rudiak, T V; Akat'ev, V E; Larin, F S


    It has been found that hydroxylated pyrimidine derivatives actively participate in metabolic proceeds related to functioning of vitamin B1-dependent enzymes (transketolase, 2-oxo acid dehydrogenase). Hydroxypyrimidines also induce a significant increase in the levels of total lipids and cholesterol in the mice liver, not changing the phospholipid content.

  12. Hydrogen-assisted versus hydroxyl-assisted CO dissociation over Co-doped Cu(111): A DFT study (United States)

    Zha, Hao; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua


    First principle based density functional theory (DFT) was used to calculate the step-by-step hydrogenation and dissociation reaction network of carbon monoxide (CO) over Co-doped Cu(111) surface as a model for understanding the lateral interaction of surface hydroxyl species (OH) on these reactions. We discussed the Csbnd O bond length and the adsorption energy changes of reaction intermediates under different adsorption circumstances for purpose of making out the effect of surface hydroxyl on the reaction selectivity. Reaction intermediates co-adsorbed with H atom and hydroxyl could undergo H-assisted or OH-assisted routes. The calculations show that the OH-assisted route prefers with the formation of COH, CHOH and CH2OH while general H-assisted route prefers with the formation of HCO, CH2O and CH3O. Considering the rather low activation barrier of COH, CHOH and CH2OH to form CHX, the existence of hydroxyl on the surface is in favor of boosting the CHX and suppressing the methanol.

  13. Radical rebound mechanism in cytochrome P-450-catalyzed hydroxylation of the multifaceted radical clocks alpha- and beta-thujone. (United States)

    He, Xiang; de Montellano, Paul R Ortiz


    Alpha-thujone (1alpha) and beta-thujone (1beta) were used to investigate the mechanism of hydrocarbon hydroxylation by cytochromes P-450(cam) (CYP101) and P-450(BM3) (CYP102). The thujones are hydroxylated by these enzymes at various positions, but oxidation at C-4 gives rise to both rearranged and unrearranged hydroxylation products. Rearranged products result from the formation of a radical intermediate that can undergo either inversion of stereochemistry or ring opening of the adjacent cyclopropane ring. Both of these rearrangements, as well as a C-4 desaturation reaction, are observed. The ring opening clock gives oxygen rebound rates that range from 0.2 x 10(10) to 2.8 x 10(10) s(-1) for the different substrate and enzyme combinations. The C-4 inversion reaction provides independent confirmation of a radical intermediate. The phenol product expected if a C-4 cationic rather than radical intermediate is formed is not detected. The results are consistent with a two-state process and provide support for a radical rebound but not a hydroperoxide insertion mechanism for cytochrome P-450 hydroxylation.

  14. TiO2 Photocatalysis Causes DNA Damage via Fenton Reaction-Generated Hydroxyl Radicals during the Recovery Period▿ (United States)

    Gogniat, Gaëtan; Dukan, Sam


    Here, we show that resistance of Escherichia coli to TiO2 photocatalysis involves defenses against reactive oxygen species. Results support the idea that TiO2 photocatalysis generates damage which later becomes deleterious during recovery. We found this to be partly due to DNA attack via hydroxyl radicals generated by the Fenton reaction during recovery. PMID:17933934

  15. Prenatal Exposure to Polychlorinated Biphenyls and Their Hydroxylated Metabolites is Associated with Neurological Functioning in 3-Month-Old Infants

    NARCIS (Netherlands)

    Berghuis, Sietske A.; Soechitram, Shalini D.; Sauer, Pieter J. J.; Bos, Arend F.


    Polychlorinated biphenyls (PCBs) are environmental chemicals which are potentially toxic to the developing brain. Their hydroxylated metabolites (OH-PCBs) are suggested to be even more toxic. Knowledge about the health effects of prenatal OH-PCB exposure is limited. We aimed to determine whether

  16. Detection of hydroxyl radicals in the post-ischemic reperfused heart using salicylate as a trapping agent. (United States)

    Onodera, T; Ashraf, M


    The formation of hydroxyl radical in the post-ischemic reperfused heart was measured with high performance liquid chromatography and ultraviolet detection using salicylic acid. Hydroxyl radicals react with salicylic acid yielding 2,3- and 2,5-dihydroxybenzoic acid, which can be separated by the liquid chromatography. Isolated rat hearts were perfused with 1 mM salicylic acid and were subjected to 30 mins of global ischemia followed by aerobic or anaerobic reperfusion at 37 degrees C. The effluent from the hearts was collected at various intervals, extracted with ether, and injected into the high performance liquid chromatography unit. 2,5-dihydroxybenzoic acid was present only after aerobic reperfusion and was not detected before ischemia. The liquid chromatography peak of 2,3-dihydroxybenzoic acid was too small for quantitation. The concentration of 2,5-dihydroxybenzoic acid was the highest within 300 s of reperfusion. 2,5-dihydroxybenzoic acid was not detected in the ischemic hearts during anaerobic reperfusion. In ischemic hearts perfused with mannitol, the amount of 2,5-dihydroxybenzoic acid after reperfusion was reduced. These data suggest that hydroxyl radicals are produced in the post-ischemic reperfused heart and that the present method is useful and reliable for the measurement of hydroxyl radicals in the heart.

  17. Enumeration of sugars and sugar alcohols hydroxyl groups by aqueous-based acetylation and MALDI-TOF mass spectrometry (United States)

    A method is described for enumerating hydroxyl groups on analytes in aqueous media is described, and applied to some common polyalcohols (erythritol, mannitol, and xylitol) and selected carbohydrates. The analytes were derivatized in water with vinyl acetate in presence of sodium phosphate buffer. ...

  18. Sugars as hydroxyl radical scavengers: proof-of-concept by studying the fate of sucralose in Arabidopsis. (United States)

    Matros, Andrea; Peshev, Darin; Peukert, Manuela; Mock, Hans-Peter; Van den Ende, Wim


    Substantial formation of reactive oxygen species (ROS) is inevitable in aerobic life forms. Due to their extremely high reactivity and short lifetime, hydroxyl radicals are a special case, because cells have not developed enzymes to detoxify these most dangerous ROS. Thus, scavenging of hydroxyl radicals may only occur by accumulation of higher levels of simple organic compounds. Previous studies have demonstrated that plant-derived sugars show hydroxyl radical scavenging capabilities during Fenton reactions with Fe(2+) and hydrogen peroxide in vitro, leading to formation of less detrimental sugar radicals that may be subject of regeneration to non-radical carbohydrates in vivo. Here, we provide further evidence for the occurrence of such radical reactions with sugars in planta, by following the fate of sucralose, an artificial analog of sucrose, in Arabidopsis tissues. The expected sucralose recombination and degradation products were detected in both normal and stressed plant tissues. Oxidation products of endogenous sugars were also assessed in planta for Arabidopsis and barley, and were shown to increase in abundance relative to the non-oxidized precursor during oxidative stress conditions. We concluded that such non-enzymatic reactions with hydroxyl radicals form an integral part of plant antioxidant mechanisms contributing to cellular ROS homeostasis, and may be more important than generally assumed. This is discussed in relation to the recently proposed roles for Fe(2+) and hydrogen peroxide in processes leading to the origin of metabolism and the origin of life. © 2015 The Authors The Plant Journal © 2015 John Wiley & Sons Ltd.

  19. Antioxidant activity and inhibition of α-glucosidase by hydroxyl-functionalized 2-arylbenzo[b]furans. (United States)

    Hsieh, Jung-Feng; Lin, Wei-Jen; Huang, Kai-Fa; Liao, Jiahn-Haur; Don, Ming-Jaw; Shen, Chien-Chang; Shiao, Young-Ji; Li, Wen-Tai


    This study synthesized a series of hydroxyl-functionalized 2-arylbenzo[b]furans based on the structure of tournefolic acid A and evaluated them for antioxidant and α-glucosidase inhibitory activities. Compounds 5a, 5e, and 5n showed remarkable inhibition of α-glucosidase (IC50 values of 1.9-3.0 μM), and they appear to be even more potent than quercetin. A kinetic binding study indicated that compounds 5a and 5n used a mechanism of mixed-competition to inhibit α-glucosidase. This study also revealed that compounds 5a and 5n bind to either the α-glucosidase or α-glucosidase-4-NPGP complex. Using the crystal structure of the Saccharomyces cerevisiae α-glucosidase, the molecular docking study has predicted the binding of compounds 5a and 5n to the active site of α-glucosidase through both hydrophobic and hydrogen interactions. A DPPH radical scavenging assay further showed that most hydroxyl-functionalized 2-arylbenzo[b]furans possess antioxidant activity. The exception was compound 5p, which has only one hydroxyl group on the 2-phenyl ring of 2-arylbenzo[b]furan. Our results indicate that hydroxyl-functionalized 2-arylbenzo[b]furans possess both antidiabetic as well as antioxidant properties. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  20. Formation of hydroxyl radicals contributes to the bactericidal activity of ciprofloxacin against Pseudomonas aeruginosa biofilms

    DEFF Research Database (Denmark)

    Jensen, Peter Østrup; Briales, Alejandra; Brochmann, Rikke Prejh


    induction of cytotoxic hydroxyl radicals (OH˙) during antibiotic treatment of planktonically grown cells may contribute to action of the commonly used antibiotic ciprofloxacin on P. aeruginosa biofilms. For this purpose, WT PAO1, a catalase deficient ΔkatA and a ciprofloxacin resistant mutant of PAO1 (gyr...

  1. A facile BPO-mediated ortho-hydroxylation and benzoylation of N-alkyl anilines for synthesis of 2-benzamidophenols. (United States)

    Zhang, Zhi-Jing; Quan, Xue-Jing; Ren, Zhi-Hui; Wang, Yao-Yu; Guan, Zheng-Hui


    A facile benzoyl peroxide (BPO) mediated ortho-hydroxylation and benzoylation of N-alkyl anilines for the synthesis of 2-benzamidophenols has been developed. The reaction tolerates a wide range of functional groups and is a good method for the straightforward synthesis of valuable 2-benzamidophenols in good yields under mild conditions.

  2. Optimization of hydroxyl radical scavenging activity of exopolysaccharides from Inonotus obliquus in submerged fermentation using response surface methodology

    NARCIS (Netherlands)

    Chen, H.; Xu, X.; Zhu, Y.


    The objectives of this study were to investigate the effect of fermentation medium on the hydroxyl radical scavenging activity of exopolysaccharides from Inonotus obliquus by response surface methodology (RSM). A two-level fractional factorial design was used to evaluate the effect of different

  3. Manganese-induced hydroxyl radical formation in rat striatum is not attenuated by dopamine depletion or iron chelation in vivo

    NARCIS (Netherlands)

    W.N. Sloot (W.); J. Korf (Jakob); J.F. Koster (Johan); L.E.A. de Wit (Elly); J.-B.P. Gramsbergen (J. B P)


    textabstractThe present studies were aimed at investigating the possible roles of dopamine (DA) and iron in production of hydroxyl radicals (.OH) in rat striatum after Mn2+ intoxication. For this purpose, DA depletions were assessed concomitant with in vivo 2,3- and 2,5-dihydroxybenzoic acid (DHBA)

  4. Manganese-induced hydroxyl radical formation in rat striatum is not attenuated by dopamine depletion or iron chelation in vivo

    NARCIS (Netherlands)

    Sloot, WN; Korf, J; Koster, JF; DeWit, LEA; Gramsbergen, JBP

    The present studies were aimed at investigating the possible roles of dopamine (DA) and iron in production of hydroxyl radicals ((OH)-O-.) in rat striatum after Mn2+ intoxication. For this purpose, DA depletions were assessed concomitant with in vivo 2,3- and 2,5-dihydroxybenzoic acid (DHBA)

  5. Kinetic data for the reaction of hydroxyl radicals with 1,1,1-trichloroacetaldehyde at 298 +- 2 K

    DEFF Research Database (Denmark)

    Barry, J.; Scollard, D.J.; Treacy, J.J.


    The rate constant for the reaction of the hydroxyl radical with 1,1,1-trichloroacetaldehyde has been determined at 298 +/- 2 K. Rate data were obtained at atmospheric pressure by a relative rate method. The rate constant was also measured at lower pressures (1-3.4 Torr) using the discharge flow t...

  6. Novel hydroxyl radical scavenging antioxidant activity assay for water-soluble antioxidants using a modified CUPRAC method. (United States)

    Bektaşoğlu, Burcu; Esin Celik, Saliha; Ozyürek, Mustafa; Güçlü, Kubilay; Apak, Reşat


    Reactive oxygen species (ROS) such as superoxide anion, hydroxyl ((*)OH), peroxyl, and alkoxyl radicals may attack biological macromolecules giving rise to oxidative stress-originated diseases. Since (*)OH is very short-lived, secondary products resulting from (*)OH attack to various probes are measured. Although the measurement of aromatic hydroxylation with HPLC/electrochemical detection is more specific than the low-yield TBARS test, it requires sophisticated instrumentation. As a more convenient and less costly alternative, we used p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of Fe(II)+EDTA with hydrogen peroxide. The produced hydroxyl radicals attacked both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2h. The CUPRAC (i.e., our original method for total antioxidant capacity assay) absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreased in the presence of (*)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. A rate constant for the reaction of the scavenger with hydroxyl radical can be deduced from the inhibition of color formation. The second-order rate constants of the scavengers were determined with competition kinetics by means of a linear plot of A(0)/A as a function of C(scavenger)/C(probe), where A(0) and A are the CUPRAC absorbances of the system in the absence and presence of scavenger, respectively, and C is the molar concentration of relevant species. The 2,4- and 3,5-dimethoxybenzoates were the best probes in terms of linearity and sensitivity. Iodide, metabisulfite, hexacyanoferrate(II), thiourea, formate, and dimethyl sulfoxide were shown by the modified CUPRAC assay to be more effective scavengers than mannitol, glucose, lysine, and simple alcohols, as in the TBARS assay. The developed method is less lengthy, more

  7. Probing the human estrogen receptor-α binding requirements for phenolic mono- and di-hydroxyl compounds: a combined synthesis, binding and docking study. (United States)

    McCullough, Christopher; Neumann, Terrence S; Gone, Jayapal Reddy; He, Zhengjie; Herrild, Christian; Wondergem Nee Lukesh, Julie; Pandey, Rajesh K; Donaldson, William A; Sem, Daniel S


    Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and was also 25-fold specific for agonist ERβ versus antagonist activity. Docking predictions suggest this specificity may be due to interaction of the aliphatic hydroxyl with His475 in the agonist form of ERβ, versus with Thr299 in the antagonist form. But, the presence of this aliphatic hydroxyl is not required in all compounds, since mono-hydroxyl (phenolic) compounds bind ERα with high affinity, via hydroxyl hydrogen bonding interactions with the ERα Arg394/Glu353/water triad, and van der Waals interactions with the rest of the molecule. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Cyp3a11-mediated testosterone-6β-hydroxylation decreased, while UGT1a9-mediated propofol O-glucuronidation increased, in mice with diabetes mellitus. (United States)

    Shi, Rong; Wu, Jiasheng; Meng, Cong; Ma, Bingliang; Wang, Tianming; Li, Yuanyuan; Ma, Yueming


    The db/db mouse is one of the most popular animal models for type 2 diabetes mellitus, but changes in the activities of important P450s and UGTs are still not completely clear. This study was designed to investigate the alterations of major hepatic cytochrome P450s and UDP-glucuronyltransferase enzymes in db/db mice. Mouse liver microsomes (MLMs) were obtained from male db/db mice and their wild type littermates. After incubation of the substrates separately with MLMs, the samples were pooled and analysed by high-throughput liquid chromatography-tandem mass spectrometry system for the simultaneous study of nine phase I metabolic reactions and three glucuronidation conjugation reactions to determine the activity of the metabolic enzymes. Compared with normal controls, the Cl int estimate for testosterone-6β-hydroxylation was lower (46%) (p coumarin-7-hydroxylation, bupropion-hydroxylation, omeprazole-5-hydroxylation, dextromethorphan-O-demethylation, tolbutamide-4-hydroxylation, chlorzoxazone-6-hydroxylation and midazolam-1-hydroxylation and in glucuronidation reactions of estradiol 3-O-glucuronidation, and 3-azido-3-deoxythymidine glucuronidation. The data suggest that, in db/db mice, the activity of Cyp3a11, catalysing testosterone-6β-hydroxylation, decreased, while the activity of UGT1a9, catalysing propofol O-glucuronidation, increased. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  9. On the nature of the electronic effect of multiple hydroxyl groups in the 6-membered ring - the effects are additive but steric hindrance plays a role too

    DEFF Research Database (Denmark)

    Pedersen, Christian Marcus; Bols, Mikael


    synthesized and their pKa and conformation were studied. The results show that the large difference in the electronic effect between the axial and equatorial hydroxyls is partially cancelled by counteracting steric hindrance from 1,3-diaxial interactions. Hydrogen bonding does not appear to play any role...... in the electronic influence of the hydroxyl groups...

  10. New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data (United States)

    Sade, Ziv; Halevy, Itay


    CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

  11. Hydroxyl radical oxidation of phospholipid-coated NaCl particles. (United States)

    Dilbeck, Christopher W; Finlayson-Pitts, Barbara J


    Biological organic compounds mixed with NaCl and other inorganic compounds in sea-salt aerosol particles react in air with oxidants such as ozone and hydroxyl (OH) radicals. Laboratory studies of model systems can provide insight into these reactions. We report here studies of the kinetics and mechanism of oxidation of unsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) on NaCl by gas phase OH in air at room temperature and 1 atm pressure using diffuse reflection infrared Fourier transform spectrometry (DRIFTS) and matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry (MALDI-TOF-MS) to identify possible structures of surface-bound reaction products. For comparison, some studies were also carried out on the saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) on NaCl. The calculated concentration of hydroxyl radicals, generated by photolysis of isopropyl nitrite, was (1.6-6.4) × 10(8) radicals cm(-3). Surface-bound aldehydes, ketones, organic nitrates and nitrate ions were identified as products of these reactions and structures of potential products were proposed based on mechanistic considerations combined with the MALDI-TOF-MS and DRIFTS spectra. The loss rate of vinyl hydrogen, =C-H, at 3008 cm(-1) was used to obtain a lower limit for the rate constant (k1) for addition of OH to the double bond, k1 > (3 ± 1) × 10(-13) cm(3) molecule(-1) s(-1) (1s), corresponding to a reaction probability of γ(add) > (4 ± 1) × 10(-3) (1s). Assuming that abstraction from -CH2- groups in POPC is the same as for DPPC, the percentage of the reaction that occurs by addition is ~80%. This is similar to the percent addition predicted using structure-reactivity relationships for gas-phase reactions. Decreasing the amount of POPC relative to NaCl resulted in more nitrate ion formation and less relative loss of POPC, and increasing the OH concentration resulted in a more rapid loss of POPC and faster product formation. These studies

  12. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates (United States)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.


    upon deprotonation of one of the bound waters in complex [ 1] because of the close proximity of a transferable proton that can convert the bound hydroxyl to a bound water. This interconversion allows the oxygen to exchange as a bound water, rather than as a bound hydroxyl, which is slow at near-neutral pH conditions.

  13. Rapid clinical induction of bupropion hydroxylation by metamizole in healthy Chinese men (United States)

    Qin, Wen-Jie; Zhang, Wei; Liu, Zhao-Qian; Chen, Xiao-Ping; Tan, Zhi-Rong; Hu, Dong-Li; Wang, Dan; Fan, Lan; Zhou, Hong-Hao


    AIMS This study aimed to investigate the effect of metamizole on bupropion hydroxylation related to different CYP2B6 genotype groups in healthy volunteers. METHODS Sixteen healthy male volunteers (6 CYP2B6*1/*1, 6 CYP2B6*1/*6 and 4 CYP2B6*6/*6) received orally administered bupropion alone and during daily treatment with metamizole 1500 mg day–1 (500 mg tablet taken three times daily) for 4 days. Serial blood samples were obtained up to 48 h after each bupropion dose. RESULTS After metamizole treatment relative to bupropion alone, the geometric mean ratios (GMRs) and 90% confidence interval (CI) of the AUC(0,∞) ratio of 4-hydroxybupropion over bupropion were 1.99 (1.57, 2.55) for the CYP2B6*1/*1 group, 2.15 (1.53, 3.05) for the CYP2B6*1/*6 group and 1.86 (1.36, 2.57) for the CYP2B6*6/*6 group. The GMRs and 90% CI of bupropion were 0.695 (0.622, 0.774) for AUC(0,∞) and 0.400 (0.353, 0.449) for Cmax, respectively. The corresponding values for 4-hydroxybupropion were 1.43 (1.28, 1.53) and 2.63 (2.07, 2.92). The t1/2 value was significantly increased for bupropion and decreased for 4-hydroxybupropion. The tmax values of bupropion and 4-hydroxybupropion were both significantly decreased. The mean percentage changes in pharmacokinetic parameters among the CYP2B6 genotype groups were not significantly different. CONCLUSIONS Oral administration of metamizole for 4 days significantly altered the pharmacokinetics of both bupropion and its active metabolite, 4-hydroxybupropion, and significantly increased the CYP2B6-catalyzed bupropion hydroxylation in all of the subjects. Cautions should be taken when metamizole is co-administered with CYP2B6 substrate drugs. PMID:22519658

  14. Differential Reactivity between Two Copper Sites in Peptidylglycine r-Hydroxylating Monooxygenase

    Energy Technology Data Exchange (ETDEWEB)

    E Chufan; S Prigge; X Siebert; B Eipper; R Mains; L Amzel


    Peptidylglycine {alpha}-hydroxylating monooxygenase (PHM) catalyzes the stereospecific hydroxylation of the C{alpha} of C-terminal glycine-extended peptides and proteins, the first step in the activation of many peptide hormones, growth factors, and neurotransmitters. The crystal structure of the enzyme revealed two nonequivalent Cu sites (Cu{sub M} and Cu{sub H}) separated by {approx}11 {angstrom}. In the resting state of the enzyme, Cu{sub M} is coordinated in a distorted tetrahedral geometry by one methionine, two histidines, and a water molecule. The coordination site of the water molecule is the position where external ligands bind. The Cu{sub H} has a planar T-shaped geometry with three histidines residues and a vacant position that could potentially be occupied by a fourth ligand. Although the catalytic mechanism of PHM and the role of the metals are still being debated, Cu{sub M} is identified as the metal involved in catalysis, while Cu{sub H} is associated with electron transfer. To further probe the role of the metals, we studied how small molecules such as nitrite (NO{sub 2}{sup -}), azide (N{sub 3}{sup -}), and carbon monoxide (CO) interact with the PHM copper ions. The crystal structure of an oxidized nitrite-soaked PHMcc, obtained by soaking for 20 h in mother liquor supplemented with 300 mM NaNO{sub 2}, shows that nitrite anion coordinates Cu{sub M} in an asymmetric bidentate fashion. Surprisingly, nitrite does not bind Cu{sub H}, despite the high concentration used in the experiments (nitrite/protein > 1000). Similarly, azide and carbon monoxide coordinate Cu{sub M} but not Cu{sub H} in the PHMcc crystal structures obtained by cocrystallization with 40 mM NaN{sub 3} and by soaking CO under 3 atm of pressure for 30 min. This lack of reactivity at the Cu{sub H} is also observed in the reduced form of the enzyme: CO binds Cu{sub M} but not Cu{sub H} in the structure of PHMcc obtained by exposure of a crystal to 3 atm CO for 15 min in the presence of 5

  15. In vivo generation of hydroxyl radicals and MPTP-induced dopaminergic toxicity in the basal ganglia. (United States)

    Chiueh, C C; Wu, R M; Mohanakumar, K P; Sternberger, L M; Krishna, G; Obata, T; Murphy, D L


    The in vivo generation of .OH free radicals in specific brain regions can be measured by intracerebral microdialysis perfusion of salicylate, avoiding many of the pitfalls inherent in systemic administration of salicylate. Direct infusion of salicylate into the brain can minimize the hepatic hydroxylation of salicylate and its contribution to brain levels of 2,5-DHBA. Levels of 2,5-DHBA detected in the brain dialysate may reflect the .OH adduct plus some enzymatic hydroxylation of salicylate in the brain. After minimizing the contribution of enzyme and/or blood-borne 2,5-DHBA, the present data demonstrate the validity of the use of 2,3-DHBA and apparently 2,5-DHBA as indices of .OH formation in the brain. Therefore, intracranial microdialysis of salicylic acid and measurement of 2,3-DHBA appears to be a useful .OH trapping procedure for monitoring the time course of .OH generation in the extracellular fluid of the brain. These results indicate that nonenzymatic and/or enzymatic oxidation of the dopamine released by MPTP analogues in the extracellular fluid may play a key role in the generation of .OH free radicals in the iron-rich basal ganglia. Moreover, a site-specific generation of cytotoxic .OH free radicals and quinone/semiquinone radicals in the striatum may cause the observed lipid peroxidation, calcium overload, and retrograde degeneration of nigrostriatal neurons. This free-radical-induced nigral injury can be suppressed by antioxidants (i.e., U-78517F, DMSO, and deprenyl) and possibly hypothermia as well. In the future, this in vivo detection of .OH generation may be useful in answering some of the fundamental questions concerning the relevance of oxidants and antioxidants in neurodegenerative disorders during aging. It could also pave the way for the research and development of novel neuroprotective antioxidants and strategies for the early or preventive treatment of neurodegenerative disorders, such as Parkinson's disease (Wu et al., this issue

  16. Measurements of soot formation and hydroxyl concentration in near critical equivalence ratio premixed ethylene flame (United States)

    Inbody, Michael Andrew


    The testing and development of existing global and detailed chemical kinetic models for soot formation requires measurements of soot and radical concentrations in flames. A clearer understanding of soot particle inception relies upon the evaluation and refinement of these models in comparison with such measurements. We present measurements of soot formation and hydroxyl (OH) concentration in sequences of flat premixed atmospheric-pressure C2H4/O2/N2 flames and 80-torr C2H4/O2 flames for a unique range of equivalence ratios bracketting the critical equivalence ratio (phi(sub c)) and extending to more heavily sooting conditions. Soot volume fraction and number density profiles are measured using a laser scattering-extinction apparatus capable of resolving a 0.1 percent absorption. Hydroxyl number density profiles are measured using laser-induced fluorescence (LIF) with broadband detection. Temperature profiles are obtained from Rayleigh scattering measurements. The relative volume fraction and number density profiles of the richer sooting flames exhibit the expected trends in soot formation. In near-phi(sub c) visibility sooting flames, particle scattering and extinction are not detected, but an LIF signal due to polycyclic aromatic hydrocarbons (PAH's) can be detected upon excitation with an argon-ion laser. A linear correlation between the argon-ion LIF and the soot volume fraction implies a common mechanistic source for the growth of PAH's and soot particles. The peak OH number density in both the atmospheric and 80-torr flames declines with increasing equivalence ratio, but the profile shape remains unchanged in the transition to sooting, implying that the primary reaction pathways for OH remain unchanged over this transition. Chemical kinetic modeling is demonstrated by comparing predictions using two current reaction mechanisms with the atmospheric flame data. The measured and predicted OH number density profiles show good agreement. The predicted benzene

  17. Flos Chrysanthemi Indici protects against hydroxyl-induced damages to DNA and MSCs via antioxidant mechanism

    Directory of Open Access Journals (Sweden)

    Xican Li


    Full Text Available Flos Chrysanthemi Indici (FCI is a Chinese herbal medicine used in China for over 2000 years. In this study, its ethanol extract (EFCL was found to protect against hydroxyl radical (·−OH induced oxidative damages to mesenchymal stem cells (MSCs and DNA. To explore the mechanism, EFCL was further determined by chemical and antioxidant assays. Folin–Ciocalteu colorimetric assay suggested that content of total phenolics was 93.85 ± 3.56 mg catechin/g and HPLC analysis indicated a content of 10.05 ± 1.44 mg/g as chlorogenic acid in EFCI. Antioxidant assays revealed that EFCI could also scavenge ·−O2− radical (IC50 58.74 ± 1.30 μg/mL, DPPH·− radical (IC50 46.46 ± 1.35 μg/mL and ABTS+·− radical (IC50 20.59 ± 0.52 μg/mL, bind Fe2+ (IC50 364.27 ± 19.57 μg/mL and Cu2+ (IC50 734.77 ± 34.69 μg/mL, reduce Fe3+ (IC50 147.11 ± 11.09 μg/mL and Cu2+ (IC50 35.69 ± 3.14 μg/mL. On the basis of mechanistic analysis, we concluded that FCI can effectively protect against hydroxyl-induced damages to DNA and MSCs, therefore FCI shows promise as a possible therapeutic reagent for many diseases. The effect may be mainly attributed to phenolics especially chlorogenic acid, which exerts the antioxidant action possibly through metal-chelating, and radical-scavenging which is via hydrogen atom transfer (HAT and/or sequential electron proton transfer (SEPT mechanisms.

  18. Rapid clinical induction of bupropion hydroxylation by metamizole in healthy Chinese men. (United States)

    Qin, Wen-Jie; Zhang, Wei; Liu, Zhao-Qian; Chen, Xiao-Ping; Tan, Zhi-Rong; Hu, Dong-Li; Wang, Dan; Fan, Lan; Zhou, Hong-Hao


    This study aimed to investigate the effect of metamizole on bupropion hydroxylation related to different CYP2B6 genotype groups in healthy volunteers. Sixteen healthy male volunteers (6 CYP2B6*1/*1, 6 CYP2B6*1/*6 and 4 CYP2B6*6/*6) received orally administered bupropion alone and during daily treatment with metamizole 1500 mg day(-1) (500 mg tablet taken three times daily) for 4 days. Serial blood samples were obtained up to 48 h after each bupropion dose. After metamizole treatment relative to bupropion alone, the geometric mean ratios (GMRs) and 90% confidence interval (CI) of the AUC(0,∞) ratio of 4-hydroxybupropion over bupropion were 1.99 (1.57, 2.55) for the CYP2B6*1/*1 group, 2.15 (1.53, 3.05) for the CYP2B6*1/*6 group and 1.86 (1.36, 2.57) for the CYP2B6*6/*6 group. The GMRs and 90% CI of bupropion were 0.695 (0.622, 0.774) for AUC(0,∞) and 0.400 (0.353, 0.449) for C(max) , respectively. The corresponding values for 4-hydroxybupropion were 1.43 (1.28, 1.53) and 2.63 (2.07, 2.92). The t(1/2) value was significantly increased for bupropion and decreased for 4-hydroxybupropion. The t(max) values of bupropion and 4-hydroxybupropion were both significantly decreased. The mean percentage changes in pharmacokinetic parameters among the CYP2B6 genotype groups were not significantly different. Oral administration of metamizole for 4 days significantly altered the pharmacokinetics of both bupropion and its active metabolite, 4-hydroxybupropion, and significantly increased the CYP2B6-catalyzed bupropion hydroxylation in all of the subjects. Cautions should be taken when metamizole is co-administered with CYP2B6 substrate drugs. © 2012 The Authors. British Journal of Clinical Pharmacology © 2012 The British Pharmacological Society.

  19. Detection of Hydroxyl and Perhydroxyl Radical Generation from Bleaching Agents with Nuclear Magnetic Resonance Spectroscopy. (United States)

    Sharma, Himanshu; Sharma, Divya S

    Children/adolescent's orodental structures are different in anatomy and physiology from that of adults, therefore require special attention for bleaching with oxidative materials. Hydroxyl radical (OH(.)) generation from bleaching agents has been considered directly related to both its clinical efficacy and hazardous effect on orodental structures. Nonetheless bleaching agents, indirectly releasing hydrogen peroxide (H2O2), are considered safer yet clinically efficient. Apart from OH(.), perhydroxyl radicals (HO2(.)) too, were detected in bleaching chemistry but not yet in dentistry. Therefore, the study aims to detect the OH(.) and HO2(.) from bleaching agents with their relative integral value (RIV) using (31)P nuclear magnetic resonance ((31)PNMR) spectroscope. Radicals were generated with UV light in 30% H2O2, 35% carbamide peroxide (CP), sodium perborate tetrahydrate (SPT) and; neutral and alkaline 30% H2O2. Radicals were spin-trapped with DIPPMPO in NMR tubes for each test agents as a function of time (0, 1, 2, 3min) at their original pH. Peaks were detected for OH(.) and HO2(.) on NMR spectrograph. RIV were read and compared for individual radicals detected. Only OH(.) were detected from acidic and neutral bleaching agent (30% acidic and neutral H2O2, 35%CP); both HO2(.) and OH(.) from 30% alkaline H2O2; while only HO2(.) from more alkaline SPT. RIV for OH(.) was maximum at 1min irradiation of acidic 30%H2O2 and 35%CP and minimum at 1min irradiation of neutral 30%H2O2. RIV for HO2(.)was maximum at 0min irradiation of alkaline 30%H2O2 and minimum at 2min irradiation of SPT. The bleaching agents having pH- neutral and acidic were always associated with OH(.); weak alkaline with both OH(.) and HO2(.); and strong alkaline with HO2(.) only. It is recommended to check the pH of the bleaching agents and if found acidic, should be made alkaline to minimize oxidative damage to enamel itself and then to pulp/periodontal tissues. H2O2: hydrogen peroxide CP: carbamide

  20. Development of a novel hydroxyl ammonium nitrate based liquid propellant for air-independent propulsion (United States)

    Fontaine, Joseph Henry

    The focus of this dissertation is the development of an Unmanned Undersea Vehicle (UUV) liquid propellant employing Hydroxyl Ammonium Nitrate (HAN) as the oxidizer. Hydroxyl Ammonium Nitrate is a highly acidic aqueous based liquid oxidizer. Therefore, in order to achieve efficient combustion of a propellant using this oxidizer, the fuel must be highly water soluble and compatible with the oxidizer to prevent a premature ignition prior to being heated within the combustion chamber. An extensive search of the fuel to be used with this oxidizer was conducted. Propylene glycol was chosen as the fuel for this propellant, and the propellant given the name RF-402. The propellant development process will first evaluate the propellants thermal stability and kinetic parameters using a Differential Scanning Calorimeter (DSC). The purpose of the thermal stability analysis is to determine the temperature at which the propellant decomposition begins for the future safe handling of the propellant and the optimization of the combustion chamber. Additionally, the thermogram results will provide information regarding any undesirable endotherms prior to the decomposition and whether or not the decomposition process is a multi-step process. The Arrhenius type kinetic parameters will be determined using the ASTM method for thermally unstable materials. The activation energy and pre-exponential factor of the propellant will be determined by evaluating the decomposition peak temperature over a temperature scan rate ranging from 1°C per minute to 10°C per minute. The kinetic parameters of the propellant will be compared to those of 81 wt% HAN to determine if the HAN decomposition is controlling the overall decomposition of the propellant RF-402. The lifetime of individual droplets will be analyzed using both experimental and theoretical techniques. The theoretical technique will involve modeling the lifetime of an individual droplet in a combustion chamber like operating environment

  1. Silver Coordination Polymers for Prevention of Implant Infection: Thiol Interaction, Impact on Respiratory Chain Enzymes, and Hydroxyl Radical Induction▿ †


    Gordon, Oliver; Slenters, Tünde Vig; Brunetto, Priscilla S.; Villaruz, Amer E.; Sturdevant, Daniel E.; Otto, Michael; Landmann, Regine; Fromm, Katharina M.


    Prosthetic joint replacements are used increasingly to alleviate pain and improve mobility of the progressively older and more obese population. Implant infection occurs in about 5% of patients and entails significant morbidity and high social costs. It is most often caused by staphylococci, which are introduced perioperatively. They are a source of prolonged seeding and difficult to treat due to antibiotic resistance; therefore, infection prevention by prosthesis coating with nonantibiotic-t...

  2. Detection of water and/or hydroxyl on asteroid (16) Psyche (United States)

    Takir, Driss; Reddy, Vishnu; Sanchez, Juan A.; Shepard, Michael K.; Emery, Joshua P.


    In order to search for evidence of hydration on M-type asteroid (16) Psyche, we observed this object in the 3 μm spectral region using the long-wavelength cross-dispersed (LXD: 1.9–4.2 μm) mode of the SpeX spectrograph/imager at the NASA Infrared Telescope Facility. Our observations show that Psyche exhibits a 3 μm absorption feature, attributed to water or hydroxyl. The 3 μm absorption feature is consistent with the hydration features found on the surfaces of water-rich asteroids, attributed to OH- and/or H2O-bearing phases (phyllosilicates). The detection of a 3 μm hydration absorption band on Psyche suggests that this asteroid may not be a metallic core, or it could be a metallic core that has been impacted by carbonaceous material over the past 4.5 Gyr. Our results also indicate rotational spectral variations, which we suggest reflect heterogeneity in the metal/silicate ratio on the surface of Psyche.


    Energy Technology Data Exchange (ETDEWEB)

    Takir, Driss [U.S. Geological Survey, Astrogeology Science Center, Flagstaff, AZ 86001 (United States); Reddy, Vishnu [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721 (United States); Sanchez, Juan A. [Planetary Science Institute, 1700 E Fort Lowell Road, Suite 106, Tucson, AZ 85719 (United States); Shepard, Michael K. [Department of Geography and Geosciences, Bloomsburg University of Pennsylvania, 400 E. Second Street, Bloomsburg, PA 17815 (United States); Emery, Joshua P., E-mail: [Earth and Planetary Science Department, Planetary Geosciences Institute, University of Tennessee, Knoxville, TN 37996 (United States)


    In order to search for evidence of hydration on M-type asteroid (16) Psyche, we observed this object in the 3 μ m spectral region using the long-wavelength cross-dispersed (LXD: 1.9–4.2 μ m) mode of the SpeX spectrograph/imager at the NASA Infrared Telescope Facility. Our observations show that Psyche exhibits a 3 μ m absorption feature, attributed to water or hydroxyl. The 3 μ m absorption feature is consistent with the hydration features found on the surfaces of water-rich asteroids, attributed to OH- and/or H{sub 2}O-bearing phases (phyllosilicates). The detection of a 3 μ m hydration absorption band on Psyche suggests that this asteroid may not be a metallic core, or it could be a metallic core that has been impacted by carbonaceous material over the past 4.5 Gyr. Our results also indicate rotational spectral variations, which we suggest reflect heterogeneity in the metal/silicate ratio on the surface of Psyche.

  4. Hydroxyl radical observations during the wintertime in Beijing and comparison with photochemical steady state predictions (United States)

    Whalley, Lisa; Woodward-Massey, Robert; Slater, Eloise; Ye, Chunxiang; Heard, Dwayne; Crilley, Leigh; Kramer, Louisa; Bloss, William; Squires, Freya; Dunmore, Rachel; Lee, James


    In Beijing, a megacity of more than 21 million inhabitants, poor urban air quality has a demonstrable effect on human health. During the wintertime, anthropogenic emissions from fossil fuel combustion can lead to high aerosol loadings and frequent haze events. A high oxidation capacity on hazy days has previously been inferred from the significant contribution secondary organic aerosol (SOA) make to total PM2.5 (Huang et al., 2014). The hydroxyl radical (OH) mediates virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and SOA. Understanding the sources and sinks of OH in the atmosphere is essential in improving predictions of the lifetimes and chemical processing of pollutants and spatial scales of their transport within urban areas. We will present OH measurements made in central Beijing during the recent 'An Integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO)' project which took place in November and December 2016. We will compare the OH observations, made over a range of meteorological conditions including a number of haze episodes, to steady state calculations constrained to the total OH reactivity and key OH precursors that were measured alongside. Through this comparison we will identify the major OH sources which sustain the wintertime oxidation capacity.

  5. The uridine diphosphate glucuronosyltransferases: quantitative structure-activity relationships for hydroxyl polychlorinated biphenyl substrates

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Degao [Dalian University of Technology, Department of Environmental Science and Technology, Dalian (China)


    Quantitative structure-activity relationships (QSARs), which relate the glucuronidation of hydroxyl polychlorinated biphenyls (OH-PCBs) - catalyzed by the uridine diphosphate glucuronosyltransferases (UGTs) - to their physicochemical properties and molecular structural parameters, can be used to predict the rate constants and interpret the mechanism of glucuronidation. In this study, QSARs have been developed that use 23 semi-empirical calculated quantum chemical descriptors to predict the logarithms of the constants 1/K{sub m} and V{sub max}, related to enzyme kinetics. A partial least squares regression method was used to select the optimal set of descriptors to minimize the multicollinearity between the descriptors, as well as to maximize the cross-validated coefficient (Q{sup 2} {sub cum}) values. The key descriptors affecting log(1/K{sub m}) were E{sub lumo}- E{sub homo} (the energy gap between the lowest unoccupied molecular orbital and the highest occupied molecular orbital) and q{sub C}{sup -} (the largest negative net atomic charge on a carbon atom), while the key descriptors affecting log V{sub max} were the polarizability {alpha}, the Connolly solvent-excluded volume (CSEV), and logP (the logarithm of the partition coefficient for octanol/water). From the results obtained it can be concluded that hydrophobic and electronic aspects of OH-PCBs are important in the glucuronidation of OH-PCBs. (orig.)

  6. A novel hydroxyl epoxy phosphate monomer enhancing the anticorrosive performance of waterborne Graphene/Epoxy coatings (United States)

    Ding, Jiheng; Rahman, Obaid ur; Peng, Wanjun; Dou, Huimin; Yu, Haibin


    Herein, we report the synthesis of a novel hydroxyl epoxy phosphate monomer (PGHEP) as an efficient dispersant for graphene to enhance the compatibility of the graphene in epoxy resin. Raman spectroscopy, Ultraviolet-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS) studies were confirmed the π-π interactions between PGHEP and graphene. Well-dispersed states of PGHEP functionalized graphene (G) sheets in water were analyzed by transmission electron microscopy (TEM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Further, microstructure of prepared G/waterborne epoxy coatings containing 0.5-1.0 wt.% of PGHEP functionalized G sheets were also observed with the help of SEM and TEM. The PGHEP functionalized G sheets dispersed composite coatings displayed enhanced corrosion resistance compared with pure epoxy resin, these coatings have higher contact angle, lower water absorption as evident from the results of electrochemical impedance spectroscopy (EIS) and salt spray tests. The superior corrosion protection performances of G/epoxy coatings were mainly attributed to the formed passive film from uniformly dispersed PGHEP functionalized G sheets which act as physical barrier on the steel surface. Therefore, this work provides a novel bio-based efficient dispersant for G sheets and an important method for preparing G/waterborne epoxy coatings with superior corrosion resistance properties.

  7. Rheological properties of N-[(2-hydroxyl)-propyl-3-trimethyl ammonium] chitosan chloride. (United States)

    Wang, Beibei; Qiao, Congde; Gao, Xinyue; Yang, Xiaodeng; Li, Yan; Li, Tianduo


    N-[(2-hydroxyl)-propyl-3-trimethyl ammonium] chitosan chloride (HTCC) was synthesized using 1-allyl-3-methylimidazole chloride (AmimCl) as a homogeneous green reaction media. The effects of polymer concentration, temperature, cation valence, anion type and concentration of inorganic salt, and degree of substitution (DS) on the rheological properties of HTCC were investigated. The apparent viscosity indicated that HTCC solution was a typical pseudoplastic fluid, which could be described by Ostwald de Waele and Cross-empirical models. The viscoelastic properties showed the formation of gel-like structures. Temperature showed slight effect on the apparent viscosity of HTCC solution, while the DS of HTCC showed remarkable effect on the apparent viscosity. At a low shear rate, the apparent viscosities of HTCC solution increased firstly with an increase of c NaCl from 0 to 40mmol/L, and then decreased with further increasing c NaCl to 60mmol/L. At a high shear rate, the opposite trends were observed. The variation of HTCC molecular construction under different inorganic salt conditions was confirmed by scanning electron microscopy, meanwhile, the variation mechanism was proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. 2-Pyridinyl Thermolabile Groups as General Protectants for Hydroxyl, Phosphate, and Carboxyl Functions. (United States)

    Brzezinska, Jolanta; Witkowska, Agnieszka; Kaczyński, Tomasz P; Krygier, Dominika; Ratajczak, Tomasz; Chmielewski, Marcin K


    Application of 2-pyridinyl thermolabile protecting groups (2-PyTPGs) for protection of hydroxyl, phosphate, and carboxyl functions is presented in this unit. Their characteristic feature is a unique removal process following the intramolecular cyclization mechanism and induced only by temperature rise. Deprotection rate of 2-PyTPGs is dependent on certain parameters, such as solvent (aqueous or non-aqueous medium), pH values, and electron distribution in a pyridine ring. The presented approach pertains not only to protecting groups but also to an advanced system of controlling certain properties of 2-pyridinyl derivatives. We improved the "chemical switch" method, allowing us to regulate the protecting group stability by inversing the electron distribution in 2-PyTPG. Together with pH values manipulation, this allows us to regulate the protecting group stability. Moreover, phosphite cyclization to oxazaphospholidine provides a very stable but easily reversible tool for phosphate protection/modifications. For all TPGs we confirmed their utility in a system of protecting groups. This concept can contribute to designing the general protecting group that could be useful in bioorganic chemistry. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  9. Role of allyl group in the hydroxyl and peroxyl radical scavenging activity of S-allylcysteine. (United States)

    Maldonado, Perla D; Alvarez-Idaboy, J Raúl; Aguilar-González, Adriana; Lira-Rocha, Alfonso; Jung-Cook, Helgi; Medina-Campos, Omar Noel; Pedraza-Chaverrí, José; Galano, Annia


    S-Allylcysteine (SAC) is the most abundant compound in aged garlic extracts, and its antioxidant properties have been demonstrated. It is known that SAC is able to scavenge different reactive species including hydroxyl radical (•OH), although its potential ability to scavenge peroxyl radical (ROO•) has not been explored. In this work the ability of SAC to scavenge ROO• was evaluated, as well as the role of the allyl group (-S-CH(2)-CH═CH(2)) in its free radical scavenging activity. Two derived compounds of SAC were prepared: S-benzylcysteine (SBC) and S-propylcysteine (SPC). Their abilities to scavenge •OH and ROO• were measured. A computational analysis was performed to elucidate the mechanism by which these compounds scavenge •OH and ROO•. SAC was able to scavenge •OH and ROO•, in a concentration-dependent way. Such activity was significantly ameliorated when the allyl group was replaced by benzyl or propyl groups. It was shown for the first time that SAC is able to scavenge ROO•.

  10. Mechanistic insight into degradation of endocrine disrupting chemical by hydroxyl radical: An experimental and theoretical approach. (United States)

    Xiao, Ruiyang; Gao, Lingwei; Wei, Zongsu; Spinney, Richard; Luo, Shuang; Wang, Donghong; Dionysiou, Dionysios D; Tang, Chong-Jian; Yang, Weichun


    Advanced oxidation processes (AOPs) based on formation of free radicals at ambient temperature and pressure are effective for treating endocrine disrupting chemicals (EDCs) in waters. In this study, we systematically investigated the degradation kinetics of bisphenol A (BPA), a representative EDC by hydroxyl radical (OH) with a combination of experimental and theoretical approaches. The second-order rate constant (k) of BPA with OH was experimentally determined to be 7.2 ± 0.34 × 10(9) M(-1) s(-1) at pH 7.55. We also calculated the thermodynamic and kinetic behaviors for the bimolecular reactions by density functional theory (DFT) using the M05-2X method with 6-311++G** basis set and solvation model based on density (SMD). The results revealed that H-abstraction on the phenol group is the most favorable pathway for OH. The theoretical k value corrected by the Collins-Kimball approach was determined to be 1.03 × 10(10) M(-1) s(-1), which is in reasonable agreement with the experimental observation. These results are of fundamental and practical importance in understanding the chemical interactions between OH and BPA, and aid further AOPs design in treating EDCs during wastewater treatment processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Direct electrochemistry of glucose oxidase and glucose biosensing on a hydroxyl fullerenes modified glassy carbon electrode. (United States)

    Gao, Yun-Fei; Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, Bao-Lin; Hong, Jun; Sheibani, Nader; Ghourchian, Hedayatollah; Hong, Tao; Moosavi-Movahedi, Ali Akbar


    Direct electrochemistry of glucose oxidase (GOD) was achieved when GOD-hydroxyl fullerenes (HFs) nano-complex was immobilized on a glassy carbon (GC) electrode and protected with a chitosan (Chit) membrane. The ultraviolet-visible absorption spectrometry (UV-vis), transmission electron microscopy (TEM), and circular dichroism spectropolarimeter (CD) methods were utilized for additional characterization of the GOD, GOD-HFs and Chit/GOD-HFs. Chit/HFs may preserve the secondary structure and catalytic properties of GOD. The cyclic voltammograms (CVs) of the modified GC electrode showed a pair of well-defined quasi-reversible redox peaks with the formal potential (E°') of 353 ± 2 mV versus Ag/AgCl at a scan rate of 0.05 V/s. The heterogeneous electron transfer constant (ks) was calculated to be 2.7 ± 0.2s(-1). The modified electrode response to glucose was linear in the concentrations ranging from 0.05 to 1.0mM, with a detection limit of 5 ± 1 μM. The apparent Michaelis-Menten constant (Km(app)) was 694 ± 8 μM. Thus, the modified electrode could be applied as a third generation biosensor for glucose with high sensitivity, selectivity and low detection limit. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Laser smoothing of sub-micron grooves in hydroxyl-rich fused silica

    Energy Technology Data Exchange (ETDEWEB)

    Shen Nan [Lawrence Livermore National Laboratory, 7000 East Avenue, L-491, Livermore, CA 94550-9234 (United States); Matthews, Manyalibo J., E-mail: [Lawrence Livermore National Laboratory, 7000 East Avenue, L-491, Livermore, CA 94550-9234 (United States); Fair, James E.; Britten, Jerald A.; Nguyen, Hoang T.; Cooke, Diane; Elhadj, Selim; Yang, Steven T. [Lawrence Livermore National Laboratory, 7000 East Avenue, L-491, Livermore, CA 94550-9234 (United States)


    Nano- to micrometer-sized surface defects on UV-grade fused silica surfaces are known to be effectively smoothed through the use of high-temperature localized CO{sub 2} laser heating, thereby enhancing optical properties. However, the details of the mass transport and the effect of hydroxyl content on the laser smoothing of defective silica at sub-micron length scales are still not completely understood. In this study, we examine the morphological evolution of sub-micron, dry-etched periodic surface structures on type II and type III SiO{sub 2} substrates under 10.6 {mu}m CO{sub 2} laser irradiation using atomic force microscopy (AFM). In situ thermal imaging was used to map the transient temperature field across the heated region, allowing assessment of the T-dependent mass transport mechanisms under different laser-heating conditions. Computational fluid dynamics simulations correlated well with experimental results, and showed that for large effective capillary numbers (N{sub c} > 2), surface diffusion is negligible and smoothing is dictated by capillary action, despite the relatively small spatial scales studied here. Extracted viscosity values over 1700-2000 K were higher than the predicted bulk values, but were consistent with the surface depletion of OH groups, which was confirmed using confocal Raman microscopy.

  13. Reaction of hydroxyl radicals with S-nitrosothiols: determination of rate constants and end product analysis. (United States)

    Manoj, Veleeparambil M; Aravindakumar, Charuvila T


    The reaction of the hydroxyl radical (.OH) with S-nitroso derivatives of cysteine, acetylcysteine and glutathione was studied at neutral and acidic pH. The second-order rate constants were determined by a competition kinetic method using a deoxyribose-thiobarbituric acid assay. The rate constants were diffusion controlled and were 2.27, 1.94 and 1.46 x 10(10) dm3 mol-1 s-1, for S-nitrosocysteine, S-nitrosoacetylcysteine and S-nitrosoglutathione respectively, at neutral pH. The major products of the degradation induced by .OH were found to be the corresponding disulfide (-S-S-) and nitrite (NO2-) at neutral pH as well as at pH 3. Simultaneous proton formation has also been observed. A plausible mechanism based on the formation of an intermediate thiol radical (RS.), as a result of electron transfer from the S-nitrosothiols (RSNOs) to .OH, is proposed for the formation of disulfide and nitrite at both pHs. The high rate constant values and the degradation of these compounds demonstrate the potential role of .OH in RSNO metabolism under physiological conditions.

  14. Hydroxyl radical-induced degradation of fenuron in pulse and gamma radiolysis: kinetics and product analysis. (United States)

    Kovács, Krisztina; Mile, Viktoria; Csay, Tamás; Takács, Erzsébet; Wojnárovits, László


    Radiolytic reactions of phenylureas were studied in detail with fenuron model compound in dilute aqueous solutions using pulse radiolysis for detection of the intermediates, gamma radiolysis with UV-Vis and HPLC-MS techniques for analysis of the final products. The kinetics of oxidation was followed by COD, TOC and toxicity measurements. During radiolysis of aerated solutions hydroxyl radical ((•)OH), eaq (-), H(•) and O2 (•-)/HO2 (•) reactive intermediates are produced, the degradation of solute takes place practically entirely through (•)OH reactions. Therefore, the product distribution is similar to the distributions reported in other advanced oxidation processes with (•)OH as main reactant. (•)OH mainly reacts with the aromatic ring, forming cyclohexadienyl radical as an intermediate. This radical in pulse radiolysis has a wide absorption band in the 310-390 nm wavelength range with a maximum at 350 nm. Cyclohexadienyl radical reacts with dissolved O2 with a rate coefficient of ∼ 4 × 10(8) mol(-1) dm(3) s(-1) forming peroxy radical. The latter may eliminate HO2 (•) giving phenols or undergoes fragmentation. The one-electron oxidant (•)OH on average induces more than two-electron oxidations. The toxicity first increases with absorbed dose, then decreases. This increase is partly due to phenols formed during the first degradation period.

  15. Hydroxylation of 1,8-cineole by Mucor ramannianus and Aspergillus niger. (United States)

    Ramos, Aline de Souza; Ribeiro, Joyce Benzaquem; Teixeira, Bruna Gomes; Ferreira, José Luiz Pinto; Silva, Jefferson Rocha de A; Ferreira, Alexandre do Amaral; de Souza, Rodrigo Octavio Mendonça Alves; Amaral, Ana Claudia F


    The monoterpenoid 1,8-cineole is obtained from the leaves of Eucalyptus globulus and it has important biological activities. It is a cheap natural substrate because it is a by-product of the Eucalyptus cultivation for wood and pulp production. In this study, it was evaluated the potential of three filamentous fungi in the biotransformation of 1,8-cineole. The study was divided in two steps: first, reactions were carried out with 1,8-cineole at 1 g/L for 24 h; afterwards, reactions were carried out with substrate at 5 g/L for 5 days. The substrate was hydroxylated into 2-exo-hydroxy-1,8-cineole and 3-exo-hydroxy-1,8-cineole by fungi Mucor ramannianus and Aspergillus niger with high stereoselectivity. Trichoderma harzianum was also tested but no transformation was detected. M. ramannianus led to higher than 99% of conversion within 24 h with a starting high substrate concentration (1 g/L). When substrate was added at 5 g/L, only M. ramannianus was able to catalyze the reaction, but the conversion level was 21.7% after 5 days. Both products have defined stereochemistry and could be used as chiral synthons. Furthermore, biological activity has been described for 3-exo-hydroxy-1,8-cineol. To the best of our knowledge, this is the first report on the use of M. ramannianus in this reaction.

  16. Hydroxylation of 1,8-cineole by Mucor ramannianusand Aspergillus niger

    Directory of Open Access Journals (Sweden)

    Aline de Souza Ramos


    Full Text Available The monoterpenoid 1,8-cineole is obtained from the leaves of Eucalyptus globulus and it has important biological activities. It is a cheap natural substrate because it is a by-product of the Eucalyptuscultivation for wood and pulp production. In this study, it was evaluated the potential of three filamentous fungi in the biotransformation of 1,8-cineole. The study was divided in two steps: first, reactions were carried out with 1,8-cineole at 1 g/L for 24 h; afterwards, reactions were carried out with substrate at 5 g/L for 5 days. The substrate was hydroxylated into 2-exo-hydroxy-1,8-cineole and 3-exo-hydroxy-1,8-cineole by fungi Mucor ramannianus and Aspergillus niger with high stereoselectivity. Trichoderma harzianum was also tested but no transformation was detected. M. ramannianus led to higher than 99% of conversion within 24 h with a starting high substrate concentration (1 g/L. When substrate was added at 5 g/L, only M. ramannianuswas able to catalyze the reaction, but the conversion level was 21.7% after 5 days. Both products have defined stereochemistry and could be used as chiral synthons. Furthermore, biological activity has been described for 3-exo-hydroxy-1,8-cineol. To the best of our knowledge, this is the first report on the use of M. ramannianus in this reaction.

  17. [7alpha-hydroxylation of steroid 5-olefins by mold fungi]. (United States)

    Andriushina, V G; Druzhinina, A V; Iaderets, V V; Stytsenko, T S; Voĭshvillo, N E


    Hydroxylation activity of the mold fungi belonging to the orders Dothideales, Hypocreales, and Mucorales towards delta(5)-3beta-hydroxysteroids was studied. The fungi Bipolaris sorokiniana, Fusarium sp., and Rhizopus nigricans were able to introduce hydroxy group at position 7alpha; however, this ability was detected only at a low substrate load and with a low yield. A 7alpha-hydroxylase activity of the Curvularia lunata VKPM F-981 culture was shown for the first time. It was demonstrated that the studied strain was capable of stereo- and regioselective transformations of androstane 5-olefins at a load not less than 2 g/l. Conversion of pregnane steroids by this culture yielded both 7alpha and 11beta-hydroxy derivatives. The introduction of 7alpha-hydroxy group by this strain occurred concurrently with enzymatic hydrolysis of ester groups, which proceeded under mild conditions to give the corresponding alcohols in the cases of both 3-acetate of delta(5)-androstenes and mono- and triacetates of delta(5)-pregnenes.

  18. Formation of fluorescent polydopamine dots from hydroxyl radical-induced degradation of polydopamine nanoparticles. (United States)

    Lin, Jia-Hui; Yu, Cheng-Ju; Yang, Ya-Chun; Tseng, Wei-Lung


    This study describes the synthesis of fluorescent polydopamine dots (PDs) through hydroxyl radical-induced degradation of polydopamine nanoparticles. The decomposition of polydopamine nanoparticles to fluorescent PDs was confirmed using transmission electron microscopy and dark-field microscopy. The analysis of PDs by using laser desorption/ionization time-of-flight mass spectrometry revealed that the PDs consisted of dopamine, 5,6-dihydroxyindole, and trihydroxyindole units. Oligomerization and self-assembly of these units produced a broad adsorption band, resulting in an excitation-wavelength-dependent emission behavior. The maximal fluorescence of PDs appeared at 440 nm with a quantum yield of 1.2%. The coordination between the catechol groups of PDs and ferric ions (Fe(3+)) quenched the fluorescence of PDs; the limit of detection at a signal-to-noise ratio of 3 for Fe(3+) was determined to be 0.3 μM. The presence of pyrophosphate switched on the fluorescence of the PD-Fe(3+) complexes. Compared to the other reported methods for sensing Fe(3+), PDs provided simple, low-cost, and reusable detection of Fe(3+).

  19. Diffusion of plasticizer in a solid propellant based on hydroxyl-terminated polybutadiene

    Directory of Open Access Journals (Sweden)

    Juliano Libardi


    Full Text Available The aim of this work was to determine the dioctyl azelate (DOZ plasticizer diffusion coefficient (D for samples containing the interfaces of rubber, liner and solid composite propellant based on hydroxyl-terminated polybutadiene (HTPB. The samples used in the diffusion study were aged up to 31 days after the cure period at 80 °C. A computer program implementing a mathematical model of Fick's second Law of diffusion was developed to calculate the diffusion coefficient based on concentration data obtained from gas chromatographic analyses. The effects of the diffusion phenomenon were also investigated by Shore A hardness and scanning electron microscope (SEM techniques. These analyses were carried out using samples aged at room temperature and at 80 °C. The hardness results showed an increasing trend for the samples aged at room temperature; however in the tests carried out at 80 °C they showed the opposite trend. The SEM analyses detected meaningful changes in the surface morphology of the propellant for both aging temperatures.

  20. Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: airborne measurements

    Directory of Open Access Journals (Sweden)

    M. Martinez


    Full Text Available Direct measurements of OH and HO2 over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy, adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2 mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2 were encountered in the boundary layer over the rainforest.

    The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission.

  1. Synthesis and Characterization of High Energy Sheet Materials Based on HMX / RDX and Hydroxyl Terminated Polybutadiene (United States)

    Elsharkawy, Karim; Guo, Lin; Taha, Elhussein; Fouda, Hany


    In this paper three types of thin sheets of highly energetic materials were prepared and characterized. The first based on 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). The second type based on 1,3,5-trinitro-1,3,5-triazinane (RDX). Both types contain polyurethane (PU), formulated by hydroxyl terminated polybutadiene (HTPB) and Isophorondiisocyanate (IPDI). The third type based on (RDX) and polyisoprene (PI) as high elastomeric material. The first and second types of thin sheets were prepared by applying the casting technique while the third type was prepared by slurry technique then followed by rolling of the prepared beads of the RDX coated by PI. These high energy sheet materials were cured in oven at 60°C. The measured explosive properties of the prepared sheets were discussed and showed that the sensitivity to impact and friction of the prepared sheets explosives materials were markedly decreased when compared to pure HMX or pure RDX, but the sensitivity to heat was close to that of pure RDX. In spite of the markedly decrease in the sensitivity of these sheets, the explosive characteristics were nearly not affected the sheets have very good stress-strain values.

  2. Formation and disposition of N-hydroxylated metabolites of aniline and nitrobenzene by isolated rat hepatocytes. (United States)

    Blaauboer, B J; Van Holsteijn, C W


    The formation and secretion of phenylhydroxylamine plus nitrosobenzene was studied in cultures of isolated rat hepatocytes after addition of aniline or nitrobenzene. With aniline concn. up to 10 mM, N-oxygenated metabolites were secreted linearly with time over 2 h. Phenobarbitone pretreatment in vivo for c. 5 d increased aniline N-hydroxylation by a factor of 2.8. Nitrobenzene reduction by isolated rat hepatocytes, yielding phenylhydroxylamine plus nitrosobenzene in the medium, was stimulated 1.9-fold and 4.3-fold after phenobarbitone pretreatment in vivo for 5 and 10 d, respectively. After reduction of nitrobenzene by isolated hepatocytes, the secretion of N-oxygenated products into the medium was non-linear with time for substrate concn. higher than 2.5 mM, probably due to the formation of cytotoxic concn. of nitrosobenzene. Isolated rat hepatocytes reduced phenylhydroxylamine to aniline. Results indicate that isolated rat hepatocytes are a reliable and sensitive system to demonstrate N-oxygenated metabolites of aromatic amino- and reduction of nitrocompounds.

  3. Mechanistic Study of the Validity of Using Hydroxyl Radical Probes To Characterize Electrochemical Advanced Oxidation Processes. (United States)

    Jing, Yin; Chaplin, Brian P


    The detection of hydroxyl radicals (OH(•)) is typically accomplished by using reactive probe molecules, but prior studies have not thoroughly investigated the suitability of these probes for use in electrochemical advanced oxidation processes (EAOPs), due to the neglect of alternative reaction mechanisms. In this study, we investigated the suitability of four OH(•) probes (coumarin, p-chlorobenzoic acid, terephthalic acid, and p-benzoquinone) for use in EAOPs. Experimental results indicated that both coumarin and p-chlorobenzoic acid are oxidized via direct electron transfer reactions, while p-benzoquinone and terephthalic acid are not. Coumarin oxidation to form the OH(•) adduct product 7-hydroxycoumarin was found at anodic potentials lower than that necessary for OH(•) formation. Density functional theory (DFT) simulations found a thermodynamically favorable and non-OH(•) mediated pathway for 7-hydroxycoumarin formation, which is activationless at anodic potentials > 2.10 V/SHE. DFT simulations also provided estimates of E° values for a series of OH(•) probe compounds, which agreed with voltammetry results. Results from this study indicated that terephthalic acid is the most appropriate OH(•) probe compound for the characterization of electrochemical and catalytic systems.

  4. Detection of hydroxyl ions in bone mineral by solid-state NMR spectroscopy. (United States)

    Cho, Gyunggoo; Wu, Yaotang; Ackerman, Jerome L


    Previous measurements of the hydroxyl (OH-) ion content of the calcium phosphate crystals of bone mineral have indicated a substantial depletion or near-absence of OH-, despite its presumed status as a constituent of the hydroxyapatite lattice. Analytical methods for determining bone crystal OH- content have depended on procedures or assumptions that may have biased the results, such as chemical pretreatment to eliminate interference from the organic matrix. We demonstrate a two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy technique that detects the proton spectrum of bone crystals while suppressing the interfering matrix signals, eliminating the need for specimen pretreatment other than cryogenic grinding. Results on fresh-frozen and ground whole bone of several mammalian species show that the bone crystal OH- is readily detectable; a rough estimate yields an OH- content of human cortical bone of about 20% of the amount expected in stoichiometric hydroxyapatite. This finding sheds light on the biochemical processes underlying normal and abnormal bone mineral metabolism.

  5. Transesterification of PHA to oligomers covalently bonded with (bioactive compounds containing either carboxyl or hydroxyl functionalities.

    Directory of Open Access Journals (Sweden)

    Iwona Kwiecień

    Full Text Available This manuscript presents the synthesis and structural characterisation of novel biodegradable polymeric controlled-release systems of pesticides with potentially higher resistance to weather conditions in comparison to conventional forms of pesticides. Two methods for the preparation of pesticide-oligomer conjugates using the transesterification reaction were developed. The first method of obtaining conjugates, which consist of bioactive compounds with the carboxyl group and polyhydroxyalkanoates (PHAs oligomers, is "one-pot" transesterification. In the second method, conjugates of bioactive compounds with hydroxyl group and polyhydroxyalkanoates oligomers were obtained in two-step method, through cyclic poly(3-hydroxybutyrate oligomers. The obtained pesticide-PHA conjugates were comprehensively characterised using GPC, 1H NMR and mass spectrometry techniques. The structural characterisation of the obtained products at the molecular level with the aid of mass spectrometry confirmed that both of the synthetic strategies employed led to the formation of conjugates in which selected pesticides were covalently bonded to PHA oligomers via a hydrolysable ester bond.

  6. Laser smoothing of sub-micron grooves in hydroxyl-rich fused silica

    Energy Technology Data Exchange (ETDEWEB)

    Shen, N; Matthews, M J; Fair, J E; Britten, J A; Nguyen, H T; Cooke, D; Elhadj, S; Yang, S T


    Nano- to micrometer-sized surface defects on UV-grade fused silica surfaces are known to be effectively smoothed through the use of high-temperature localized CO{sub 2} laser heating, thereby enhancing optical properties. However, the details of the mass transport and the effect of hydroxyl content on the laser smoothing of defective silica at submicron length scales is still not completely understood. In this study, we examine the morphological evolution of sub-micron, dry-etched periodic surface structures on type II and type III SiO{sub 2} substrates under 10.6 {micro}m CO{sub 2} laser irradiation using atomic force microscopy (AFM). In-situ thermal imaging was used to map the transient temperature field across the heated region, allowing assessment of the T-dependent mass transport mechanisms under different laser-heating conditions. Computational fluid dynamics simulations correlated well with experimental results, and showed that for large effective capillary numbers (N{sub c} > 2), surface diffusion is negligible and smoothing is dictated by capillary action, despite the relatively small spatial scales studied here. Extracted viscosity values over 1700-2000K were higher than the predicted bulk values, but were consistent with the surface depletion of OH groups, which was confirmed using confocal Raman microscopy.

  7. Binding of hydroxylated polybrominated diphenyl ethers with human serum albumin: Spectroscopic characterization and molecular modeling. (United States)

    Yang, Lulu; Yang, Wu; Wu, Zhiwei; Yi, Zhongsheng


    Three hydroxylated polybrominated diphenyl ethers (OH-PBDEs), 3-OH-BDE-47, 5-OH-BDE-47, and 6-OH-BDE-47, were selected to investigate the interactions between OH-PBDEs with human serum albumin (HSA) under physiological conditions. The observed fluorescence quenching can be attributed to the formation of complexes between HSA and OH-PBDEs. The thermodynamic parameters at different temperatures indicate that the binding was caused by hydrophobic forces and hydrogen bonds. Molecular modeling and three-dimensional fluorescence spectrum showed conformational and microenvironmental changes in HSA. Circular dichroism analysis showed that the addition of OH-PBDEs changed the conformation of HSA with a minor reduction in α-helix content and increase in β-sheet content. Furthermore, binding distance r between the donor (HSA) and acceptor (three OH-PBDEs) calculated using Förster's nonradiative energy transfer theory was molecular dynamics simulations, the binding free energies (ΔGbind ) were calculated using molecular mechanics/Poisson - Boltzmann surface area method, and the crucial residues in HSA were identified. Copyright © 2017 John Wiley & Sons, Ltd.

  8. Numerical analysis of quantitative measurement of hydroxyl radical concentration using laser-induced fluorescence in flame (United States)

    Shuang, Chen; Tie, Su; Yao-Bang, Zheng; Li, Chen; Ting-Xu, Liu; Ren-Bing, Li; Fu-Rong, Yang


    The aim of the present work is to quantitatively measure the hydroxyl radical concentration by using LIF (laser-induced fluorescence) in flame. The detailed physical models of spectral absorption lineshape broadening, collisional transition and quenching at elevated pressure are built. The fine energy level structure of the OH molecule is illustrated to understand the process with laser-induced fluorescence emission and others in the case without radiation, which include collisional quenching, rotational energy transfer (RET), and vibrational energy transfer (VET). Based on these, some numerical results are achieved by simulations in order to evaluate the fluorescence yield at elevated pressure. These results are useful for understanding the real physical processes in OH-LIF technique and finding a way to calibrate the signal for quantitative measurement of OH concentration in a practical combustor. Project supported by the National Natural Science Foundation of China (Grant No. 11272338) and the Fund from the Science and Technology on Scramjet Key Laboratory, China (Grant No. STSKFKT2013004).

  9. Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation. (United States)

    Rohrer, Franz; Berresheim, Harald


    The most important chemical cleaning agent of the atmosphere is the hydroxyl radical, OH. It determines the oxidizing power of the atmosphere, and thereby controls the removal of nearly all gaseous atmospheric pollutants. The atmospheric supply of OH is limited, however, and could be overcome by consumption due to increasing pollution and climate change, with detrimental feedback effects. To date, the high variability of OH concentrations has prevented the use of local observations to monitor possible trends in the concentration of this species. Here we present and analyse long-term measurements of atmospheric OH concentrations, which were taken between 1999 and 2003 at the Meteorological Observatory Hohenpeissenberg in southern Germany. We find that the concentration of OH can be described by a surprisingly linear dependence on solar ultraviolet radiation throughout the measurement period, despite the fact that OH concentrations are influenced by thousands of reactants. A detailed numerical model of atmospheric reactions and measured trace gas concentrations indicates that the observed correlation results from compensations between individual processes affecting OH, but that a full understanding of these interactions may not be possible on the basis of our current knowledge of atmospheric chemistry. As a consequence of the stable relationship between OH concentrations and ultraviolet radiation that we observe, we infer that there is no long-term trend in the level of OH in the Hohenpeissenberg data set.

  10. Hydroxyl radical scavenging activities of isoquinoline alkaloids isolated from Coptis chinensis. (United States)

    Jang, Moon Hee; Kim, Hyun Young; Kang, Ki Sung; Yokozawa, Takako; Park, Jeong Hill


    The hydroxyl radical (*OH) scavenging and ferrous ion chelating activities of four isoquinoline alkaloids isolated from Coptis chinensis Franch were studied for the identification of their structural characteristics to scavenge *OH. The *OH was generated via Fe(II)-catalazed Fenton reaction in this study and the reliable measurement of *OH scavenging activities of isoquinoline alkaloids were achieved using electron spin resonance (ESR) spectrometry method. At the 1 mM concentration, berberrubine (85%) showed the strongest *OH scavenging activity and the next were in the decreasing order of coptisine (79%), berberine (23%), and palmatine (22%). The ferrous ion chelating effects of the alkaloids showed similar pattern with their *OH scavenging effects. These results suggest that *OH scavenging effects of the alkaloids were closely related to their ferrous ion chelating activities. In addition, metal chelating functional groups such as hydroxy group at C-9 and methylenedioxy group at C-9 and C-10 were thought to contribute to the *OH scavenging activities of the isoquinoline alkaloids.

  11. Surface hydroxyl configuration of various crystal faces of hematite and goethite

    Energy Technology Data Exchange (ETDEWEB)

    Barron, V.; Torrent, J. [Universidad de Cordoba (Spain). Dept. de Ciencias y Recursos Agricolas y Forestales


    The surface properties of oxides and hydroxides depend on their surface hydroxyl configuration (SHC). Unfortunately, the SHC of the various Fe (hydr) oxides has not been systematically studied to date. This paper reports the SHC of the hematite {l_brace}100{r_brace}, {l_brace}110{r_brace}, {l_brace}012{r_brace}, {l_brace}104{r_brace}, {l_brace}018{r_brace}, {l_brace}113{r_brace}, and {l_brace}001{r_brace}, and the goethite {l_brace}100{r_brace}, {l_brace}010{r_brace}, {l_brace}110{r_brace}, and {l_brace}021{r_brace} faces, which are the most common in natural and synthetic specimens. Both minerals exhibit marked differences between faces, particularly with regard to the presence and proportion of singly, doubly, and triply coordinated OH groups. Pairs of contiguous singly coordinated OH groups, which are involved in the specific adsorption of phosphate and other ions, occur on all the goethite faces studied, but not on those of hematite. According to the hypotheses inherent in some models, the variable SHC of hematite and goethite faces should result in marked differences in proton and adsorption and, hence, surface charging properties.

  12. Effects of reduction products of ortho-hydroxyl substituted azo dyes on biodecolorization of azo dyes

    Energy Technology Data Exchange (ETDEWEB)

    Liu Guangfei [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China); Wang Jing, E-mail: [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China); Lu Hong; Jin Ruofei; Zhou Jiti; Zhang Long [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China)


    The mediated effects of reduction products of some ortho-hydroxyl substituted azo dyes on biodecolorization were investigated. The results indicated that the addition of reduction products could effectively accelerate dye decolorization by Shigella sp. QRZ-1. The best accelerating effect was obtained with the addition of reduction products of Acid Red 14 (AR14), resulting in an over 3-fold increase in decolorization efficiency of many azo dyes. In sequencing batch reactor experiments, the accelerating effect of reduction products of AR14 was more obvious (1.5-fold) during the startup of the system. When the dye concentration was increased to 500 mg L{sup -1}, the accelerated decolorization efficiency was still maintained around 95%. The presence of AR14 in the feed enhanced the decolorization performance of anaerobic sludge, indicating that the strategy may be beneficial for practical application. 1-Naphthol-2-amino-4-sulfonic acid, which is one of the reduction products of AR14, may function as redox mediator to speed up azo dye biodecolorization.

  13. Characterization of a polycyclic aromatic ring-hydroxylation dioxygenase from Mycobacterium sp. NJS-P. (United States)

    Zeng, Jun; Zhu, Qinghe; Wu, Yucheng; Chen, Hong; Lin, Xiangui


    Ring-hydroxylating dioxygenases (RHDs) play a critical role in the biodegradation of polycyclic aromatic hydrocarbons (PAHs). In this study, genes pdoAB encoding a dioxygenase capable of oxidizing various PAHs with up to five-ring benzo[a]pyrene were cloned from Mycobacterium sp. NJS-P. The α-subunit of the PdoAB showed 99% and 93% identity to that from Mycobacterium sp. S65 and Mycobacterium sp. py136, respectively. An Escherichia coli expression experiment revealed that the enzyme is able to oxidize anthracene, phenanthrene, pyrene and benzo[a]pyrene, but not to fluoranthene and benzo[a]anthracene. Furthermore, the results of in silico analysis showed that PdoAB has a large substrate-binding pocket satisfying for accommodation of HMW PAHs, and suggested that the binding energy of intermolecular interaction may predict the substrate conversion of RHDs towards HMW PAHs, especially those may have steric constraints on the substrate-binding pocket, such as benzo[a]pyrene and benzo[a]anthracene. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Two Cytochrome P450 Monooxygenases Catalyze Early Hydroxylation Steps in the Potato Steroid Glycoalkaloid Biosynthetic Pathway. (United States)

    Umemoto, Naoyuki; Nakayasu, Masaru; Ohyama, Kiyoshi; Yotsu-Yamashita, Mari; Mizutani, Masaharu; Seki, Hikaru; Saito, Kazuki; Muranaka, Toshiya


    α-Solanine and α-chaconine, steroidal glycoalkaloids (SGAs) found in potato (Solanum tuberosum), are among the best-known secondary metabolites in food crops. At low concentrations in potato tubers, SGAs are distasteful; however, at high concentrations, SGAs are harmful to humans and animals. Here, we show that POTATO GLYCOALKALOID BIOSYNTHESIS1 (PGA1) and PGA2, two genes that encode cytochrome P450 monooxygenases (CYP72A208 and CYP72A188), are involved in the SGA biosynthetic pathway, respectively. The knockdown plants of either PGA1 or PGA2 contained very little SGA, yet vegetative growth and tuber production were not affected. Analyzing metabolites that accumulated in the plants and produced by in vitro enzyme assays revealed that PGA1 and PGA2 catalyzed the 26- and 22-hydroxylation steps, respectively, in the SGA biosynthetic pathway. The PGA-knockdown plants had two unique phenotypic characteristics: The plants were sterile and tubers of these knockdown plants did not sprout during storage. Functional analyses of PGA1 and PGA2 have provided clues for controlling both potato glycoalkaloid biosynthesis and tuber sprouting, two traits that can significantly impact potato breeding and the industry. © 2016 American Society of Plant Biologists. All Rights Reserved.

  15. Hyperfine structure of the hydroxyl free radical (OH) in electric and magnetic fields (United States)

    Maeda, Kenji; Wall, Michael L.; Carr, Lincoln D.


    We investigate single-particle energy spectra of the hydroxyl free radical (OH) in the lowest electronic and rovibrational level under combined static electric and magnetic fields, as an example of heteronuclear polar diatomic molecules. In addition to the fine-structure interactions, the hyperfine interactions and centrifugal distortion effects are taken into account to yield the zero-field spectrum of the lowest 2Π3 / 2 manifold to an accuracy of less than 2kHz. We also examine level crossings and repulsions in the hyperfine structure induced by applied electric and magnetic fields. Compared to previous work, we found more than 10 percent reduction of the magnetic fields at level repulsions in the Zeeman spectrum subjected to a perpendicular electric field. In addition, we find new level repulsions, which we call Stark-induced hyperfine level repulsions, that require both an electric field and hyperfine structure. It is important to take into account hyperfine structure when we investigate physics of OH molecules at micro-Kelvin temperatures and below. This research was supported in part by AFOSR Grant No.FA9550-11-1-0224 and by the NSF under Grants PHY-1207881 and NSF PHY-1125915. We appreciate the Aspen Center for Physics, supported in part by the NSF Grant No.1066293, for hospitality.

  16. Cryptic indole hydroxylation by a non-canonical terpenoid cyclase parallels bacterial xenobiotic detoxification (United States)

    Kugel, Susann; Baunach, Martin; Baer, Philipp; Ishida-Ito, Mie; Sundaram, Srividhya; Xu, Zhongli; Groll, Michael; Hertweck, Christian


    Terpenoid natural products comprise a wide range of molecular architectures that typically result from C-C bond formations catalysed by classical type I/II terpene cyclases. However, the molecular diversity of biologically active terpenoids is substantially increased by fully unrelated, non-canonical terpenoid cyclases. Their evolutionary origin has remained enigmatic. Here we report the in vitro reconstitution of an unusual flavin-dependent bacterial indoloterpenoid cyclase, XiaF, together with a designated flavoenzyme-reductase (XiaP) that mediates a key step in xiamycin biosynthesis. The crystal structure of XiaF with bound FADH2 (at 2.4 Å resolution) and phylogenetic analyses reveal that XiaF is, surprisingly, most closely related to xenobiotic-degrading enzymes. Biotransformation assays show that XiaF is a designated indole hydroxylase that can be used for the production of indigo and indirubin. We unveil a cryptic hydroxylation step that sets the basis for terpenoid cyclization and suggest that the cyclase has evolved from xenobiotics detoxification enzymes.

  17. "The Effect of Hydroxyl Containing Tablet Excipients on the Adhesive Duration of Some Mucoadhesive Polymers "

    Directory of Open Access Journals (Sweden)

    Seyed Alireza Mortazavi


    Full Text Available In order to investigate the effect of hydroxyl group containing tablet excipients on the duration of adhesion of mucoadhesive polymers, discs containing Carbopol 934 (C934, polycarbophil (PC, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose (HPMC, tragacanth (trag. and sodium alginate (Na alg., either alone or in the presence of various amounts of excipients were prepared. The duration of adhesion of the prepared discs were determined in pH 7.0 phosphate buffer at 37°C. All the excipients examined reduced the duration of adhesion and the relative durability of the polymer containing discs. HPMC discs despite showing the longest duration of mucoadhesion, suffered the greatest reduction in adhesive properties in the presence of excipients which were examined. Following HPMC, Na alg. and then trag. discs showed the greatest sensitivity to the presence of excipients. The least reduction in the duration of adhesion was observed with PC and C934. Among the excipients tested, spray-dried lactose produced the greatest reduction in the duration of adhesion, followed by polyethylene glycol 6000 and pregelatinized starch. The smallest reduction in the adhesive properties of the test polymers was due to talc powder. Hence, it seems that addition of the tablet excipients adversely reduce the adhesive properties of mucoadhesive dosage forms, which should be carefully considered during their formulation.

  18. The Effect of Highly Hydroxylated Fullerenol C60(OH36 on Human Erythrocyte Membrane Organization

    Directory of Open Access Journals (Sweden)

    Jacek Grebowski


    Full Text Available The mechanism of the interaction of highly hydroxylated fullerenol C60(OH36 with erythrocyte membranes was studied by electron spin resonance spectroscopy (ESR of stearic acid derivatives labeled with a nitroxyl radical at C-12 or C-16 and with a nitroxyl derivative of maleimide covalently attached to sulfhydryl groups of membrane proteins. A significant increase in membrane fluidity in the hydrophobic region of the lipid bilayer was observed for 12-doxylstearic acid at fullerenol concentrations of 100 mg/L or 150 mg/L, while for 16-doxylstearic acid significant increase in fluidity was only observed at 150 mg/L. Fullerenol at 100 mg/L or 150 mg/L caused conformational changes in membrane proteins, expressed as an increase in the hw/hs parameter, when fullerenol was added before the maleimide spin label (MSL to the membrane suspension. The increase of the hw/hs parameter may be caused by changes in lipid-protein or protein-protein interactions which increase the mobility of the MSL label and as a result increase the membrane fluidity. Incubation of the membranes with the MSL before the addition of fullerenol blocked the available membrane protein –SH groups and minimized the interaction of fullerenol with them. This confirms that fullerenol interacts with erythrocyte membrane proteins via available protein –SH groups.

  19. Activation of PVDF membranes through facile hydroxylation of the polymeric dope

    KAUST Repository

    Al-Gharabli, Samer


    A method comprising a two-step alkali/acid treatment of poly (vinylidene fluoride) (PVDF) polymer is developed for the fabrication of flat-sheet PVDF membranes functionalized with labile hydroxyl groups. This method involves the application of a short-duration modification in alkali medium (5% KOH). Extensive characterizations were performed on the prepared membranes. Modification of the polymer altered the crystallinity of the PVDF from a mixture of both α and β phases to a predominant β phase. Lower work of adhesion of the modified membrane indicated the formation of a more hydrophobic and wetting-resistant membrane surface. Centrifugation of the polymer dope after the modification had a pronounced impact on the properties of the resultant membranes. This protocol could be utilized in fine-tuning the properties of PVDF membranes for various target-specific applications such as membrane distillation. This method can also be used in functionalizing PVDF membranes further by exploiting the labile –OH group present on the membrane surface.

  20. Temperature estimation from hydroxyl airglow emission in the Venus night side mesosphere (United States)

    Migliorini, A.; Snels, M.; Gérard, J.-C.; Soret, L.; Piccioni, G.; Drossart, P.


    The temperature of the night side of Venus at about 95 km has been determined by using spectral features of the hydroxyl airglow emission around 3 μm, recorded from July 2006 to July 2008 by VIRTIS onboard Venus Express. The retrieved temperatures vary from 145.5 to about 198.1 K with an average value of 176.3 ± 14.3 K and are in good agreement with previous ground-based and space observations. The variability with respect to latitude and local time has been studied, showing a minimum of temperature at equatorial latitudes, while temperature values increase toward mid latitudes with a local maximum at about 35°N. The present work provides an independent contribution to the temperature estimation in the transition region between the Venus upper mesosphere and the lower thermosphere, by using the OH emission as a thermometer, following the technique previously applied to the high-resolution O2(a1Δg) airglow emissions observed from ground.

  1. Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue (United States)

    Lerch, R.N.; Thurman, E.M.; Kruger, E.L.


    This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

  2. Mechanisms of electron transfer from structrual Fe(II) in reduced nontronite to oxygen for production of hydroxyl radicals (United States)

    Yuan, Songhu; Liu, Xixiang; Liao, Wenjuan; Zhang, Peng; Wang, Xiaoming; Tong, Man


    Production of hydroxyl radicals (radOH) has been recently revealed upon oxygenation of sediments in redox-dynamic subsurface environments. In particular, Fe(II)-bearing clay minerals are the major sediment components contributing to radOH production upon oxygenation, and the produced radOH can oxidize contaminants and inactivate bacteria. Whereas, the mechanisms of radOH production from oxygenation of Fe(II)-bearing clay minerals remain elusive. The objectives of this study were to identify the structural variation of Fe(II) entities during the oxidation of Fe(II)-bearing clay minerals by O2, and to unravel the mechanisms of electron transfer within the mineral structure and from mineral to O2 for radOH production. Nontronite (NAu-2, 23% Fe) which was chemically reduced to 54.5% Fe(II) in total Fe was used as a model Fe(II)-bearing clay mineral. Production of radOH and oxidation of Fe(II) were measured during the oxidation of reduced NAu-2 by O2. A wide spectrum of spectroscopic techniques, including Fourier transform infrared spectroscopy (FTIR), Fe K-edge X-ray absorption spectroscopy (XAS), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS), were employed to explore the structural variation of Fe(II) entities in NAu-2 and the electron transfer within NAu-2 and from NAu-2 to O2. For 180 min oxidation of 1 g/L reduced NAu-2, a biphasic radOH production was observed, being quick within the initial 15 min and slow afterwards. Production of radOH correlates well with oxidation of Fe(II) in the reduced NAu-2. Within the initial 15 min, trioctahedral Fe(II)-Fe(II)-Fe(II) entities and edge Fe(II) in the reduced NAu-2 were preferentially and quickly oxidized, and electrons from the interior Fe(II)-Fe(II)-Fe(II) entities were most likely ejected from the basal siloxane plane to O2. Meanwhile, trioctahedral Fe(II)-Fe(II)-Fe(II) entities were mainly transformed to dioctahedral Fe(II)-Fe(II) entities. When the time of oxygenation was longer than 15 min

  3. Role of the phenolic hydroxyl group in the biological activities of simplified analogue of aplysiatoxin with antiproliferative activity. (United States)

    Yanagita, Ryo C; Kamachi, Hiroaki; Tanaka, Keisuke; Murakami, Akira; Nakagawa, Yu; Tokuda, Harukuni; Nagai, Hiroshi; Irie, Kazuhiro


    The 18-deoxy derivative (3) of a simplified analogue (1) of aplysiatoxin with antiproliferative activity was synthesized to examine the role of the phenolic hydroxyl group at position 18 in the biological activities of 1. Compound 3 as well as 1 showed significant affinity for protein kinase Cδ (PKCδ), and the antiproliferative activity of 3 was slightly higher than that of 1. However, the anti-tumor-promoting activity of 3 was less than that of 1 in vitro, suggesting that the phenolic hydroxyl group of 1 is necessary for the anti-tumor-promoting activity but not for the binding of PKCδ and antiproliferative activity. Moreover, PKC isozyme selectivity of 3 was similar to that of 1, suggesting non-PKC receptors for these compounds to play some roles in the anti-tumor-promoting activity of 1. Copyright © 2010 Elsevier Ltd. All rights reserved.

  4. Grape skins (Vitis vinifera L.) catalyze the in vitro enzymatic hydroxylation of p-coumaric acid to caffeic acid

    DEFF Research Database (Denmark)

    Arnous, Anis; Meyer, Anne S.


    The ability of grape skins to catalyze in vitro conversion of p-coumaric acid to the more potent antioxidant caffeic acid was studied. Addition of different concentrations of p-coumaric to red grape skins (Cabernet Sauvignon) resulted in formation of caffeic acid. This caffeic acid formation (Y......) correlated positively and linearly to p-coumaric acid consumption (X): Y = 0.5 X + 9.5; R 2 = 0.96, P skin concentrations, indicated that the grape skins harboured an o......-hydroxylation activity, proposedly a monophenol- or a flavonoid 3′-monooxygenase activity (EC or EC The K m of this crude o-hydroxylation activity in the red grape skin was 0.5 mM with p-coumaric acid....

  5. Oxime ether lipids containing hydroxylated head groups are more superior siRNA delivery agents than their nonhydroxylated counterparts (United States)

    Gupta, Kshitij; Mattingly, Stephanie J; Knipp, Ralph J; Afonin, Kirill A; Viard, Mathias; Bergman, Joseph T; Stepler, Marissa; Nantz, Michael H; Puri, Anu; Shapiro, Bruce A


    Aim: To evaluate the structure–activity relationship of oxime ether lipids (OELs) containing modifications in the hydrophobic domains (chain length, degree of unsaturation) and hydrophilic head groups (polar domain hydroxyl groups) toward complex formation with siRNA molecules and siRNA delivery efficiency of resulting complexes to a human breast cancer cell line (MDA-MB-231). Materials & methods: Ability of lipoplex formation between oxime ether lipids with nucleic acids were examined using biophysical techniques. The potential of OELs to deliver nucleic acids and silence green fluorescent protein (GFP) gene was analyzed using MDA-MB-231 and MDA-MB-231/GFP cells, respectively. Results & conclusion: Introduction of hydroxyl groups to the polar domain of the OELs and unsaturation into the hydrophobic domain favor higher transfection and gene silencing in a cell culture system. PMID:26107486

  6. Synthesis of D- and L-apio nucleoside analogues with 2'-hydroxyl group as potential anti-HIV agents. (United States)

    Jin, Dong Zhe; Kwon, Sung Hee; Moon, Hyung Ryong; Gunaga, Prashantha; Kim, Hea Ok; Kim, Dae-Kee; Chun, Moon Woo; Jeong, Lak Shin


    The present work describes the asymmetric synthesis of D- and L-apio-2',3'-dideoxynucleoside analogues, 4 and 5 with 2'-hydroxyl group via a common intermediate 9, starting from D-galactose. Stereoselective dihydroxylation and deoxygenation through radical inversion were successfully employed to synthesize the key intermediate 12 with D-apio structure, while stereoselecetive hydroboration-oxidation was used for the synthesis of another key intermediate 18 with L-apio structure.

  7. The evaluation of hydroxyl ions as a nucleating agent for apatite on electrospun non-woven poly( ϵ -caprolactone) fabric. (United States)

    Kim, Hyung-Sup; Um, Seung-Hoon; Rhee, Sang-Hoon


    The capacity of hydroxyl ions when used as a nucleating agent to form apatite in simulated body fluid (SBF) was investigated. A 25 wt% poly(ϵ-caprolactone) solution was prepared using 1,1,3,3-hexafluoro-2-propanol as a solvent and was electrospun under an electric field of 1 kV/cm. Subsequently, non-woven poly(ϵ-caprolactone) fabrics were dipped into 4 M NaOH solution and the experimental group was then directly air-dried (NaOH coated), while the control group was washed with deionized water and air-dried (NaOH treated) under ambient conditions. The non-woven poly(ϵ-caprolactone) fabrics that were coated and treated with NaOH were exposed to SBF for 1 week, which resulted in the deposition of a layer of apatite crystals on the non-woven poly(ϵ-caprolactone) fabric coated with NaOH only. On the other hand, when the non-woven poly(ϵ-caprolactone) fabrics were dipped into 0.05, 0.1, 1 and 4 M NaOH solutions, respectively, air-dried, and then soaked in SBF, the apatite forming capacity was gradually increased according to the concentration of NaOH solution. These results were explained in terms of the degree of apatite supersaturation in SBF induced by the release of hydroxyl ions from the coated NaOH because hydroxyl ions are one of the constituent elements of apatite. These results suggest that hydroxyl ions have a good potential for use as a nucleating agent for apatite on a previously non-bioactive polymer surface.

  8. Photocatalytic activity of Pt-TiO2 films supported on hydroxylated fly ash cenospheres under visible light (United States)

    Wang, Bing; Yang, Zewei; An, Hao; Zhai, Jianping; Li, Qin; Cui, Hao


    TiO2 was coated on the surface of hydroxylated fly ash cenospheres (FACs) by the sol-gel method. Platinum (Pt) was then deposited on these TiO2/FAC particles by a photoreduction method to form PTF photocatalyst. The photocatalytic activity of PTF for the degradation of methylene blue (MB) under visible-light irradiation was determined. The PTF sample that was calcined at 450 °C and had a Pt/TiO2 mass ratio of 1.5% exhibited the optimal photocatalytic activity for degradation of MB with a catalyst concentration of 3 g L-1. MB was photodecomposed by PTF in aqueous solution more effectively at alkali pH than at acidic pH, because more MB molecules were adsorbed on the surface of PTF under alkaline conditions than that under acidic. The effect of various inorganic anions (HCO3-, F-, SO42-, NO3-, and Cl-) on the photodegradation of MB by PTF was also investigated. Addition of anions with a concentration of 5 mM enhanced the photocatalytic efficiency of PTF because of the improved adsorption of MB. This effect weakened as the anion concentration was increased, which was attributed to the ability of the anions to scavenge hydroxyl radicals and holes. Our results indicated that the photodegradation of MB took place mainly on the catalyst surface. The generation of hydroxyl radicals in the photocatalytic reaction was measured by the fluorescence method. KI was used to determine the participation of holes in the photocatalytic reaction. Both hydroxyl radicals and valence-band holes were detected in the PTF system. Recycling tests revealed that calcination of the used PTF helped to regain its photocatalytic activity.

  9. Validation of an extended method for the detection of the misuse of endogenous steroids in sports, including new hydroxylated metabolites. (United States)

    Van Renterghem, P; Van Eenoo, P; Van Thuyne, W; Geyer, H; Schänzer, W; Delbeke, F T


    Endogenous steroids are amongst the most misused doping agents in sports. Their presence poses a major challenge for doping control laboratories. Current threshold levels do not allow for the detection of all endogenous steroid misuse due to great interindividual variations in urinary steroid concentrations. A method has been developed and validated to screen for traditionally monitored endogenous steroids in doping control as well as specific hydroxylated/oxygenated metabolites in order to enhance the detection capabilities for the misuse of endogenous steroids.

  10. Combinatorial Alanine Substitution Enables Rapid Optimization of Cytochrome P450BM3 for Selective Hydroxylation of Large Substrates

    KAUST Repository

    Lewis, Jared C.


    Made for each other: Combinatorial alanine substitution of active site residues in a thermostable cytochrome P450BM3 variant was used to generate an enzyme that is active with large substrates. Selective hydroxylation of methoxymethylated monosaccharides, alkaloids, and steroids was thus made possible (see Scheme). This approach could be useful for improving the activity of enzymes that show only limited activity with larger substrates. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Molecular insights into the local anesthetic receptor within voltage-gated sodium channels using hydroxylated analogues of mexiletine

    Directory of Open Access Journals (Sweden)

    Jean-François eDesaphy


    Full Text Available We previously showed that the β-adrenoceptor modulators, clenbuterol and propranolol, directly blocked voltage-gated sodium channels, whereas salbutamol and nadolol did not (Desaphy et al., 2003, suggesting the presence of two hydroxyl groups on the aromatic moiety of the drugs as a molecular requisite for impeding sodium channel block. To verify such an hypothesis, we synthesized five new mexiletine analogues by adding one or two hydroxyl groups to the aryl moiety of the sodium channel blocker and tested these compounds on hNav1.4 channels expressed in HEK293 cells. Concentration-response relationships were constructed using an holding potential of -120 mV at 0.1 Hz (tonic block and 10 Hz (use-dependent block stimulation frequencies. The half-maximum inhibitory concentrations (IC50 were linearly correlated to drug lipophilicity: the less lipophilic the drug, minor was the block. The same compounds were also tested on F1586C and Y1593C hNav1.4 channel mutants, to gain further information on the molecular interactions of mexiletine with its receptor within the sodium channel pore. Alteration of tonic block suggests that the aryl moiety of mexiletine may interact either directly or indirectly with Phe1586 in the closed sodium channel to produce low-affinity binding block, and that this interaction depends on the electrostatic potential of the drug aromatic tail. Alteration of use-dependent block suggests that addition of hydroxyl groups to the aryl moiety may modify high-affinity binding of the drug ammine terminal to Phe1586 through cooperativity between the two pharmacophores, this effect being mainly related to drug lipophilicity. Mutation of Tyr1593 further impaired such cooperativity. In conclusion, these results confirm our former hypothesis showing that the presence of hydroxyl groups to the aryl moiety of mexiletine greatly reduced sodium channel block, and provide molecular insights into the intimate interaction of local anesthetics with

  12. Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters (United States)

    Kaur, R.; Anastasio, C.


    The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, photoformation rates and steady-state concentrations of two photooxidants - hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) - in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000-15,000 cm2 g-C-1 at 300 nm, and absorption extends to wavelengths as long as 450-600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h-1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10-15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M-1 s-1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M-1 s-1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1-3.0) × 10-13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and

  13. Formation and Retention of Hydroxyl and Water on the Lunar Surface (United States)

    Kramer, G. Y.; Clark, R. N.; Combe, J.; Noble, S. K.


    Spectral reflectance observations by the Moon Mineralogy Mapper (M3) showed that both hydroxyl and (molecular) water (hereafter referred to collectively as H/OH) vary spatially as a function of solar illumination geometry. At low solar incidence angles, the observed strengths of the H/OH spectral features are stronger than at higher angles, suggesting that the abundance varies with the diurnal cycle. This is also demonstrated in the increasing abundances with increasing latitude, such that above ~60 degrees there is little reduction in the depth of the water-related spectral absorption bands. It was immediately recognized that the wide-spread occurrence of H/OH across the lunar surface was the result of solar wind-induced hydroxylation, a phenomenon that was predicted almost 50 years ago. The lunar soil has a finite capacity to retain implanted hydrogen, and over time, the surface reaches a steady state, or background H/OH abundance, which is manifested in spectra of the mature soil. In addition to maturity, the retention of H/OH is a function of composition and texture (i.e., crystallinity and surface/volume). There are two hypotheses for how solar wind-implanted H/OH is retained in the soil: 1) H/OH adsorbs onto active surface sites on fresh soil particles. 2) H/OH is trapped in vesicles in agglutinates and amorphous coatings on soil grains created by space weathering. Undoubtedly both of these mechanisms occur, but one process is ultimately responsible for the observed steady state mature soil abundance, and this can be studied by measuring the strength of the H/OH spectral feature from soils as a function of variable composition, texture, and maturity. Space weathering is capable of both activating and neutralizing grain surfaces. Micrometeorite and larger impacts can activate mineral surfaces through mechanical forces, such as crushing and shattering of minerals, which creates fresh surfaces with partially unsatisfied chemical bonds. The freshly fractured

  14. Development and analytical application of a glucose biosensor based on glucose oxidase/O-(2-hydroxyl)propyl-3-trimethylammonium chitosan chloride nanoparticle-immobilized onion inner epidermis. (United States)

    Wang, Fei; Yao, Jun; Russel, Mohammad; Chen, Huilun; Chen, Ke; Zhou, Yong; Ceccanti, Brunello; Zaray, Gyula; Choi, Martin M F


    A glucose biosensor comprising a glucose oxidase/O-(2-hydroxyl)propyl-3-trimethylammonium chitosan chloride nanoparticle (O-HTCC NP)-immobilized onion inner membrane and a dissolved oxygen (O(2)) sensor has been successfully developed. The detection scheme is based on the depletion of dissolved O(2) content upon exposure to glucose. The decrease in O(2) level was monitored and related to the glucose concentration. The biosensor shows linear response to glucose from 0.0 to 0.60 mM with a detection limit of 50 microM (S/N=3). The effect of O-HTCC NP and enzyme loading, pH, temperature, and phosphate buffer concentration on the sensitivity of the biosensor was studied in detail. The biosensor exhibits fast response time (70s), good repeatability (3.2%, n=10) and storage stability (90% of initial sensitivity after 3-week storage). Common interferents including acetic acid, lactic acid, propionic acid, butyric acid, folic acid, methanol, glycine, DL-alpha-alanine and DL-cysteine do not cause significant interferences on the biosensor. The proposed biosensor method was successfully applied to determine the glucose content in real samples such as orange juice, red wine and tea drink and the results were comparable to that obtained from a spectrophotometric method. The glucose recovery test demonstrates that the proposed glucose biosensor offers an excellent, accurate and precise method for the determination of glucose in real samples. Copyright 2010 Elsevier B.V. All rights reserved.

  15. CYP703 is an ancient cytochrome P450 in land plants catalyzing in-chain hydroxylation of lauric acid to provide building blocks for sporopollenin synthesis in pollen. (United States)

    Morant, Marc; Jørgensen, Kirsten; Schaller, Hubert; Pinot, Franck; Møller, Birger Lindberg; Werck-Reichhart, Danièle; Bak, Søren


    CYP703 is a cytochrome P450 family specific to land plants. Typically, each plant species contains a single CYP703. Arabidopsis thaliana CYP703A2 is expressed in the anthers of developing flowers. Expression is initiated at the tetrad stage and restricted to microspores and to the tapetum cell layer. Arabidopsis CYP703A2 knockout lines showed impaired pollen development and a partial male-sterile phenotype. Scanning electron and transmission electron microscopy of pollen from the knockout plants showed impaired pollen wall development with absence of exine. The fluorescent layer around the pollen grains ascribed to the presence of phenylpropanoid units in sporopollenin was absent in the CYP703A2 knockout lines. Heterologous expression of CYP703A2 in yeast cells demonstrated that CYP703 catalyzes the conversion of medium-chain saturated fatty acids to the corresponding monohydroxylated fatty acids, with a preferential hydroxylation of lauric acid at the C-7 position. Incubation of recombinant CYP703 with methanol extracts from developing flowers confirmed that lauric acid and in-chain hydroxy lauric acids are the in planta substrate and product, respectively. These data demonstrate that in-chain hydroxy lauric acids are essential building blocks in sporopollenin synthesis and enable the formation of ester and ether linkages with phenylpropanoid units. This study identifies CYP703 as a P450 family specifically involved in pollen development.

  16. Insights into the O-Acetylation Reaction of Hydroxylated Heterocyclic Amines by Human Arylamine N-Acetyltransferases: A Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Lau, E Y; Felton, J S; Lightstone, F C


    A computational study was performed to better understand the differences between human arylamine N-acetyltransferase (NAT) 1 and 2. Homology models were constructed from available crystal structures and comparisons of the active site residues 125, 127, and 129 for these two enzymes provide insight into observed substrate differences. The NAT2 model provided a basis for understanding how some of the common mutations may affect the structure of the protein. Molecular dynamics simulations of the human NAT models and the template structure (NAT from Mycobacterium smegmatis) were performed and showed the models to be stable and reasonable. Docking studies of hydroxylated heterocyclic amines in the models of NAT1 and NAT2 probed the differences exhibited by these two proteins with mutagenic agents. The hydroxylated heterocyclic amines were only able to fit into the NAT2 active site, and an alternative binding site by the P-loop was found using our models and will be discussed. Additionally, quantum mechanical calculations were performed to study the O-acetylation reaction of the hydroxylated heterocyclic amines N-OH MeIQx and N-OH PhIP. This study has given us insight into why there are substrate differences among isoenzymes and explains some of the polymorphic activity differences.

  17. Quantum Mechanics/Molecular Mechanics Modeling of Drug Metabolism: Mexiletine N-Hydroxylation by Cytochrome P450 1A2. (United States)

    Lonsdale, Richard; Fort, Rachel M; Rydberg, Patrik; Harvey, Jeremy N; Mulholland, Adrian J


    The mechanism of cytochrome P450(CYP)-catalyzed hydroxylation of primary amines is currently unclear and is relevant to drug metabolism; previous small model calculations have suggested two possible mechanisms: direct N-oxidation and H-abstraction/rebound. We have modeled the N-hydroxylation of (R)-mexiletine in CYP1A2 with hybrid quantum mechanics/molecular mechanics (QM/MM) methods, providing a more detailed and realistic model. Multiple reaction barriers have been calculated at the QM(B3LYP-D)/MM(CHARMM27) level for the direct N-oxidation and H-abstraction/rebound mechanisms. Our calculated barriers indicate that the direct N-oxidation mechanism is preferred and proceeds via the doublet spin state of Compound I. Molecular dynamics simulations indicate that the presence of an ordered water molecule in the active site assists in the binding of mexiletine in the active site, but this is not a prerequisite for reaction via either mechanism. Several active site residues play a role in the binding of mexiletine in the active site, including Thr124 and Phe226. This work reveals key details of the N-hydroxylation of mexiletine and further demonstrates that mechanistic studies using QM/MM methods are useful for understanding drug metabolism.

  18. Fabrication and characterization of a novel hydrophobic CaCO{sub 3} grafted by hydroxylated poly(vinyl chloride) chains

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Lixia [State Key Laboratory of Polymer Materials Engineering, Sichuan University (China); School of Chemical Science and Technology, Yunnan University (China); Yang, Simei; Luo, Xin [School of Chemical Science and Technology, Yunnan University (China); Lei, Jingxin [State Key Laboratory of Polymer Materials Engineering, Sichuan University (China); Cao, Qiue [School of Chemical Science and Technology, Yunnan University (China); Wang, Jiliang, E-mail: [School of Chemical Science and Technology, Yunnan University (China)


    Highlights: • Hydroxylated poly(vinyl chloride) (PVC-OH) with different molecular weight and hydroxyl value was successfully prepared by the suspension copolymerization. • PVC-OH was grafted onto the surface of CaCO{sub 3} particles by the urethane formation reaction. • The modified CaCO{sub 3} particles show excellent hydrophobicity. - Abstract: The hydroxylated PVC (PVC-OH) was successfully synthesized by a suspension polymerization of vinyl chloride (VC), butyl acrylate (BA) and hydroxyethyl acrylate (HEA). Novel hydrophobic CaCO{sub 3} was then prepared by a urethane formation reaction between methylene diphenyl diisocyanate (MDI) and the −OH groups both in the PVC-OH chains and on the surface of pristine CaCO{sub 3} particles. The effect of the PVC-OH content on the grafting ratio of treated CaCO{sub 3} particles was extensively investigated. Combining the result of Fourier transform infrared (FTIR) with that of water contact angle, it can be concluded that the hydrophobicity of CaCO{sub 3} had been efficiently improved by the PVC-OH segments grafted on the surface of CaCO{sub 3} particles. X-ray diffraction (XRD), thermal gravity analysis (TGA), scanning electron microscope (SEM) and transmission electron microscope (TEM) were also used to study crystalline behaviors, thermal stability and surface morphology of the modified CaCO{sub 3} particles, respectively. The change of specific surface area implying surface modification was investigated as well.

  19. Arbutin, an intracellular hydroxyl radical scavenger, protects radiation-induced apoptosis in human lymphoma U937 cells. (United States)

    Wu, Li-Hua; Li, Peng; Zhao, Qing-Li; Piao, Jin-Lan; Jiao, Yu-Fei; Kadowaki, Makoto; Kondo, Takashi


    Ionizing radiation (IR) can generate reactive oxygen species (ROS). Excessive ROS have the potential to damage cellular macromolecules including DNA, proteins, and lipids and eventually lead to cell death. In this study, we evaluated the potential of arbutin, a drug chosen from a series of traditional herbal medicine by measuring intracellular hydroxyl radical scavenging ability in X-irradiated U937 cells. Arbutin (hydroquinone-β-D-glucopyranoside), a naturally occurring glucoside of hydroquinone, has been traditionally used to treat pigmentary disorders. However, there are no reports describing the effect of arbutin on IR-induced apoptosis. We confirmed that arbutin can protect cells from apoptosis induced by X-irradiation. The combination of arbutin and X-irradiation could reduce intracellular hydroxyl radical production and prevent mitochondrial membrane potential loss. It also could down-regulate the expression of phospho-JNK, phospho-p38 in whole cell lysate and activate Bax in mitochondria. Arbutin also inhibits cytochrome C release from mitochondria to cytosol. To verify the role of JNK in X-irradiation-induced apoptosis, the cells were pretreated with a JNK inhibitor, and found that JNK inhibitor could reduce apoptosis induced by X-irradiation. Taken together, our data indicate that arbutin plays an anti-apoptotic role via decreasing intracellular hydroxyl radical production, inhibition of Bax-mitochondria pathway and activation of the JNK/p38 MAPK pathway.

  20. Imidacloprid is hydroxylated by Laodelphax striatellus CYP6AY3v2. (United States)

    Wang, R; Zhu, Y; Deng, L; Zhang, H; Wang, Q; Yin, M; Song, P; Elzaki, M E A; Han, Z; Wu, M


    Laodelphax striatellus (Fallén) is one of the most destructive pests of rice, and has developed high resistance to imidacloprid. Our previous work indicated a strong association between imidacloprid resistance and the overexpression of a cytochrome P450 gene CYP6AY3v2 in a L. striatellus imidacloprid resistant strain (Imid-R). In this study, a transgenic Drosophila melanogaster line that overexpressed the L. striatellus CYP6AY3v2 gene was established and was found to confer increased levels of imidacloprid resistance. Furthermore, CYP6AY3v2 was co-expressed with D. melanogaster cytochrome P450 reductase (CPR) in Spodoptera frugiperda 9 (SF9) cells. A carbon monoxide difference spectra analysis indicated that CYP6AY3v2 was expressed predominately in its cytochrome P450 (P450) form, which is indicative of a good-quality functional enzyme. The recombinant CYP6AY3v2 protein efficiently catalysed the model substrate P-nitroanisole to p-nitrophenol with a maximum velocity (Vmax ) of 60.78 ± 3.93 optical density (mOD)/min/mg protein. In addition, imidacloprid itself was metabolized by the recombinant CYP6AY3v2/nicotinamide adenine dinucleotide 2'-phosphate reduced tetrasodium salt (NADPH) CPR microsomes in in vitro assays (catalytic constant (Kcat ) = 0.34 pmol/min/pmol P450, michaelis constant (Km ) = 41.98 μM), and imidacloprid depletion and metabolite peak formation were with a time dependence. The data provided direct evidence that CYP6AY3v2 is capable of hydroxylation of imidacloprid and conferring metabolic resistance in L. striatellus. © 2017 The Royal Entomological Society.

  1. Hydroxyl-containing antimony oxide bromide nanorods combined with chitosan for biosensors. (United States)

    Lu, Xianbo; Wen, Zhenhai; Li, Jinghong


    A hydroxyl-containing antimony oxide bromide (AOB) nanorods was synthesized by a hydrothermal method. TEM and SEM images showed that the as-prepared AOB nanorods were very copious with diameters of about 50 nm. The AOB nanorods could be easily combined with biopolymer chitosan (Chi) to form an organic-inorganic hybrid material, and a biocompatible, crack-free and porous Chi-AOB composite film could be readily obtained. Horseradish peroxidase (HRP) was chosen as a model protein to construct a reagentless mediator-free third-generation HRP biosensor. UV-visible and FTIR spectroscopy revealed that HRP entrapped in the composite film could retain its native secondary structure. A pair of stable and well-defined redox peaks of HRP with a formal potential of about -0.24 V (vs. Ag/AgCl) in a pH 7.0 phosphate-buffered solution (PBS) were obtained at the HRP-Chi-AOB composite film modified glassy carbon (GC) electrode. With advantages of organic-inorganic hybrid materials, dramatically facilitated direct electron transfer of HRP and excellent bioelectrocatalytic activity towards H(2)O(2) were demonstrated. The apparent Michaelis-Menten constant K(M)(app) was calculated to be 7.5mum, indicating that HRP entrapped in the composite film possessed high affinity to H(2)O(2) and exhibited high enzymatic activity. The prepared biosensor displayed good sensitivity and reproducibility, wide linear range, low detection limit, fast response and excellent long-term stability. The Chi-AOB composite film could be used efficiently for the entrapment of other redox-active proteins and may find wide potential applications in biosensors, biocatalysis, biomedical devices and bioelectronics.

  2. Quantitative structure-reactivity relationships of hydroxyl radical rate constants for linear and cyclic volatile methylsiloxanes. (United States)

    Kim, Jaeshin; Xu, Shihe


    An accurate understanding of the fate of volatile methylsiloxanes (VMS) in air is crucial for determining their persistence and concentrations in the environment. Although oxidation by atmospheric hydroxyl radicals (•OH) is considered as a major degradation mechanism for airborne VMS, the existing bimolecular rate constants with •OH measured and modeled for any given VMS compound varied greatly, depending on the approaches used to generate the data. The objectives of the present study were to measure •OH reaction rate constants for 4 cyclic and 4 linear VMS based on a relative rate method using a newly designed atmospheric chamber and to establish structure-reactivity relationships for the kinetics. In the past, the reaction rate constants for VMS were generally recognized to increase with the number of the methyl groups per molecule, the only differential factor in the existing models. However, the new measurements indicated that molecular structure should also be considered in the prediction of the reaction rates. Better empirical models were developed by simple and multiple linear regressions of the measured values from the present study and the literature. A high correlation existed for the reaction rates with the number of the methyl group attached at 2 distinct siloxane structures (i.e., linear and cyclic VMS). Even better correlations were obtained with one or 2 molecular descriptors that are directly related to the size of VMS, which, in turn, not only depend on the number of methyl groups, but the linear/cyclic structures as well for permethylsiloxanes. Environ Toxicol Chem 2017;9999:1-6. © 2017 SETAC. © 2017 SETAC.

  3. Human milk enhances antioxidant defenses against hydroxyl radical aggression in preterm infants. (United States)

    Ledo, Ana; Arduini, Alessandro; Asensi, Miguel A; Sastre, Juan; Escrig, Raquel; Brugada, María; Aguar, Marta; Saenz, Pilar; Vento, Maximo


    Preterm infants endowed with an immature antioxidant defense system are prone to oxidative stress. Hydroxyl radicals are very aggressive reactive oxygen species that lack specific antioxidants. These radicals cannot be measured directly, but oxidation byproducts of DNA or phenylalanine in urine are reliable markers of their activity. Human milk has a higher antioxidant capacity than formula. We hypothesized that oxidative stress associated with prematurity could be diminished by feeding human milk. We recruited a cohort of stable preterm infants who lacked perinatal conditions associated with oxidative stress; were not receiving prooxidant or antioxidant drugs, vitamins, or minerals before recruitment; and were fed exclusively human milk (HM group) or preterm formula (PTF group). Collected urine was analyzed for oxidative bases of DNA [8-hydroxy-2'-deoxyguanosine (8-oxodG)/2'-deoxyguanosine (2dG) ratio] and oxidative derivatives of phenylalanine [ortho-tyrosine (o-Tyr)/Phe ratio] by HPLC coupled to tandem mass spectrometry. Healthy term newborn infants served as control subjects. Both preterm groups eliminated greater amounts of metabolites than did the control group. However, the PTF group eliminated significantly (P group (8-oxodG/2dG ratio: 9.05 +/- 2.19) and significantly (P group (o-Tyr/Phe ratio: 12.53 +/- 3.49). When data were lumped together independently of the type of feeding received, a significant correlation was established between the 8-oxodG/2dG and o-Tyr/Phe ratios in urine, dependent on gestational age and birth weight. Prematurity is associated with protracted oxidative stress, and human milk is partially protective.

  4. Anticancer effect of linalool via cancer-specific hydroxyl radical generation in human colon cancer. (United States)

    Iwasaki, Kenichi; Zheng, Yun-Wen; Murata, Soichiro; Ito, Hiromu; Nakayama, Ken; Kurokawa, Tomohiro; Sano, Naoki; Nowatari, Takeshi; Villareal, Myra O; Nagano, Yumiko N; Isoda, Hiroko; Matsui, Hirofumi; Ohkohchi, Nobuhiro


    To investigate the anticancer mechanisms of the monoterpenoid alcohol linalool in human colon cancer cells. The cytotoxic effect of linalool on the human colon cancer cell lines and a human fibroblast cell line was examined using the WST-8 assay. The apoptosis-inducing effect of linalool was measured using the terminal deoxynucleotidyl transferase dUTP nick-end labeling assay and flow cytometry with Annexin V. Oxidative stress was investigated by staining for diphenyl-1-pyrenylphosphine, which is a cellular lipid peroxidation marker, and electron spin resonance spectroscopy. Sixteen SCID mice xenografted with human cancer cells were randomized into 3 groups for in vivo analysis: control and low-dose and high-dose linalool groups. The control group was administered tap water orally every 3 d. The linalool treatment groups were administered 100 or 200 μg/kg linalool solution orally for the same period. All mice were sacrificed under anesthesia 21 d after tumor inoculation, and tumors and organs were collected for immunohistochemistry using an anti-4-hydroxynonenal antibody. Tumor weights were measured and compared between groups. Linalool induced apoptosis of cancer cells in vitro, following the cancer-specific induction of oxidative stress, which was measured based on spontaneous hydroxyl radical production and delayed lipid peroxidation. Mice in the high-dose linalool group exhibited a 55% reduction in mean xenograft tumor weight compared with mice in the control group (P < 0.05). In addition, tumor-specific lipid peroxidation was observed in the in vivo model. Linalool exhibited an anticancer effect via cancer-specific oxidative stress, and this agent has potential for application in colon cancer therapy.

  5. Hydroxyl and Hydroperoxy Radical Chemistry during the MCMA-2006 Field Campaign: Measurement and Model Comparison (United States)

    Dusanter, S.; Vimal, D.; Stevens, P. S.; Volkamer, R.; Molina, L. T.


    The Mexico City Metropolitan Area (MCMA) field campaign, held in March 2006, was a unique opportunity to collect data in one of the most polluted megacities in the world. Such environments exhibit a complex oxidation chemistry involving a strong coupling between odd hydrogen radicals (HOX=OH+HO2) and nitrogen oxides species (NOX=NO+NO2). High levels of volatile organic compounds (VOCs) and NOX control the HOX budget and lead to elevated tropospheric ozone formation. The HOX-NOX coupling can be investigated by comparing measured and model-predicted HOx concentrations. Atmospheric HOX concentrations were measured by the Indiana University laser-induced fluorescence instrument and data were collected at the Instituto Mexicano del Petroleo between 14 and 31 March. Measured hydroxyl radical (OH) concentrations are comparable to that measured in less polluted urban environments and suggest that the OH concentrations are highly buffered under high NOX conditions. In contrast, hydroperoxy radical (HO2) concentrations are more sensitive to the NOX levels and are highly variable between different urban sites. Enhanced levels of OH and HO2 radicals were observed on several days between 9h30-11h00 AM and suggest an additional HOX source for the morning hours and/or a fast HOX cycling under the high NOX conditions of the MCMA. A preliminary investigation of the HOX chemistry occurring in the MCMA urban atmosphere was performed using a photochemical box model based on the Regional Atmospheric Chemistry Mechanism (RACM). Model comparisons will be presented and the agreement between measured and predicted HOX concentrations will be discussed.

  6. Improved Identification and Relative Quantification of Sites of Peptide and Protein Oxidation for Hydroxyl Radical Footprinting (United States)

    Li, Xiaoyan; Li, Zixuan; Xie, Boer; Sharp, Joshua S.


    Protein oxidation is typically associated with oxidative stress and aging and affects protein function in normal and pathological processes. Additionally, deliberate oxidative labeling is used to probe protein structure and protein-ligand interactions in hydroxyl radical protein footprinting (HRPF). Oxidation often occurs at multiple sites, leading to mixtures of oxidation isomers that differ only by the site of modification. We utilized sets of synthetic, isomeric "oxidized" peptides to test and compare the ability of electron-transfer dissociation (ETD) and collision-induced dissociation (CID), as well as nano-ultra high performance liquid chromatography (nanoUPLC) separation, to quantitate oxidation isomers with one oxidation at multiple adjacent sites in mixtures of peptides. Tandem mass spectrometry by ETD generates fragment ion ratios that accurately report on relative oxidative modification extent on specific sites, regardless of the charge state of the precursor ion. Conversely, CID was found to generate quantitative MS/MS product ions only at the higher precursor charge state. Oxidized isomers having multiple sites of oxidation in each of two peptide sequences in HRPF product of protein Robo-1 Ig1-2, a protein involved in nervous system axon guidance, were also identified and the oxidation extent at each residue was quantified by ETD without prior liquid chromatography (LC) separation. ETD has proven to be a reliable technique for simultaneous identification and relative quantification of a variety of functionally different oxidation isomers, and is a valuable tool for the study of oxidative stress, as well as for improving spatial resolution for HRPF studies.

  7. Sorption behavior of cesium, cobalt and europium radionuclides onto hydroxyl magnesium silicate

    Energy Technology Data Exchange (ETDEWEB)

    Hamed, Mostafa M.; Holiel, M.; Ahmed, I.M. [Atomic Energy Authority, Cairo (Egypt). Hot Laboratories and Waste Management Center


    The radioactive wastes from different activities have to be safely disposed of and isolated from the human environment. The retardation of radioactive materials by designed barriers is originally controlled by the sorption ability of the mineral compositions. In this work, a naturally available mineral composite, a hydroxyl magnesium silicate (HMS) was investigated as potential natural inorganic sorbent for the retention of long-lived radionuclides ({sup 134}Cs, {sup 60}Co and {sup 152+154}Eu) from aqueous solutions. The factors affecting the sorption process, such as contact time and pH were evaluated. Furthermore X-ray fluorescence (XRF), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), differential thermal and thermogravimetry analyses (DTA/TGA) measurements were examined in order to assess the physicochemical properties of the magnesium silicate mineral. Langmuir and Freundlich isotherms fitted the result s substantially better than the Flory-Huggins isotherm and the sorption was found to follow pseudo-first order kinetic model. The proposed mineral has been successfully applied for the sorption of {sup 134}Cs, {sup 60}Co and {sup 152+154}Eu radionuclides from real radioactive waste. The results indicated that about 97.4-99% of {sup 134}Cs, {sup 60}Co and {sup 152+154}Eu radionuclides were efficiently retained onto the HMS mineral. Based on the results obtained, it can be concluded that the HMS mineral is an economic and efficient retaining material for environmental hazardous migration and/or leakage of some radionuclides such as {sup 134}Cs, {sup 60}Co and {sup 152+154}Eu and trivalent actinide ({sup 241}Am, {sup 242m}Am and {sup 243}Am) ions. Therefore, this study could be used as a starting point to establish and consider that mineral as an engineered barrier around the disposal facilities at the nuclear activity centres.

  8. Hydroxylated and methoxylated polybrominated diphenyl ethers in mollusks from Chinese coastal areas. (United States)

    Sun, Jianteng; Liu, Jiyan; Liu, Yanwei; Jiang, Guibin


    Hydroxylated polybrominated diphenyl ethers (OH-PBDEs), methoxylated PBDEs (MeO-PBDEs) and PBDEs were determined in three mollusk species collected from three Chinese coastal regions in 2007, 2009, 2010 and 2011. The dominant MeO- and OH-PBDEs isomers detected in mollusks were 6-MeO-BDE-47, 2'-MeO-BDE-68, 6-OH-BDE-47 and 2'-OH-BDE-68. Concentrations of ΣMeO-PBDEs ranged from 9.20 to 2090pgg(-1) dry weight (mean: 450pgg(-1) dry weight). Concentrations of ΣOH-PBDEs ranged from 118 to 2540pgg(-1) dry weight (mean: 534pgg(-1) dry weight). Species differences in accumulation were found for the three mollusk species. Spatial distribution showed that OH- and MeO-PBDEs levels were higher in Weihai than in Tianjin. The temporal trends of OH- and MeO-PBDEs in mollusks were studied during period of 2007 to 2011, rising of ΣOH-PBDEs in Rap from Penglai and Ost from Weihai and declining of ΣMeO-PBDEs in Ost in Penglai were observed. Significant correlations were found between OH- and MeO-PBDEs, but neither between PBDEs and OH-PBDEs, nor between PBDEs and MeO-PBDEs, suggesting that OH- and MeO-PBDEs may have a common source or similar accumulation behavior in mollusks. OH- and MeO-PBDEs were likely not to originate from PBDE precursors. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Enhanced lignin monomer production caused by cinnamic Acid and its hydroxylated derivatives inhibits soybean root growth.

    Directory of Open Access Journals (Sweden)

    Rogério Barbosa Lima

    Full Text Available Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H, guaiacyl (G and syringyl (S monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway in a growth chamber for 24 h. In general, the results showed that 1 cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2 cinnamic and p-coumaric acids increased p-hydroxyphenyl (H monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G content, and sinapic acid increased sinapyl (S content; 3 when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H, cinnamic acid reduced H, G and S contents; and 4 when applied in conjunction with 3,4-(methylenedioxycinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL, p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth.

  10. Reaction mechanism of sterol hydroxylation by steroid C25 dehydrogenase - Homology model, reactivity and isoenzymatic diversity. (United States)

    Rugor, Agnieszka; Wójcik-Augustyn, Anna; Niedzialkowska, Ewa; Mordalski, Stefan; Staroń, Jakub; Bojarski, Andrzej; Szaleniec, Maciej


    Steroid C25 dehydrogenase (S25DH) is a molybdenum-containing oxidoreductase isolated from the anaerobic Sterolibacterium denitrificans Chol-1S. S25DH is classified as 'EBDH-like' enzyme (EBDH, ethylbenzene dehydrogenase) and catalyzes the introduction of an OH group to the C25 atom of a sterol aliphatic side-chain. Due to its regioselectivity, S25DH is proposed as a catalyst in production of pharmaceuticals: calcifediol or 25-hydroxycholesterol. The aim of presented research was to obtain structural model of catalytic subunit α and investigate the reaction mechanism of the O2-independent tertiary carbon atom activation. Based on homology modeling and theoretical calculations, a S25DH α subunit model was for the first time characterized and compared to other S25DH-like isoforms. The molecular dynamics simulations of the enzyme-substrate complexes revealed two stable binding modes of a substrate, which are stabilized predominantly by van der Waals forces in the hydrophobic substrate channel. However, H-bond interactions involving polar residues with C3=O/C3-OH in the steroid ring appear to be responsible for positioning the substrate. These results may explain the experimental kinetic results which showed that 3-ketosterols are hydroxylated 5-10-fold faster than 3-hydroxysterols. The reaction mechanism was studied using QM:MM and QM-only cluster models. The postulated mechanism involves homolytic CH cleavage by the MoO ligand, giving rise to a radical intermediate with product obtained in an OH rebound process. The hypothesis was supported by kinetic isotopic effect (KIE) experiments involving 25,26,26,26-[2H]-cholesterol (4.5) and the theoretically predicted intrinsic KIE (7.0-7.2). Finally, we have demonstrated that the recombinant S25DH-like isoform catalyzes the same reaction as S25DH. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Aging of secondary organic aerosol from α-pinene ozonolysis: Roles of hydroxyl and nitrate radicals. (United States)

    Qi, Li; Nakao, Shunsuke; Cocker, David R


    This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from α-pinene ozonolysis (∼100 ppbv hydrocarbon [HCx] with excess of O3) within the University of California-Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO3) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H2O2 (UV on), and N2O5 (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO3 reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H2O2, or N2O5 is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO3 radicals can further alter the chemical composition of SOA from α-pinene ozonolysis, which is proved to consist of first-generation products. [Box: see text].

  12. Antioxidant, prooxidant and cytotoxic activity of hydroxylated resveratrol analogues: structure-activity relationship. (United States)

    Murias, Marek; Jäger, Walter; Handler, Norbert; Erker, Thomas; Horvath, Zsuzsanna; Szekeres, Thomas; Nohl, Hans; Gille, Lars


    Resveratrol (trans-3,4',5-trihydroxystilbene), a naturally occurring hydroxystilbene, is considered an essential antioxidative constituent of red wine possessing chemopreventive properties. However, resveratrol and even more its metabolite piceatannol were reported to have also cytostatic activities. In order to find out whether this is related to antioxidative properties of those compounds, we synthesized five other polyhydroxylated resveratrol analogues and studied structure-activity relationships between pro-/antioxidant properties and cytotoxicity. Radical scavenging experiments with O(2)(*-) (5,5-dimethyl-1-pyrroline-N-oxide/electron spin resonance (DMPO/ESR)) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) (photometry) revealed that 3,3',4',5-tetrahydroxystilbene (IC(50): 2.69microM; k(9): 443000M(-1)s(-1)), 3,4,4',5-tetrahydroxystilbene (IC(50): 41.5microM; k(9): 882000M(-1)s(-1)) and 3,3',4,4',5,5'-hexahydroxystilbene (IC(50): 5.02microM), exerted a more than 6600-fold higher antiradical activity than resveratrol and its two other analogues. Furthermore, in HL-60 leukemic cells hydroxystilbenes with ortho-hydroxyl groups exhibited a more than three-fold higher cytostatic activity compared to hydroxystilbenes with other substitution patterns. Oxidation of ortho-hydroxystilbenes in a microsomal model system resulted in the existence of ortho-semiquinones, which were observed by ESR spectroscopy. Further experiments revealed that these intermediates undergo redox-cycling thereby consuming additional oxygen and forming cytotoxic oxygen radicals. In contrast to compounds with other substitution patterns hydroxystilbenes with one or two resorcinol groups (compounds 1 and 3) did not show an additional oxygen consumption or semiquinone formation. These findings suggest that the increased cytotoxicity of ortho-hydroxystilbenes is related to the presence of ortho-semiquinones formed during metabolism or autoxidation.

  13. A Novel High-Throughput Approach to Measure Hydroxyl Radicals Induced by Airborne Particulate Matter

    Directory of Open Access Journals (Sweden)

    Yeongkwon Son


    Full Text Available Oxidative stress is one of the key mechanisms linking ambient particulate matter (PM exposure with various adverse health effects. The oxidative potential of PM has been used to characterize the ability of PM induced oxidative stress. Hydroxyl radical (•OH is the most destructive radical produced by PM. However, there is currently no high-throughput approach which can rapidly measure PM-induced •OH for a large number of samples with an automated system. This study evaluated four existing molecular probes (disodium terephthalate, 3′-p-(aminophenylfluorescein, coumarin-3-carboxylic acid, and sodium benzoate for their applicability to measure •OH induced by PM in a high-throughput cell-free system using fluorescence techniques, based on both our experiments and on an assessment of the physicochemical properties of the probes reported in the literature. Disodium terephthalate (TPT was the most applicable molecular probe to measure •OH induced by PM, due to its high solubility, high stability of the corresponding fluorescent product (i.e., 2-hydroxyterephthalic acid, high yield compared with the other molecular probes, and stable fluorescence intensity in a wide range of pH environments. TPT was applied in a high-throughput format to measure PM (NIST 1648a-induced •OH, in phosphate buffered saline. The formed fluorescent product was measured at designated time points up to 2 h. The fluorescent product of TPT had a detection limit of 17.59 nM. The soluble fraction of PM contributed approximately 76.9% of the •OH induced by total PM, and the soluble metal ions of PM contributed 57.4% of the overall •OH formation. This study provides a promising cost-effective high-throughput method to measure •OH induced by PM on a routine basis.

  14. PBDEs, hydroxylated PBDEs and methoxylated PBDEs in bivalves from Beijing markets. (United States)

    Liu, Xitao; Jiao, Ying; Lin, Chunye; Sun, Ke; Zhao, Ye


    The structural analogues of polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have been attracting increasing concern in recent years. Five bivalve species (blue mussel, short-necked clam, surf clam, ark shell and razor clam) were collected from Beijing markets, and the concentrations of seven PBDEs, four OH-PBDEs and fourteen MeO-PBDEs in the bivalves were measured. The seasonal variations of these three types of polybrominated compound in blue mussels were also monitored. The results indicate that the levels of ΣPBDEs in this study were comparable to those in short-necked clams from Liaodong Bay, China, with BDE47 as the dominant congener. For the ortho-MeO-PBDEs, 6-MeO-BDE47 was found at higher concentrations than the others, while for the meta- and para-MeO-PBDEs, 4'-MeO-BDE17 was found at higher concentrations. 6-OH-BDE-47 was the most abundant congener among the 4 measured OH-PBDEs, followed by 6-OH-BDE-137 and 6-OH-BDE-85. The levels of OH-PBDEs and MeO-PBDEs in bivalves from Beijing markets were much lower than the corresponding compounds in blue mussels from the Baltic Sea. In the blue mussels collected in April, June and September of 2012, apparent seasonal variations were observed for these three types of polybrominated compounds, but the acidic components displayed different trends from the neutral components, with PBDEs and MeO-PBDEs showing the highest concentrations in June, while OH-PBDEs had the lowest concentrations in June. This difference in seasonal variations between the neutral components and the acidic components may be explained by their different sources and transformation/elimination mechanisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Antimicrobial activity of hydroxyl radicals generated by hydrogen peroxide photolysis against Streptococcus mutans biofilm. (United States)

    Nakamura, Keisuke; Shirato, Midori; Kanno, Taro; Örtengren, Ulf; Lingström, Peter; Niwano, Yoshimi


    Prevention of dental caries with maximum conservation of intact tooth substance remains a challenge in dentistry. The present study aimed to evaluate the antimicrobial effect of H2O2 photolysis on Streptococcus mutans biofilm, which may be a novel antimicrobial chemotherapy for treating caries. S. mutans biofilm was grown on disk-shaped hydroxyapatite specimens. After 1-24 h of incubation, growth was assessed by confocal laser scanning microscopy and viable bacterial counting. Resistance to antibiotics (amoxicillin and erythromycin) was evaluated by comparing bactericidal effects on the biofilm with those on planktonic bacteria. To evaluate the effect of the antimicrobial technique, the biofilm was immersed in 3% H2O2 and was irradiated with an LED at 365 nm for 1 min. Viable bacterial counts in the biofilm were determined by colony counting. The thickness and surface coverage of S. mutans biofilm increased with time, whereas viable bacterial counts plateaued after 6 h. When 12- and 24-h-old biofilms were treated with the minimum concentration of antibiotics that killed viable planktonic bacteria with 3 log reduction, their viable counts were not significantly decreased, suggesting the biofilm acquired antibiotic resistance by increasing its thickness. By contrast, hydroxyl radicals generated by photolysis of 3% H2O2 effectively killed S. mutans in 24-h-old biofilm, with greater than 5 log reduction. The technique based on H2O2 photolysis is a potentially powerful adjunctive antimicrobial chemotherapy for caries treatment. Copyright © 2016 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

  16. Importance of iron complexation for Fenton-mediated hydroxyl radical production at circumneutral pH

    Directory of Open Access Journals (Sweden)

    Christopher J. Miller


    Full Text Available The reaction between Fe(II and H2O2 to yield hydroxyl radicals (HO•, the Fenton reaction, is of interest due to its role in trace metal and natural organic matter biogeochemistry, its utility in water treatment and its role in oxidative cell degradation and associated human disease. There is significant dispute over whether HO•, the most reactive of the so-called reactive oxygen species, is formed in this reaction, particularly under circumneutral conditions relevant to natural systems. In this work we have studied the oxidation kinetics of Fe(II complexed by L = citrate, ethylenediaminetetraacetic acid (EDTA and diethylenetriaminepentaacetic acid (DTPA and also measured HO• production using phthalhydrazide as a probe compound at pH 8.2. It is shown that HO• is the sole product of the Fe(IIL-H2O2 reaction for L = EDTA and DTPA, with kinetic modelling of the full reaction pathway utilized to confirm this finding. Quantitative HO• production also appears likely for L = citrate, although uncertainties with the speciation of Fe(II-citrate complexes as well as difficulties in modelling the oxidation kinetics of these complexes has prevented a definitive conclusion. In the absence of ligands at circumneutral pH, inorganic Fe(II reacts with H2O2 to yield a species other than HO•, contrary to the well-established production of HO• from inorganic Fe(II at low pH. Our results suggest that at high pH Fe(II must be complexed for HO• production to occur.

  17. Transformation pathways and acute toxicity variation of 4-hydroxyl benzophenone in chlorination disinfection process. (United States)

    Liu, Wei; Wei, Dongbin; Liu, Qi; Du, Yuguo


    Benzophenones compounds (BPs) are widely used as UV filters, and have been frequently found in multiple environmental matrices. The residual of BPs in water would cause potential threats on ecological safety and human health. Chlorination disinfection is necessary in water treatment process, in which many chemicals remained in water would react with disinfectant chlorine and form toxic by-products. By using ultra performance liquid phase chromatography quadrupole time of flight mass spectrometer (UPLC-QTOF-MS), nuclear magnetic resonance (NMR), the transformation of 4-hydroxyl benezophenone (4HB) with free available chlorine (FAC) was characterized. Eight major products were detected and seven of them were identified. Transformation pathways of 4HB under acid, neutral, and alkaline conditions were proposed respectively. The transformation mechanisms involved electrophilic chlorine substitution of 4HB, Baeyer-Villiger oxidation of ketones, hydrolysis of esters and oxidative breakage of benzene ring. The orthogonal experiments of pH and dosages of disinfectant chlorine were conducted. The results suggested that pH conditions determined the occurrence of reaction types, and the dosages of disinfectant chlorine affected the extent of reactions. Photobacterium assay demonstrated that acute toxicity had significant increase after chlorination disinfection of 4HB. It was proved that 3,5-dichloro-4HB, one of the major transformation products, was responsible for the increasing acute toxicity after chlorination. It is notable that, 4HB at low level in real ambient water matrices could be transformed during simulated chlorination disinfection practice. Especially, two major products 3-chloro-4HB and 3,5-dichloro-4HB were detected out, implying the potential ecological risk after chlorination disinfection of 4HB. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Novel aromatic ring-hydroxylating dioxygenase genes from coastal marine sediments of Patagonia

    Directory of Open Access Journals (Sweden)

    Ferrero Marcela A


    Full Text Available Abstract Background Polycyclic aromatic hydrocarbons (PAHs, widespread pollutants in the marine environment, can produce adverse effects in marine organisms and can be transferred to humans through seafood. Our knowledge of PAH-degrading bacterial populations in the marine environment is still very limited, and mainly originates from studies of cultured bacteria. In this work, genes coding catabolic enzymes from PAH-biodegradation pathways were characterized in coastal sediments of Patagonia with different levels of PAH contamination. Results Genes encoding for the catalytic alpha subunit of aromatic ring-hydroxylating dioxygenases (ARHDs were amplified from intertidal sediment samples using two different primer sets. Products were cloned and screened by restriction fragment length polymorphism analysis. Clones representing each restriction pattern were selected in each library for sequencing. A total of 500 clones were screened in 9 gene libraries, and 193 clones were sequenced. Libraries contained one to five different ARHD gene types, and this number was correlated with the number of PAHs found in the samples above the quantification limit (r = 0.834, p nahAc-like genes, phnAc-like genes as identified in Alcaligenes faecalis AFK2, and phnA1-like genes from marine PAH-degraders from the genus Cycloclasticus. Conclusion These results show the presence of hitherto unidentified ARHD genes in this sub-Antarctic marine environment exposed to anthropogenic contamination. This information can be used to study the geographical distribution and ecological significance of bacterial populations carrying these genes, and to design molecular assays to monitor the progress and effectiveness of remediation technologies.

  19. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren


    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  20. Rate laws and kinetic modeling of N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE) transformation by hydroxyl radical in aqueous solution. (United States)

    Nguyen, Tung Viet; Reinhard, Martin; Gin, Karina Yew-Hoong


    The degradation of perfluorochemicals (PFCs) by hydroxyl radical ((·)OH) follows complex pathways resulting in stable products. Kinetic models are needed to predict the product distribution of (·)OH-initiated PFC degradation under environmental and treatment conditions. The bimolecular rate constants were measured in water for the reaction of (·)OH and N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE), and intermediates, N-ethyl perfluorooctane sulfonamidoacetate (N-EtFOSAA), N-ethyl perfluorooctane sulfonamide (N-EtFOSA) and perfluorooctane sulfonamidoacetate (FOSAA). Under standard conditions (pH = 6, 25 ± 2 °C, Co PFC = 5-10 μg L(-1), Co H2O2 = 10 mM, irradiation intensity = 765 W m(-2)), the measured constants for N-EtFOSE, N-EtFOSAA, N-EtFOSA and FOSAA were (1.05 ± 0.12) × 10(9) M(-1) s(-1), (0.68 ± 0.05) × 10(9) M(-1) s(-1), (0.68 ± 0.05) × 10(9) M(-1) s(-1) and (0.53 ± 0.05) × 10(9) M(-1) s(-1), respectively. Constants in the pH range from 1 to 10 varied within a factor of 2-4 for most compounds. Over a period of 2-days, N-EtFOSE reacted directly (without forming long-lived intermediates) to perfluorooctane sulfonamide (FOSA) (18.8%) and perfluorooctanoic acid (PFOA) (39.1%). N-EtFOSE reacted via oxidation of the ethanolic hydroxyl group to N-EtFOSAA (12.4%) and N-dealkylation to N-EtFOSA (13.3%) and FOSAA (0.2%) and unknown intermediates. In sunlit surface waters, the (·)OH-induced transformation of N-substituted sulfonamide compounds to photostable products occurs on a time scale of days to weeks by model prediction. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Insights into the mechanism of the reaction between tetrachloro-p-benzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial. (United States)

    Li, Ping; Wang, Weihua; Sun, Qiao; Li, Zhen; Du, Aijun; Bi, Siwei; Zhao, Yan


    Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Inhibition of growth of microcultured Hancornia speciosa shoots by 3beta-hydroxylated gibberellins and one of their C-3 deoxy precursors. (United States)

    Pereira-Netto, A B; McCown, B H; Pharis, R P


    Gibberellins (GAs) A(1), A(3), A(4) and A(7), all 3beta-hydroxylated, growth-active GAs, significantly inhibited shoot elongation and the formation of nodes in in vitro-grown Hancornia speciosa, as did GA(20), a 3-deoxy precursor of GA(1). Ancymidol, an early-stage inhibitor of GA biosynthesis, significantly retarded shoot elongation without affecting the formation of nodes. Co-application of ancymidol and GA(1 )did not overcome the ancymidol-induced growth retardation. Trinexapac-ethyl, which can inhibit 3beta-hydroxylation (GA activation) and 2beta-hydroxylation (GA inactivation), gave no significant response on either shoot elongation or node formation, while two isomers of 16,17-dihydro GA(5), also inhibitors of GA 3beta-hydroxylation, significantly inhibited both shoot growth and the formation of nodes. These unusual results may indicate a unique metabolism for GAs in microcultured shoots of H. speciosa.

  3. Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution

    National Research Council Canada - National Science Library

    Peng Liu; Qiong Wang; Meixing Niu; Dunyou Wang


    Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution...

  4. Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: Influence of alkyl-chain length. (United States)

    Gao, Yanpeng; Ji, Yuemeng; Li, Guiying; An, Taicheng


    As emerging organic contaminants (EOCs), the ubiquitous presence of preservative parabens in water causes a serious environmental concern. Hydroxyl radical ((•)OH) is a strong oxidant that can degrade EOCs through photochemistry in surface water environments as well as in advanced oxidation processes (AOPs). To better understand the degradation mechanisms, kinetics, and products toxicity of the preservative parabens in aquatic environments and AOPs, the (•)OH-initiated degradation reactions of the four parabens were investigated systematically using a computational approach. The four studied parabens with increase of alkyl-chain length were methylparaben (MPB), ethylparaben (EPB), propylparaben (PPB), and dibutylparaben (BPB). Results showed that the four parabens can be initially attacked by (•)OH through (•)OH-addition and H-abstraction routes. The (•)OH-addition route was more important for the degradation of shorter alkyl-chain parabens like MPB and EPB, while the H-abstraction route was predominant for the degradation of parabens with longer alkyl-chain for example PPB and BPB. In assessing the aquatic toxicity of parabens and their degradation products using the model calculations, the products of the (•)OH-addition route were found to be more toxic to green algae than original parabens. Although all degradation products were less toxic to daphnia and fish than corresponding parental parabens, they could be still harmful to these aquatic organisms. Furthermore, as alkyl-chain length increased, the ecotoxicity of parabens and their degradation products was found to be also increased. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Hydroxyl radical recycling in isoprene oxidation driven by hydrogen bonding and hydrogen tunneling: the upgraded LIM1 mechanism. (United States)

    Peeters, Jozef; Müller, Jean-François; Stavrakou, Trissevgeni; Nguyen, Vinh Son


    The Leuven isoprene mechanism, proposed earlier to aid in rationalizing the unexpectedly high hydroxyl radical (OH) concentrations in isoprene-rich, low-nitric-oxide (NO) regions ( Peeters ; et al. Phys. Chem. Chem. Phys . 2009 , 11 , 5935 ), is presented in an upgraded and extended version, LIM1. The kinetics of the crucial reactions in the proposed isoprene-peroxy radical interconversion and isomerization pathways are re-evaluated theoretically, on the basis of energy barriers computed at the much higher CCSD(T)/aug-cc-pVTZ//QCISD/6-311G(d,p) level of theory, and using multiconformer partition functions obtained at the M06-2X/6-311++G(3df,2p) level that, different from the B3LYP level used in our earlier work, accounts for the crucial London dispersion effects in the H-bonded systems involved. The steady-state fraction of the specific Z-δ-OH-peroxy radical isomers/conformers that can isomerize by a 1,6-H shift is shown to be largely governed by hydrogen-bond strengths, whereas their isomerization itself is found to occur quasi-exclusively by hydrogen atom tunneling. The isomer-specific Z-δ-OH-peroxy 1,6-H-shift rate coefficients are predicted to be of the order of 1 s(-1) at 298 K, but the experimentally accessible bulk rate coefficients, which have to be clearly distinguished from the former, are 2 orders of magnitude lower due to the very low Z-δ-OH-peroxy steady-state fractions that are only around or below 0.01 at low to moderate NO and depend on the peroxy lifetime. Two pathways subsequent to the peroxy radical 1,6-H shift are identified, the earlier predicted route yielding the photolabile hydroperoxy-methylbutenals (HPALDs), and a second, about equally important path, to dihydroperoxy-carbonyl peroxy radicals (di-HPCARP). Taking this into account, our predicted bulk peroxy isomerization rate coefficients are about a factor 1.8 higher than the available experimental results for HPALD production ( Crounse ; et al. Phys. Chem. Chem. Phys. 2011 , 13 , 13607

  6. Hydroxyl layer: trend of number density and intra-annual variability

    Directory of Open Access Journals (Sweden)

    G. R. Sonnemann


    Full Text Available The layer of vibrationally excited hydroxyl (OH* near the mesopause in Earth's atmosphere is widely used to derive the temperature at this height and to observe dynamical processes such as gravity waves. The concentration of OH* is controlled by the product of atomic hydrogen, with ozone creating a layer of enhanced concentration in the mesopause region. However, the basic influences on the OH* layer are atomic oxygen and temperature. The long-term monitoring of this layer provides information on a changing atmosphere. It is important to know which proportion of a trend results from anthropogenic impacts on the atmosphere and which proportion reflects natural variations. In a previous paper (Grygalashvyly et al., 2014, the trend of the height of the layer and the trend in temperature were investigated particularly in midlatitudes on the basis of our coupled dynamic and chemical transport model LIMA (Leibniz Institute Middle Atmosphere. In this paper we consider the trend for the number density between the years 1961 and 2009 and analyze the reason of the trends on a global scale. Further, we consider intra-annual variations. Temperature and wind have the strongest impacts on the trend. Surprisingly, the increase in greenhouse gases (GHGs has no clear influence on the chemistry of OH*. The main reason for this lies in the fact that, in the production term of OH*, if atomic hydrogen increases due to increasing humidity of the middle atmosphere by methane oxidation, ozone decreases. The maximum of the OH* layer is found in the mesopause region and is very variable. The mesopause region is a very intricate domain marked by changeable dynamics and strong gradients of all chemically active minor constituents determining the OH* chemistry. The OH* concentration responds, in part, very sensitively to small changes in these parameters. The cause for this behavior is given by nonlinear reactions of the photochemical system being a nonlinear enforced

  7. Vascular leakage induced by exposure to arsenic via increased production of NO, hydroxyl radical and peroxynitrite. (United States)

    Chen, Shih-Chieh; Chen, Wei-Chi


    Previous studies have shown that in situ exposure to arsenic induced increased vascular leakage. However, the underlying mechanism remains unclear. Reactive nitrogen and oxygen species such as nitric oxide (NO) and hydroxyl radical (OH(-)) are known to affect vascular permeability. Therefore, the goal of our present studies is to investigate the functional impact of the generation of NO or OH(-) on arsenic-induced vascular leakage. Vascular permeability changes were evaluated by means of Evans blue (EB) assay. Rats were anesthetized and intravenously injected with EB. Permeability changes were induced in back skin by intradermal injections of sodium arsenite mixed with NOS inhibitor: N(omega)-Nitro-L-arginine methyl ester (L-NAME) or aminoguanidine (AG) and OH(-) scavenger: 1,3 Dimethyl-2 thiourea (DMTU). Experiments were also performed to determine whether DMTU mixed with L-NAME would further inhibit arsenic-induced vascular leakage as compared with attenuation effects by either DMTU or L-NAME. One hour after administration, EB accumulated in the skin was extracted and quantified. Both L-NAME (0.02, 0.1 and 0.5 micromol/site) and DMTU (0.05, 0.2 and 1.2 micromol/site) inhibited the increase in vascular leakage induced by arsenite. However, only high dose (1 micromol/site) of AG significantly attenuated arsenite-induced vascular leakage. In contrast, neither D-NAME (0.02, 0.1 and 0.5 micromol/site) nor AG (0.04 and 0.2 micromol/site) attenuated increased vascular leakage by arsenic. DMTU mixed with L-NAME caused no further inhibition of arsenic-induced vascular leakage by either DMTU or L-NAME. The techniques of India ink and immunostaining were used to demonstrate both vascular labeling and nitrotyrosine staining in tissue treated with arsenic. L-NAME apparently reduced the density of leaky vessels and the levels of peroxynitrite staining induced by arsenite. These results suggest that NO, OH(-) and peroxynitrite play a role in increased vascular permeability

  8. Hydroxyl-Containing Aromatic Polyimides for Carbon Dioxide Removal from Natural Gas

    KAUST Repository

    Alaslai, Nasser Y.


    Natural gas is among the most dominant resources to provide energy supplies and Saudi Arabia ranks among the top 5 producers worldwide. However, prior to use of methane, natural gas has to be treated to remove other feed gas components, such as H2O, CO2, H2S, N2 and C2+ hydrocarbons. Most NG fields in KSA contain about 10 mol% carbon dioxide that has to be reduced to less than 2 mol% for pipeline delivery. The conventional unit operations for natural gas separations, that is, molecular sieves, amine absorption, cryogenic distillation, and turbo expansion exhibit some disadvantages in terms of economics, operational flexibility or system footprint. One of the most attractive alternative is membrane technology in either standalone- or hybrid system configuration. Currently, the only two membrane materials used in industrial natural gas applications are cellulose acetate and polyimide, which have moderate permeability and fairly low selectivity when tested under realistic industrial conditions. The goal for future research is to develop unique polymeric membranes, which can at least partially replace conventional gas processing in future natural gas projects. This will support global economics and specifically the economy of Saudi Arabia. Newly developed polymeric materials must meet certain criteria to be used on a commercial scale. These criteria include: (i) high permeability and selectivity, (ii) processability into thin films, (iii) mechanical and thermal stability, and (iv) chemical stability against feed gas components. This project focused on the removal of carbon dioxide from natural gas by developing and characterizing functionalized aromatic polyimide membrane materials that exhibit very high selectivity under aggressive mixed-gas conditions. 6FDA-DAR demonstrated a mixed-gas CO2/CH4 selectivity of 78 at a CO2 partial pressure of 10 bar with no pronounced indication of plasticization. Combining hydroxyl- and carboxyl groups in a miscible polyimide blend led

  9. Sources of Nitrous Acid, Formaldehyde, and Hydroxyl Radical in Doha, Qatar. (United States)

    Ackermann, Luis; Rappenglueck, Bernhard; Ayoub, Mohammed


    One of the most important species in the atmosphere is the hydroxyl radical (OH), due to its role controlling the oxidizing capacity of an air shed. The main formation processes of OH include the photolysis of ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), and the ozonolysis of alkenes. Still, the sources of HONO in the atmosphere are not sufficiently well known, with indications that heterogeneous reactions on surfaces may contribute to the observed concentrations. The city of Doha in Qatar presents a unique opportunity to explore photochemical processes including the effects of high particulates concentrations under extreme weather conditions (high temperatures and humidity) and complex emission sources. Two Intensive Observational Periods (IOP) were conducted in Doha in 2016, one during the winter and the other during the summer. These consisted of meteorological measurements, ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), nitrogen monoxide (NO), direct nitrogen dioxide (NO2), sulfur dioxide (SO2), carbon monoxide (CO), as well as particulate matter with an aerodynamic diameter ≤ 10 μm and 2.5 μm (PM10 and PM2.5). In addition photolysis rates of HONO, HCHO, NO2, and singlet oxygen (O1D) were measured. The photostationary state concentration of OH was calculated from its known sources and sinks. The maximum hourly average concentration of OH was determined to be around 1.1 ppt for summer and 0.5 ppt for winter IOP. For the 24-hr average, the photolysis of HONO was the main precursor for OH production with 54.3 % and 72.7 % (summer and winter IOP), while the photolysis of O3 was responsible for 23.8 % and 19.7 % and the photolysis of HCHO accounted for 21.9 % and 7.6 % (summer and winter IOP, respectively). In this study we present source apportionment analysis for the radical precursors HONO and HCHO during the winter and summer IOP and its diurnal variation and elucidate their impact on OH production. We also infer NOx vs VOC limitation of O3

  10. Hydroxyl radical-scavenging property of secoisolariciresinol diglucoside (SDG) isolated from flax-seed. (United States)

    Prasad, K


    Recently there has been a moderate resurgence in the use of flax-seed in a variety of ways including bread. The scientific basis of its use is very limited. There is some claim for beneficial effects in cancer and lupus nephritis. These claims could be due to its ability to scavenge oxygen radicals. However, its antioxidant activity is not known. Recently a method has been developed to isolate secoisolariciresinol diglucoside (SDG) from defatted flax-seed in large quantity (patent pending). We investigated the ability of SDG to scavenge .OH using high pressure liquid chromatography (HPLC) method. .OH was generated by photolysis of H2O2 (1.25-10.0 mumoles/ml) with ultraviolet light and was trapped with salicylic acid which is hydroxylated to produce .OH-adduct products 2,3-dihydroxybenzoic acid (DHBA) and 2,5-DHBA. H2O2 produced a concentration-dependent .OH as estimated by 2,3-DHBA and 2,5-DHBA. A standard curve was constructed for known concentrations of 2,3-DHBA and 2,5-DHBA against corresponding area under the peaks which then was used for measurement of 2,3-DHBA and 2,5-DHBA generated by UV irradiation of H2O2 in the presence of salicylic acid. SDG in the concentration range of 25, 50, 100, 250, 500, 750, 1000 and 2000 micrograms/ml (36.4, 72.8, 145.6, 364.0, 728.0, 1092.0, 1456.0 and 2912.0 microM respectively) produced a concentration-dependent decrease in the formation of 2,3-DHBA and 2,5-DHBA, the inhibition being 4 and 4.65% respectively with 25 micrograms/ml (36.4 microM) and 82 and 74% respectively with 2000 micrograms/ml (2912.0 microM). The decrease in .OH-adduct products was due to scavenging of .OH and not by scavenging of formed 2,3-DHBA and 2,5-DHBA. SDG prevented the lipid peroxidation of liver homogenate in a concentration-dependent manner in the concentration range from 319.3-2554.4 microM. These results suggest that SDG scavenges .OH and therefore has an antioxidant activity.

  11. Aflatoxins, hydroxylated metabolites, and aflatoxicol from breast muscle of laying hens. (United States)

    Díaz-Zaragoza, M; Carvajal-Moreno, M; Méndez-Ramírez, I; Chilpa-Galván, N C; Avila-González, E; Flores-Ortiz, C M


    Aflatoxins (AF) are toxic fungal secondary metabolites that are pathological to animals and humans. This study identified and quantified AF (AFB(1), AFB(2), AFG(1), AFG(2)) and their hydroxylated metabolites (AFM(1), AFM(2), AFP(1)) and aflatoxicol (AFL) from laying hen breast muscles. Aflatoxins pass from cereal feed to the laying hen tissues, causing economic losses, and from there to humans. To detect the passage of AF from feed to hen breast muscle tissues, an experiment that included 25 Hy-Line W36 121-wk-old hens was performed for 8 d. Hens in individual cages were distributed into 3 groups: a control group, with feed free of AFB(1), and 2 experimental groups, with feed spiked with 2 AFB(1) dosages: 30 µg·kg(-1) (low) or 500 µg·kg(-1) (high). The daily feed consumption per hen was recorded and afterward hens were euthanized and breast muscles were collected, weighed, and dried individually. Aflatoxins were extracted by 2 chemical methods and quantified by HPLC. Both methods were validated by lineality (calibration curves), recovery percentage (>80%), limit of detection, and limit of quantification. The AF (µg·kg(-1)) averages recovered in control breast muscles were as follows: AFB(1) (18); AFG(1), AFM(2), and AFL (0); AFG(2) (1.3); AFM(1) (52), and AFP1 (79). Hens fed with feed spiked with 30 µg·kg(-1) of AFB(1) had AFG(1) (16); AFG(2) (72); AFM(1) (0); AFM(2) (18); AFP(1) (145); and AFL (5 µg·kg(-1)). Hens with feed spiked with 500 µg·kg(-1) of AFB(1) had AFG(1) (512); AFG(2) (7); AFM(1) (4,775); AFM(2) (0); AFP(1) (661); and AFL (21 µg·kg(-1)). The best AF extraction method was Qian and Yang's method, modified by adding additional AF from both Supelclean LC18 SPE columns; its limit of detection (0.5 ng·mL(-1)) was lower compared with that of Koeltzow and Tanner, which was 1 ng·mL(-1). ©2014 Poultry Science Association Inc.

  12. Calcitriol/calcifediol ratio: An indicator of vitamin D hydroxylation efficiency? (United States)

    Pasquali, Marzia; Tartaglione, Lida; Rotondi, Silverio; Muci, Maria Luisa; Mandanici, Giusi; Farcomeni, Alessio; Marangella, Martino; Mazzaferro, Sandro


    Calcifediol (25D) availability is crucial for calcitriol (1,25D) synthesis, but regulation of vitamin D hydroxylases is majorly responsible for 1,25D synthesis. The net efficiency of vitamin D hydroxylases might be informative. We assume that the ratio between calcitriol and calcifediol (25D/1,25D) serum concentrations could suggest the vitamin D hydroxylation efficiency. We evaluated 25D/1,25D in different patient populations: hemodialysis (HD, n = 76), CKD stage 2-5 (n = 111), renal transplant (TX, n = 135), patients with no renal disease (No-CKD, n = 290), and primary hyperparathyroidism (PHP, n = 20). The geometric mean of 1,25D/25D (pg/ng) averaged 1.11 (HD), 1.36 (CKD), 1.77 (TX), 2.22 (No-CKD), and 4.11 (PHP), with a progressive increment from HD to PHP (p-value for the trend indicated levels of Cas, Ps, PTH, and 25D as predictors of 25D/1,25D. Both in vitamin D deficient and replete subjects (25Dtrend <0.0001). Regression analysis between 25D (substrate) and 25D/1,25D (efficiency) revealed an exponential negative correlation in No-CKD (r(2)Exp = 0.53, p < 0.001) with sharp increments of 25D/1,25D when 25D values are <20 ng/ml. At variance, in CKD (r(2)lin = 0.19) and in TX (r(2)lin = 0.32) the regression was linear as if, in case of deficit, some inhibition of the system were operating. In conclusion 1,25D/25D can reflect the efficiency of vitamin D hydroxylases more than separate evaluation of 25D and 1,25D and can facilitate the therapeutic choices in different patient populations.

  13. Effect of rb-bFGF eye drops and hydroxyl indican eye drops on tear film stability and dry eye symptoms after age-related cataract surgery

    Directory of Open Access Journals (Sweden)

    Jing Chen


    Full Text Available AIM: To compare and analyze the effect of recombinant bovine basic fibroblast growth factor(bFGFeye drops and hydroxyl indican eye drops on the tear film stability and dry eye symptoms after age-related cataract surgery. METHODS: A total of 115 patients(115 affected eyeswith dry eyes after age-related cataract surgery were divided into the bFGF group, the hydroxyl indican group and the blank control group by the random number table method. The blank control group was only given routine anti-inflammatory treatment, and on the basis, the bFGF group and the hydroxyl indican group were treated with bFGF eye drops and hydroxyl indican eye drops respectively. The clinical efficacy, adverse reactions, changes in scores of dry eye symptoms, Schirmer test(SⅠt, tear film break-up time(BUTand corneal fluorescein staining(CFSscores at different time points were compared among the three groups. RESULTS: The total markedly effective rates in the bFGF group(89.5%was higher than that in the hydroxyl indican group(70.3%or the blank control group(47.5%(PPPCONCLUSION: The tear film is unstable in early stage after age-related cataract surgery, and there are dry eye symptoms. The intervention with bFGF eye drops and hydroxyl indican eye drops can effectively restore the tear film stability and significantly relieve dry eye symptoms, and the effect of bFGF eye drops is more significant.

  14. Efficacy of puffer fish (Takifugu rubripes) sauce in reducing hydroxyl radical damage to DNA assessed using the apurinic/apyrimidinic site method. (United States)

    Harada, Kazuki; Makino, Yoshio; Yamauchi, Tomio; Fukuda, Nami; Tamaru, Miki; Okubo, Yasue; Maeda, Toshimichi; Fukuda, Yutaka; Shiba, Tsuneo


    Apurinic/apyrimidinic (AP) sites are frequently observed DNA lesions when cells are exposed to hydroxyl radicals. We developed a new method for measurement of the antioxidative activity of foods using the occurrence frequency of AP sites on DNA. Combined with the electron spin resonance (ESR) method as a standard method, we examined whether fish and soy sauces including puffer fish [Takifugu rubripes (Temminck et Schlegel)] sauce could protect DNA from damage caused by hydroxyl radicals. The results showed that the ratios of DNA protection by puffer fish sauce, salmon fish sauce, sandfish fish sauce (Shottsuru), colorless soy sauce, squid fish sauce (Ishiru), dark color soy sauce and light color soy sauce were 68.9, 67.0, 60.1, 49.7, 34.1, 28.2 and -4.4%, respectively. Puffer, salmon, and sandfish fish sauces showed high ratios of DNA protection against hydroxyl radicals. On the other hand, IC(50) values of hydroxyl radical scavenging of the puffer, salmon, sandfish, squid fish sauces and colorless, dark and light color soy sauces were 0.20, 0.09, 4.16, 0.26% and 0.28, 0.14 and 0.18%, respectively. Though the puffer fish sauce exhibited the highest level of DNA protection among the examined samples and a high hydroxyl radical scavenging capability, a correlation between the radical scavenging capability and DNA protection against hydroxyl radicals among the examined fish and soy sauces was not found.

  15. The B-ring hydroxylation pattern of intermediates of anthocyanin synthesis in pelargonidin-and cyanidin-producing lines of Matthiola incana. (United States)

    Forkmann, G


    In flowers of Matthiola incana, the B-ring hydroxylation pattern of anthocyanins is controlled by the locus b. Recessive genotypes produce pelargonidin and genotypes with wild-type alleles cyanidin as the aglycone. Supplementation experiments on acyanic flowers using extracts of pelargonidin-and cyanidin-producing flowers, respectively, showed not only the presence of compounds with a precursor function for anthocyanin synthesis in the cyanic flowers but also differences in the B-ring hydroxylation pattern of these compounds. Chromatographic investigations proved that flavanones and dihydroflavonols occur in extracts of cyanic flowers. Naringenin, dihydrokaempferol, and their 7-glucosides could be demonstrated in all flower extracts, but in extracts of cyanidin-producing flowers, dihydroquercetin and a further 3', 4'-hydroxylated dihydroflavonol, tentatively identified as dihydroquercetin 3-glycoside, were additionally found. In no case, however, could eriodictyol be detected. From these results and from the ready hydroxylation of dihydrokaempferol to dihydroquercetin in a white mutant line of Matthiola incana, it can be concluded that introduction of the 3'-hydroxyl group of anthocyanins is not achieved by specific incorporation of caffeic acid during synthesis of the flavonoid skeleton, but by hydroxylation at the dihydroflavonol stage.

  16. Initialized Fractional Calculus (United States)

    Lorenzo, Carl F.; Hartley, Tom T.


    This paper demonstrates the need for a nonconstant initialization for the fractional calculus and establishes a basic definition set for the initialized fractional differintegral. This definition set allows the formalization of an initialized fractional calculus. Two basis calculi are considered; the Riemann-Liouville and the Grunwald fractional calculi. Two forms of initialization, terminal and side are developed.

  17. Cytochrome P450 125 (CYP125) catalyses C26-hydroxylation to initiate sterol side-chain degradation in Rhodococcus jostii RHA1

    NARCIS (Netherlands)

    Rosloniec, Kamila Z.; Wilbrink, Maarten H.; Capyk, Jenna K.; Mohn, William W.; Ostendorf, Martin; van der Geize, Robert; Dijkhuizen, Lubbert; Eltis, Lindsay D.; Rosłoniec, Kamila Z.


    P>The cyp125 gene of Rhodococcus jostii RHA1 was previously found to be highly upregulated during growth on cholesterol and the orthologue in Mycobacterium tuberculosis (rv3545c) has been implicated in pathogenesis. Here we show that cyp125 is essential for R. jostii RHA1 to grow on 3-hydroxysterols

  18. Mechanism of DNA cleavage by cationic manganese porphyrins: hydroxylations at the 1'-carbon and 5'-carbon atoms of deoxyriboses as initial damages

    National Research Council Canada - National Science Library

    Pratviel, G; Pitié, M; Bernadou, J; Meunier, B


    Cationic manganese-porphyrin complexes, free or targetted with an intercalating agent, are able to cleave DNA using oxygen atom donors like potassium monopersulfate or magnesium monoperphthalate as coreactants...

  19. Extended ischemia prevents HIF1alpha degradation at reoxygenation by impairing prolyl-hydroxylation: role of Krebs cycle metabolites. (United States)

    Serra-Pérez, Anna; Planas, Anna M; Núñez-O'Mara, Analía; Berra, Edurne; García-Villoria, Judit; Ribes, Antònia; Santalucía, Tomàs


    Hypoxia-inducible factor (HIF) is a heterodimeric transcription factor that activates the cellular response to hypoxia. The HIF1alpha subunit is constantly synthesized and degraded under normoxia, but degradation is rapidly inhibited when oxygen levels drop. Oxygen-dependent hydroxylation by prolyl-4-hydroxylases (PHD) mediates HIF1alpha proteasome degradation. Brain ischemia limits the availability not only of oxygen but also of glucose. We hypothesized that this circumstance could have a modulating effect on HIF. We assessed the separate involvement of oxygen and glucose in HIF1alpha regulation in differentiated neuroblastoma cells subjected to ischemia. We report higher transcriptional activity and HIF1alpha expression under oxygen deprivation in the presence of glucose (OD), than in its absence (oxygen and glucose deprivation, OGD). Unexpectedly, HIF1alpha was not degraded at reoxygenation after an episode of OGD. This was not due to impairment of proteasome function, but was associated with lower HIF1alpha hydroxylation. Krebs cycle metabolites fumarate and succinate are known inhibitors of PHD, while alpha-ketoglutarate is a co-substrate of the reaction. Lack of HIF1alpha degradation in the presence of oxygen was accompanied by a very low alpha-ketoglutarate/fumarate ratio. Furthermore, treatment with a fumarate analogue prevented HIF1alpha degradation under normoxia. In all, our data suggest that postischemic metabolic alterations in Krebs cycle metabolites impair HIF1alpha degradation in the presence of oxygen by decreasing its hydroxylation, and highlight the involvement of metabolic pathways in HIF1alpha regulation besides the well known effects of oxygen.

  20. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies. (United States)

    Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa


    Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.