WorldWideScience

Sample records for aryl boronic acids

  1. A convenient catalyst system for microwave accelerated cross-coupling of a range of aryl boronic acids with aryl chlorides

    Directory of Open Access Journals (Sweden)

    Milton Edward J

    2007-05-01

    Full Text Available Abstract A convenient microwave accelerated cross-coupling procedure between aryl chlorides with a range of boronic acids has been developed. An explanation for the low reactivity of highly fluorinated boronic acids in Suzuki coupling is provided.

  2. Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature.

    Science.gov (United States)

    Liu, Wenbo; Yang, Xiaobo; Gao, Yang; Li, Chao-Jun

    2017-06-28

    Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.

  3. Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

    2013-01-01

    A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

  4. Interaction of model aryl- and alkyl-boronic acids and 1,2-diols in aqueous solution.

    Science.gov (United States)

    Marinaro, William A; Prankerd, Richard; Kinnari, Kaisa; Stella, Valentino J

    2015-04-01

    The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  5. Diols and anions can control the formation of an exciplex between a pyridinium boronic acid with an aryl group connected via a propylene linker.

    Science.gov (United States)

    Huang, Yan-Jun; Jiang, Yun-Bao; Bull, Steven D; Fossey, John S; James, Tony D

    2010-11-21

    The exciplex formation between a pyridinium boronic acid and phenyl group connected via a propylene linker can be monitored using fluorescence. Addition of pinacol affords a cyclic boronate ester with enhanced Lewis acidity that increases the strength of its cation-π stacking interaction causing a four-fold fluorescence enhancement.

  6. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...... no effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  7. Fine-tuning the nucleophilic reactivities of boron ate complexes derived from aryl and heteroaryl boronic esters.

    Science.gov (United States)

    Berionni, Guillaume; Leonov, Artem I; Mayer, Peter; Ofial, Armin R; Mayr, Herbert

    2015-02-23

    Boron ate complexes derived from thienyl and furyl boronic esters and aryllithium compounds have been isolated and characterized by X-ray crystallography. Products and mechanisms of their reactions with carbenium and iminium ions have been analyzed. Kinetics of these reactions were monitored by UV/Vis spectroscopy, and the influence of the aryl substituents, the diol ligands (pinacol, ethylene glycol, neopentyl glycol, catechol), and the counterions on the nucleophilic reactivity of the boron ate complexes were examined. A Hammett correlation confirmed the polar nature of their reactions with benzhydrylium ions, and the correlation lg k(20 °C)=sN (E+N) was employed to determine the nucleophilicities of the boron ate complexes and to compare them with those of other borates and boronates. The neopentyl and ethylene glycol derivatives were found to be 10(4) times more reactive than the pinacol and catechol derivatives. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. N-Benzylhydroxylamine addition to beta-aryl enoates. Enantioselective synthesis of beta-aryl-beta-amino acid precursors

    Science.gov (United States)

    Sibi; Liu

    2000-10-19

    Chiral Lewis acid catalyzed N-benzylhydroxylamine addition to pyrrolidinone-derived enoates afforded beta-aryl-beta-amino acid derivatives in high enantiomeric purity with moderate to very good chemical efficiency.

  9. Chemoselective N-arylation of aminobenzamides via copper catalysed Chan-Evans-Lam reactions.

    Science.gov (United States)

    Liu, Shuai; Zu, Weisai; Zhang, Jinli; Xu, Liang

    2017-11-15

    Chemoselective N-arylation of unprotected aminobenzamides was achieved via Cu-catalysed Chan-Evans-Lam cross-coupling with aryl boronic acids for the first time. Simple copper catalysts enable the selective arylation of amino groups in ortho/meta/para-aminobenzamides under open-flask conditions. The reactions were scalable and compatible with a wide range of functional groups.

  10. Menthone aryl acid hydrazones: a new class of anticonvulsants.

    Science.gov (United States)

    Jain, Jainendra; Kumar, Y; Sinha, Reema; Kumar, Rajeev; Stables, James

    2011-01-01

    A series of ten compounds (Compounds J(1)-J(10)) of (±) 3-menthone aryl acid hydrazone was synthesized and characterized by thin layer chromatography and spectral analysis. Synthesized compounds were evaluated for anticonvulsant activity after intraperitoneal (i.p) administration to mice by maximal electroshock (MES) and subcutaneous pentylenetetrazole (scPTZ) induced seizure method and minimal clonic seizure test. Minimal motor impairment was also determined for these compounds. Results obtained showed that four compounds out of ten afforded significant protection in the minimal clonic seizure screen at 6 Hz. Compound J(6), 4-Chloro-N-(2-isopropyl-5-methylcyclohexylidene) benzohydrazide was found to be the most active compound with MES ED(50) of 16.1 mg/kg and protective index (pI) of greater than 20, indicating that (±) 3-menthone aryl acid hydrazone possesses better and safer anticonvulsant properties than other reported menthone derivatives viz. menthone Schiff bases, menthone semicarbazides and thiosemicarbazides.

  11. Synthesis and Suzuki Cross-Coupling Reactions of 2,6-Bis(trifluoromethyl)pyridine-4-boronic Acid Pinacol Ester

    KAUST Repository

    Batool, Farhat

    2016-11-18

    Iridium-catalyzed aromatic borylation provides quick one-step access to 2,6-bis(trifluoromethyl)pyridine-4-boronic acid pinacol ester. Suzuki couplings of this highly electron-deficient pyridine-4-boronic ester with various (hetero)aryl bromides was successfully carried out and the coupled products were obtained in 46–95% isolated yields. Double and triple Suzuki couplings, with dibromo- and tribromoarenes, respectively, were also achieved. Thus demonstrating that this pyridine-4-boronic ester can be a useful source for the installation of one of the strongest electron-withdrawing aromatic group in organic compounds. Copyright © 2016, Georg Thieme Verlag. All rights reserved.

  12. Synthesis and Suzuki Cross-Coupling Reactions of 2,6-Bis(trifluoromethyl)pyridine-4-boronic Acid Pinacol Ester

    KAUST Repository

    Batool, Farhat; Emwas, Abdul-Hamid M.; Gao, Xin; Munawar, Munawar A.; Chotana, Ghayoor A.

    2016-01-01

    Iridium-catalyzed aromatic borylation provides quick one-step access to 2,6-bis(trifluoromethyl)pyridine-4-boronic acid pinacol ester. Suzuki couplings of this highly electron-deficient pyridine-4-boronic ester with various (hetero)aryl bromides was successfully carried out and the coupled products were obtained in 46–95% isolated yields. Double and triple Suzuki couplings, with dibromo- and tribromoarenes, respectively, were also achieved. Thus demonstrating that this pyridine-4-boronic ester can be a useful source for the installation of one of the strongest electron-withdrawing aromatic group in organic compounds. Copyright © 2016, Georg Thieme Verlag. All rights reserved.

  13. Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

    Science.gov (United States)

    Crossley, Daniel L; Cid, Jessica; Curless, Liam D; Turner, Michael L; Ingleson, Michael J

    2015-12-28

    The addition of AlCl 3 to four-coordinate boranes of the general formula (C-N-chelate)BCl 2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl] + . The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl 3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl 2 . Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

  14. Design and synthesis of aryl ether and sulfone hydroxamic acids as potent histone deacetylase (HDAC) inhibitors.

    Science.gov (United States)

    Pabba, Chittari; Gregg, Brian T; Kitchen, Douglas B; Chen, Zhen Jia; Judkins, Angela

    2011-01-01

    A series of novel hydroxamic acid based histone deacetylases (HDAC) inhibitors with aryl ether and aryl sulfone residues at the terminus of a substituted, unsaturated 5-carbon spacer moiety have been synthesized for the first time and evaluated. Compounds with meta- and para-substitution on the aryl ring of ether hydroxamic acids 19c, 20c, 19e, 19f and 19g are potent HDAC inhibitors with activities at low nanomolar levels. Copyright © 2010 Elsevier Ltd. All rights reserved.

  15. Palladium-catalysed arylation of acetoacetate esters to yield 2-arylacetic acid esters

    CSIR Research Space (South Africa)

    Zeevaart, JG

    2004-05-24

    Full Text Available , was developed simultaneously by Hart- wig and Buchwald.5 Typically the tert-butyl ester of propionic acid is treated with an aryl halide (bromide or chloride) in the presence of a strong base, palladium and a bulky phosphine ligand or a bulky imidazolinium CO2t... novel palladium- catalysed conditions for the arylation of acetoacetate esters resulting in the formation of 2-arylacetic acid esters. When we attempted the arylation of tert-butyl aceto- acetate 1a with bromobenzene 2a using mild reaction conditions (K3...

  16. Induction of the p75NTR by Aryl Propionic Acids in Prostate Cancer Cells

    National Research Council Canada - National Science Library

    Quann, Emily

    2007-01-01

    .... I have found that treatment of prostate cancer cells with the aryl propionic acids R-flurbiprofen and ibuprofen induces reexpression of p75NTR, decreases cell survival, and increases apoptosis...

  17. New applications of the interaction between diols and boronic acids

    NARCIS (Netherlands)

    Duval, F.L.

    2015-01-01

    Florine Duval - New applications of the interaction between diols and boronic acids – Summary

    Chapter 1 introduces the theory and known applications of the interaction between boronic acids and diols, and explains the context of this thesis. Diagnosis of

  18. Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

    Science.gov (United States)

    Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto

    2014-05-16

    Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

  19. Boronic acids for fluorescence imaging of carbohydrates.

    Science.gov (United States)

    Sun, Xiaolong; Zhai, Wenlei; Fossey, John S; James, Tony D

    2016-02-28

    "Fluorescence imaging" is a particularly exciting and rapidly developing area of research; the annual number of publications in the area has increased ten-fold over the last decade. The rapid increase of interest in fluorescence imaging will necessitate the development of an increasing number of molecular receptors and binding agents in order to meet the demand in this rapidly expanding area. Carbohydrate biomarkers are particularly important targets for fluorescence imaging given their pivotal role in numerous important biological events, including the development and progression of many diseases. Therefore, the development of new fluorescent receptors and binding agents for carbohydrates is and will be increasing in demand. This review highlights the development of fluorescence imaging agents based on boronic acids a particularly promising class of receptors given their strong and selective binding with carbohydrates in aqueous media.

  20. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-01-01

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

  1. Boronic acid-based chemical sensors for saccharides.

    Science.gov (United States)

    Zhang, Xiao-Tai; Liu, Guang-Jian; Ning, Zhang-Wei; Xing, Guo-Wen

    2017-11-27

    During the past decades, the interaction between boronic acids-functionalized sensors and saccharides is of great interest in the frontier domain of the interdiscipline concerning both biology and chemistry. Various boronic acid-based sensing systems have been developed to detect saccharides and corresponding derivatives in vitro as well as in vivo, which embrace unimolecular sensors, two-component sensing ensembles, functional assemblies, and boronic acid-loaded nanomaterials or surfaces. New sensing strategies emerge in endlessly with excellent selectivity and sensitivity. In this review, several typical sensing systems were introduced and some promising examples were highlighted to enable the deep insight of saccharides sensing on the basis of boronic acids. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Boron complexing with H-resorcinol and acidic hydroxyxanthene dyes

    International Nuclear Information System (INIS)

    Nazarenko, V.A.; Flyantikova, G.V.; Chekirda, T.N.

    1984-01-01

    Complex formation of boron with H-resorcinol (hr; 2,4-dihydroxybenzene-azo -8-hydroxynaphtalene-3,6-disulfonic acid) and acidic hydroxyxanthene dyes (hxd: fluorescein, eosine, erathrosine). Mixed-ligand complexes with a ratio of r:hr:hxd=1:1:1 are formed at pH=5-6. The chemism of the complex formation of boron with H-resorcinol and fluorescein has been studied. The stability consta nt of the complex is 1.12x10 21 , the conditional molar absorptivitis 1.80x10 0 . This complex formation reaction was used for photometric determination of boron in natural water

  3. Spectrophotometric determination of boric acid in boron powder with curcumin

    International Nuclear Information System (INIS)

    Grotheer, E.W.

    1979-01-01

    A rapid and accurate method was needed to determine trace amounts of boric acid for quality control and specification testing of elemental boron. The reaction between boric acid and curcumin occurs at a measurable rate only when the curcumin molecule is protonated. Protonation takes place at the carbonyl groups in the presence of a strong acid and occurs completely and rapidly when sulfuric acid is added to a solution of curcumin in acetic acid. Spectrophotometric measurements were made. The extraction of boric acid from boron powder was found to be complete within 2h when either water or the diol solution was used. Whatman No. 40 cr 42 filter paper was used to obtain diol samples free of boron particles. The extraction efficiency of 2-ethyl-1,3-hexanediol was evaluated by adding 1 ml of 500 ppM aqueous boric acid and 1 drop of 10% NaOH to accurately weighed samples of boron powder. The water then was evaporated at room temperature and the samples were extracted with diol solution. The data obtained are included. The extraction efficiency also was evaluated by determining the boric acid content of boron which had been recovered from a previous extraction and boric acid determination. The determination of boric acid using curcumin is unaffected by the presence of other compounds, except for fluoride and nitrate ions. 2 tables

  4. Boronic species as promising inhibitors of the Staphylococcus aureus NorA efflux pump: study of 6-substituted pyridine-3-boronic acid derivatives.

    Science.gov (United States)

    Fontaine, Fanny; Héquet, Arnaud; Voisin-Chiret, Anne-Sophie; Bouillon, Alexandre; Lesnard, Aurélien; Cresteil, Thierry; Jolivalt, Claude; Rault, Sylvain

    2015-05-05

    In response to the extensive use of antibiotics, bacteria have evolved numerous mechanisms of defense against antimicrobial agents. Among them, extrusion of the antimicrobial agents outside the bacterial cell through efflux pumps is a major cause of concern. At first limited to one or few structurally-related antibiotics, bacterial resistance have then progressed towards cross-resistance between different classes of antibiotics, leading to multidrug-resistant microorganisms. Emergence of these pathogens requires development of novel therapeutic strategies and inhibition of efflux pumps appears to be a promising strategy that could restore the potency of existing antibiotics. NorA is the most studied chromosomal efflux pump of Staphylococcus aureus; it is known to be implied in resistance of Methicillin-resistant S. aureus (MRSA) strains against a wide range of unrelated substrates, including hydrophilic fluoroquinolones. Starting from 6-benzyloxypyridine-3-boronic acid I that we previously identified as a potential inhibitor of the NorA efflux pump against the NorA-overexpressing S. aureus 1199B strain (SA1199B), we describe here the synthesis and biological evaluation of a series of 6-(aryl)alkoxypyridine-3-boronic acids. 6-(3-Phenylpropoxy)pyridine-3-boronic acid 3i and 6-(4-phenylbutoxy)pyridine-3-boronic acid 3j were found to potentiate ciprofloxacin activity by a 4-fold increase compared to the parent compound I. In addition, it has been shown that both compounds promote Ethidium Bromide (EtBr) accumulation in SA1199B, thus corroborating their potential mode of action as NorA inhibitors. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  5. Microwave-assisted cyclizations promoted by polyphosphoric acid esters: a general method for 1-aryl-2-iminoazacycloalkanes

    Directory of Open Access Journals (Sweden)

    Jimena E. Díaz

    2016-09-01

    Full Text Available The first general procedure for the synthesis of 5 to 7-membered 1-aryl-2-iminoazacycloalkanes is presented, by microwave-assisted ring closure of ω-arylaminonitriles promoted by polyphosphoric acid (PPA esters. 1-Aryl-2-iminopyrrolidines were easily prepared from the acyclic precursors employing a chloroformic solution of ethyl polyphosphate (PPE. The use of trimethylsilyl polyphosphate (PPSE in solvent-free conditions allowed for the synthesis of 1-aryl-2-iminopiperidines and hitherto unreported 1-aryl-2-iminoazepanes. The cyclization reaction involves good to high yields and short reaction times, and represents a novel application of PPA esters in heterocyclic synthesis.

  6. Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

    Directory of Open Access Journals (Sweden)

    Elizabeth P. Jones

    2011-11-01

    Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

  7. From boron analogues of amino acids to boronated DNA: potential new pharmaceuticals and neutron capture agents

    International Nuclear Information System (INIS)

    Spielvogel, B.F.; Sood, Anup; Duke Univ., Durham, NC; Shaw, B.R.; Hall, I.H.

    1991-01-01

    Isoelectronic and isostructural boron analogues of the α-amino acids ranging from simple glycine analogues such as H 3 NBH 2 COOH and Me 2 NHBH 2 COOH to alanine analogues have been synthesised. A diverse variety of analogues, including precursors and derivatives (such as peptides) have potent pharmacological activity, including anticancer, antiinflammatory, analgesic, and hypolipidemic activity in animal model studies and in vitro cell cultures. Boronated nucleosides and (oligo)nucleotides, synthetic oligonucleotide analogues of ''antisense'' agents interact with a complementary nucleic acid sequence blocking the biological effect of the target sequence. Nucleosides boronated on the pyrimidine and purine bases have been prepared. It has been established that an entirely new class of nucleic acid derivatives is feasible in which one of the non-bridging oxygens in the internucleotide phosphodiester linkage can be replaced by an isoelectronic analogue, the borane group, (BH 3 ). The boronated oligonucleotides can be viewed as hybrids of the normal oxygen oligonucleotides and the methylphosphonate oligonucleotides. (author)

  8. Boron

    Science.gov (United States)

    Boron is an essential micronutrient element required for plant growth. Boron deficiency is wide-spread in crop plants throughout the world especially in coarse-textured soils in humid areas. Boron toxicity can also occur, especially in arid regions under irrigation. Plants respond directly to the...

  9. Solvent-Free Synthesis of Aryl Iodide Using Nano SiO2/HIO4 as a Reusable Acid Catalyst

    Directory of Open Access Journals (Sweden)

    A. Bamoniri

    2014-07-01

    Full Text Available An efficient and environmentally benign   method for the synthesis of aryl iodides have been developed by diazotization of aromatic amines with NaNO2 and nanosilica periodic acid (nano-SPIA as a green catalyst via grinding followed by a sandmeyer iodination by KI under solvent-free conditions at room temperature. The ensuing aryl diazonium salts supported on nano-SPIA were sufficiently stable to be kept at room temperature in the dry state. This method is a novel, efficient, eco-friendly route for solvent-free synthesis of aryl iodides.

  10. Base free aryl coupling of diazonium compounds and boronic esters: self-activation allowing an overall highly practical process.

    Science.gov (United States)

    Bonin, Hélène; Delbrayelle, Dominique; Demonchaux, Patrice; Gras, Emmanuel

    2010-04-21

    Boronic esters have long been considered as poor partners in cross-coupling reactions with arene diazoniums. Here is reported an unprecedented application of self-activated boronic esters in a base-free cross-coupling reaction with diazonium salts under mild and user friendly conditions.

  11. Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds.

    Science.gov (United States)

    Best, Daniel; Burns, David J; Lam, Hon Wai

    2015-06-15

    A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N-H groups are tolerated on the barbituric acid, with no complications arising from N-H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  12. Docking of oxalyl aryl amino benzoic acid derivatives into PTP1B

    Science.gov (United States)

    Verma, Neelam; Mittal, Minakshi; Verma, Raman kumar

    2008-01-01

    Protein Tyrosine Phosphatases (PTPs) that function as negative regulators of the insulin signaling cascade have been identified as novel targets for the therapeutic enhancement of insulin action in insulin resistant disease states. Reducing Protein Tyrosine Phosphatase1B (PTP1B) abundance not only enhances insulin sensitivity and improves glucose metabolism but also protects against obesity induced by high fat feeding. PTP1B inhibitors such as Formylchromone derivatives, 1, 2-Naphthoquinone derivatives and Oxalyl aryl amino benzoic derivatives may eventually find an important clinical role as insulin sensitizers in the management of Type-II Diabetes and metabolic syndrome. We have carried out docking of modified oxalyl aryl amino benzoic acid derivatives into three dimensional structure of PTP1B using BioMed CAChe 6.1. These compounds exhibit good selectivity for PTP1B over most of phosphatases in selectivity panel such as SHP-2, LAR, CD45 and TCPTP found in literature. This series of compounds identified the amino acid residues such as Gly220 and Arg221 are important for achieving specificity via H-bonding interactions. Lipophilic side chain of methionine in modified oxalyl aryl amino benzoic acid derivative [1b (a2, b2, c1, d)] lies in closer vicinity of hydrophobic region of protein consisted of Meth258 and Phe52 in comparison to active ligand. Docking Score in [1b (a2, b2, c1, d)] is -131.740Kcal/mol much better than active ligand score -98.584Kcal/mol. This information can be exploited to design PTP1B specific inhibitors. PMID:19238234

  13. Thermometric titration of beta-aryl-alpha-mercaptopropenoic acids and determination of the stoichiometry of their metal complexes.

    Science.gov (United States)

    Izquierdo, A; Carrasco, J

    1981-05-01

    Automatic thermometric titration was applied to some beta-aryl-alpha-mercaptopropenoic acids and the stoichiometry of their complexes with several metal ions was investigated. The heats of neutralization of the mercapto-acids with sodium hydroxide and the heats of their reaction with metal ions were calculated.

  14. Design, synthesis and structure of new potential electrochemically active boronic acid-based glucose sensors

    DEFF Research Database (Denmark)

    Norrild, Jens Chr.; Søtofte, Inger

    2002-01-01

    In the course of our investigations on new boronic acid based carbohydrate sensors three new boronic acids 3, 7 and 11 containing a ferrocene moiety were synthesised. Their design includes an intramolecular B-N bonding motif in order to facilitate binding at physiological pH. We report the synthe......In the course of our investigations on new boronic acid based carbohydrate sensors three new boronic acids 3, 7 and 11 containing a ferrocene moiety were synthesised. Their design includes an intramolecular B-N bonding motif in order to facilitate binding at physiological pH. We report...

  15. Scope and Mechanism of a True Organocatalytic Beckmann Rearrangement with a Boronic Acid/Perfluoropinacol System under Ambient Conditions.

    Science.gov (United States)

    Mo, Xiaobin; Morgan, Timothy D R; Ang, Hwee Ting; Hall, Dennis G

    2018-04-18

    Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18 O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11 B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst

  16. Chemical basis for the phytotoxicity of N-aryl hydroxamic acids and acetanilide analogues.

    Science.gov (United States)

    Bravo, Héctor R; Villarroel, Elisa; Copaja, Sylvia V; Argandoña, Victor H

    2008-01-01

    Germination inhibition activity of N-aryl hydroxamic acids and acetanilide analogues was measured on lettuce seeds (Lactuca sativa). Lipophilicity of the compounds was determined by HPLC. A correlation between lipophilicity values and percentage of germination inhibition was established. A model mechanism of action for auxin was used for analyzing the effect of the substituent at the alpha carbon atom (Ca) on the polarization of hydroxamic and amide functions in relation to the germination inhibition activity observed. Results suggest that the lipophilic and acidic properties play an important role in the phytotoxicity of the compounds. A test with the microalga Chlorella vulgaris was used to evaluate the potential herbicide activity of the hydroxamic acids and acetanilides.

  17. Efficient and Simple Synthesis of 6-Aryl-1,4-dimethyl-9H-carbazoles

    Directory of Open Access Journals (Sweden)

    Sylvain Rault

    2008-06-01

    Full Text Available A synthetic method for the preparation of 6-aryl-1,4-dimethyl-9H-carbazoles involving a palladium catalyzed coupling reaction of 1,4-dimethyl-9H-carbazole-6-boronic acids and (heteroaryl halides is described.

  18. Determination of boron as boric acid by automatic potentiometric titration

    International Nuclear Information System (INIS)

    Midgley, D.

    1988-06-01

    Boron in PWR primary coolant and related waters may be determined as boric acid by titration with sodium hydroxide, using a glass electrode as a pH indicator. With a modern automatic titrator, the analysis is quick, convenient, accurate and precise. In the titration of 8 mg B (e.g. 4 ml of 2000 mg 1 -1 solution), no significant bias was observed and relative standard deviations were about 0.25%. With 0.8 g B, a bias of about 2% appears, although this could be reduced by restandardizing the titrant, but the relative standard deviation was still -1 B, depending on the stage of the fuel cycle. (author)

  19. Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

    2005-06-23

    [reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

  20. Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

    Science.gov (United States)

    Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

    2008-01-01

    Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

  1. Ion-tagged π-acidic alkene ligands promote Pd-catalysed allyl-aryl couplings in an ionic liquid

    NARCIS (Netherlands)

    Bäuerlein, P.S.; Fairlamb, I.J.S.; Jarvis, A.G.; Lee, A.F.; Müller, C.; Slattery, J.M.; Thatcher, R.J.; Vogt, D.; Whitwood, A.C.

    2009-01-01

    Ionic p-acidic alkene ligands based on chalcone and benzylidene acetone frameworks have been ?doped? into ionic liquids to provide functional reaction media for Pd-catalysed cross-couplings of a cyclohexenyl carbonate with aryl siloxanes that allow simple product isolation, free from Pd (

  2. Boron removal from aqueous solutions by activated carbon impregnated with salicylic acid

    International Nuclear Information System (INIS)

    Celik, Z. Ceylan; Can, B.Z.; Kocakerim, M. Muhtar

    2008-01-01

    In this study, the removal of boric acid from aqueous solution by activated carbon impregnated with salicylic acid was studied in batch system. pH, adsorbent amount, initial boron concentration, temperature, shaking rate and salicylic acid film thickness were chosen as parameters. Boron removal efficiencies increased with increasing adsorbent amount, temperature and pH, decreasing initial boron concentration. As thickness of salicylic acid film on activated carbon becomes thin up to 0.088 nm, the efficiency increased, and then, the efficiency decreased with becoming thinner than 0.088 nm of salicylic acid film. Shaking rate was no effect on removal efficiency. In result, it was determined that the use of salicylic acid as an impregnant for activated carbon led to the increase of the amount of boron adsorbed. A lactone ring, being the most appropriate conformation, forms between boric acid and -COOH and -OH groups of salicylic acid

  3. Boron removal from aqueous solutions by activated carbon impregnated with salicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Celik, Z. Ceylan [Department of Environmental Engineering, Atatuerk University, Faculty of Engineering, Erzurum (Turkey)], E-mail: zcelik@atauni.edu.tr; Can, B.Z. [Department of Environmental Engineering, Atatuerk University, Faculty of Engineering, Erzurum (Turkey); Kocakerim, M. Muhtar [Department of Chemical Engineering, Atatuerk University, Faculty of Engineering, 25240 Erzurum (Turkey)

    2008-03-21

    In this study, the removal of boric acid from aqueous solution by activated carbon impregnated with salicylic acid was studied in batch system. pH, adsorbent amount, initial boron concentration, temperature, shaking rate and salicylic acid film thickness were chosen as parameters. Boron removal efficiencies increased with increasing adsorbent amount, temperature and pH, decreasing initial boron concentration. As thickness of salicylic acid film on activated carbon becomes thin up to 0.088 nm, the efficiency increased, and then, the efficiency decreased with becoming thinner than 0.088 nm of salicylic acid film. Shaking rate was no effect on removal efficiency. In result, it was determined that the use of salicylic acid as an impregnant for activated carbon led to the increase of the amount of boron adsorbed. A lactone ring, being the most appropriate conformation, forms between boric acid and -COOH and -OH groups of salicylic acid.

  4. Boron Stress Activates the General Amino Acid Control Mechanism and Inhibits Protein Synthesis

    Science.gov (United States)

    Uluisik, Irem; Kaya, Alaattin; Fomenko, Dmitri E.; Karakaya, Huseyin C.; Carlson, Bradley A.; Gladyshev, Vadim N.; Koc, Ahmet

    2011-01-01

    Boron is an essential micronutrient for plants, and it is beneficial for animals. However, at high concentrations boron is toxic to cells although the mechanism of this toxicity is not known. Atr1 has recently been identified as a boron efflux pump whose expression is upregulated in response to boron treatment. Here, we found that the expression of ATR1 is associated with expression of genes involved in amino acid biosynthesis. These mechanisms are strictly controlled by the transcription factor Gcn4 in response to boron treatment. Further analyses have shown that boron impaired protein synthesis by promoting phosphorylation of eIF2α in a Gcn2 kinase dependent manner. The uncharged tRNA binding domain (HisRS) of Gcn2 is necessary for the phosphorylation of eIF2α in the presence of boron. We postulate that boron exerts its toxic effect through activation of the general amino acid control system and inhibition of protein synthesis. Since the general amino acid control pathway is conserved among eukaryotes, this mechanism of boron toxicity may be of general importance. PMID:22114689

  5. Boron stress activates the general amino acid control mechanism and inhibits protein synthesis.

    Directory of Open Access Journals (Sweden)

    Irem Uluisik

    Full Text Available Boron is an essential micronutrient for plants, and it is beneficial for animals. However, at high concentrations boron is toxic to cells although the mechanism of this toxicity is not known. Atr1 has recently been identified as a boron efflux pump whose expression is upregulated in response to boron treatment. Here, we found that the expression of ATR1 is associated with expression of genes involved in amino acid biosynthesis. These mechanisms are strictly controlled by the transcription factor Gcn4 in response to boron treatment. Further analyses have shown that boron impaired protein synthesis by promoting phosphorylation of eIF2α in a Gcn2 kinase dependent manner. The uncharged tRNA binding domain (HisRS of Gcn2 is necessary for the phosphorylation of eIF2α in the presence of boron. We postulate that boron exerts its toxic effect through activation of the general amino acid control system and inhibition of protein synthesis. Since the general amino acid control pathway is conserved among eukaryotes, this mechanism of boron toxicity may be of general importance.

  6. Boronic acid-modified magnetic materials for antibody purification

    Science.gov (United States)

    Dhadge, Vijaykumar L.; Hussain, Abid; Azevedo, Ana M.; Aires-Barros, Raquel; Roque, Ana C. A.

    2014-01-01

    Aminophenyl boronic acids can form reversible covalent ester interactions with cis-diol-containing molecules, serving as a selective tool for binding glycoproteins as antibody molecules that possess oligosaccharides in both the Fv and Fc regions. In this study, amino phenyl boronic acid (APBA) magnetic particles (MPs) were applied for the magnetic separation of antibody molecules. Iron oxide MPs were firstly coated with dextran to avoid non-specific binding and then with 3-glycidyloxypropyl trimethoxysilane to allow further covalent coupling of APBA (APBA_MP). When contacted with pure protein solutions of human IgG (hIgG) and bovine serum albumin (BSA), APBA_MP bound 170 ± 10 mg hIgG g−1 MP and eluted 160 ± 5 mg hIgG g−1 MP, while binding only 15 ± 5 mg BSA g−1 MP. The affinity constant for the interaction between hIgG and APBA_MP was estimated as 4.9 × 105 M−1 (Ka) with a theoretical maximum capacity of 492 mg hIgG adsorbed g−1 MP (Qmax), whereas control particles bound a negligible amount of hIgG and presented an estimated theoretical maximum capacity of 3.1 mg hIgG adsorbed g−1 MP (Qmax). APBA_MPs were also tested for antibody purification directly from CHO cell supernatants. The particles were able to bind 98% of IgG loaded and to recover 95% of pure IgG (purity greater than 98%) at extremely mild conditions. PMID:24258155

  7. Boronic acid-based autoligation of nucleic acids

    DEFF Research Database (Denmark)

    Barbeyron, R.; Vasseur, J.-J.; Smietana, M.

    2013-01-01

    Abstract: The development of synthetic systems displaying dynamic and adaptive characteristics is a formidable challenge with wide applications from biotechnology to therapeutics. Recently, we described a dynamic and programmable nucleic acid-based system relying on the formation of reversible bo....... Evidence suggests that geometric and steric factors are key features for controlling the equilibria. Graphical Abstract: [Figure not available: see fulltext.]...

  8. Spectrophotometric determination of boron by solvent extraction with 2-hydroxy-2-methylbutyric acid and malachite green

    International Nuclear Information System (INIS)

    Sato, Shigeya; Uchikawa, Sumio

    1984-01-01

    A very simple and sensitive method for the spectrophotometric determination of boron was developed. Boron was found to react with 2-hydroxy-2-methylbutyric acid in weak acidic aqueous solution at room temperature to form a complex anion which can be extracted into chlorobenzene with malachite green in a single extraction; boron is determined indirectly by measuring the absorbance of malachite green in the extract at 629 nm. The calibration graph is linear over the range (7.50 x 10 -7 - 2.00 x 10 -5 ) mol dm -3 boron; the apparent molar absorptivity is 6.50 x 10 4 dm 3 mol -1 cm -1 . The method is applied to the determination of micro amounts of boron in natural waters with satisfactory results. (author)

  9. Spectrophotometric determination of boron by solvent extraction with 2-hydroxy-2-methylbutyric acid and malachite green

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Shigeya; Uchikawa, Sumio [Kumamoto Univ. (Japan). Faculty of Education

    1984-03-01

    A very simple and sensitive method for the spectrophotometric determination of boron was developed. Boron was found to react with 2-hydroxy-2-methylbutyric acid in weak acidic aqueous solution at room temperature to form a complex anion which can be extracted into chlorobenzene with malachite green in a single extraction; boron is determined indirectly by measuring the absorbance of malachite green in the extract at 629 nm. The calibration graph is linear over the range (7.50 x 10/sup -7/ - 2.00 x 10/sup -5/) mol dm/sup -3/ boron; the apparent molar absorptivity is 6.50 x 10/sup 4/ dm/sup 3/ mol/sup -1/ cm/sup -1/. The method is applied to the determination of micro amounts of boron in natural waters with satisfactory results.

  10. SYNTHESIS AND STUDY OF ANTIOXIDANT ACTIVITY OF [(1-ARYL-5-FORMYL-1H-IMIDAZOLE-4-ILTHIO]PROPIONIC ACIDS

    Directory of Open Access Journals (Sweden)

    A. O. Palamar

    2014-12-01

    Full Text Available Introduction. Derivatives of imidazole belong to the promising group of compounds for antioxidant activity study, due to the series of recent publications. This is defined by special features of their structure, specific reactivity and significant potential of pharmacological action. Earlier during process of looking for new antioxidants we studied significant amount of imidazole derivatives, among which the [(1-aryl-5-formylimidazole-4-ilthio]acetic acids structurally modified by the formyl group and thioacetic acid fragment, are especially worth noting. The purpose of the study. Synthesis of [(1-aryl-5-formylimidazole-4-ilthio]propionic acids and comparison of their antioxidant effect with [(1-aryl-5-formylimidazole-4-ilthio]acetic acids with to identify prospects of in-depth study of the most active compounds as antioxidants. Materials and methods. The method based on interaction of available 4-chloro-5-formylimidazoles with thiopropionic acid was proposed for the synthesis of [(1-aryl-5-formylimidazole-4-ilthio]propionic acids. The reaction takes place in ethanol in presence of potassium hydroxide and leads to the target compounds with yields of 81-86%. The study of antioxidant activity of synthesized compounds was conducted in vitro by speed inhibition value of rats’ liver endogenous lipids ascorbate-dependent peroxide oxidation. It was determined by concentration of one of the final products of free radical oxidation of lipids (FROL – maleic aldehyde (MA in the investigated sample. Concentrations of synthesized compounds were chosen within concentrations which were studied for thiotriazolin (manufactured by corporation “Arterium”, Ukraine, solution for injection, 25 mg/ml. The results of the study and their discussion. Preparative method for the synthesis of [(1-aryl-5-formylimidazole-4-ilthio]propionic acids has been designed. Imidazolylthiopropionic acids have been synthesized; they are crystalline compounds, of light

  11. Responsive Boronic Acid-Decorated (Co)polymers: From Glucose Sensors to Autonomous Drug Delivery.

    Science.gov (United States)

    Vancoillie, Gertjan; Hoogenboom, Richard

    2016-10-19

    Boronic acid-containing (co)polymers have fascinated researchers for decades, garnering attention for their unique responsiveness toward 1,2- and 1,3-diols, including saccharides and nucleotides. The applications of materials that exert this property are manifold including sensing, but also self-regulated drug delivery systems through responsive membranes or micelles. In this review, some of the main applications of boronic acid containing (co)polymers are discussed focusing on the role of the boronic acid group in the response mechanism. We hope that this summary, which highlights the importance and potential of boronic acid-decorated polymeric materials, will inspire further research within this interesting field of responsive polymers and polymeric materials.

  12. Responsive Boronic Acid-Decorated (Copolymers: From Glucose Sensors to Autonomous Drug Delivery

    Directory of Open Access Journals (Sweden)

    Gertjan Vancoillie

    2016-10-01

    Full Text Available Boronic acid-containing (copolymers have fascinated researchers for decades, garnering attention for their unique responsiveness toward 1,2- and 1,3-diols, including saccharides and nucleotides. The applications of materials that exert this property are manifold including sensing, but also self-regulated drug delivery systems through responsive membranes or micelles. In this review, some of the main applications of boronic acid containing (copolymers are discussed focusing on the role of the boronic acid group in the response mechanism. We hope that this summary, which highlights the importance and potential of boronic acid-decorated polymeric materials, will inspire further research within this interesting field of responsive polymers and polymeric materials.

  13. Selective antagonists at group I metabotropic glutamate receptors: synthesis and molecular pharmacology of 4-aryl-3-isoxazolol amino acids

    DEFF Research Database (Denmark)

    Kromann, Hasse; Sløk, Frank A; Stensbøl, Tine B

    2002-01-01

    Homologation of (S)-glutamic acid (Glu, 1) and Glu analogues has previously provided ligands with activity at metabotropic Glu receptors (mGluRs). The homologue of ibotenic acid (7), 2-amino-3-(3-hydroxy-5-isoxazolyl)propionic acid (HIBO, 8), and the 4-phenyl derivative of 8, compound 9a, are bot...... antagonists at group I mGluRs. Here we report the synthesis and molecular pharmacology of HIBO analogues 9b-h containing different 4-aryl substituents. All of these compounds possess antagonist activity at group I mGluRs but are inactive at group II and III mGluRs....

  14. Magnetic Vinylphenyl Boronic Acid Microparticles for Surface Catalytic Performance in Esterification of Propionic Acid with Methanol

    Directory of Open Access Journals (Sweden)

    Ali Kara

    2016-12-01

    Full Text Available Magnetic vinylphenyl boronic acid microparticles, poly(ethylene glycol dimethacrylate-vinylphenyl boronic acid [m-poly(EGDMA-VPBA], produced by suspension polymerization, was found to be efficient solid acid catalyst for the esterification of methanol and propionic acid. Characterization techniques such as FT-IR, Elemental analyses, ICP-AES, ESR, SEM and N2 sorption showed that both of Fe3O4 and H2SO4 are bonded to the polymer successfully. Esterification was studied for different molar percentages of H2SO4 at temperature range of 50-70 oC. The apparent activation energy was found to be 27.7 kj.mol-1 for 10% H2SO4 doped m-poly(EGDMA-VPBA. Combining of strong acid H2SO4 with m-poly(EGDMA-VPBA, leads to materials with different functional properties. In addition, H2SO4 species could be introduced into the structure as acid centers, therefore this micro-dimensional catalyst has potential candidate for applications in the catalytic esterifications such as propionic acid with methanol.

  15. Bromosubstituted aryl hydroxamic acids and their analytical application towards some transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Salah Elnaiem [Department of Chemistry, Faculty of Science, University of Khartoum, Khartoum (Sudan)

    1997-07-01

    Four aryl substituted hydroxamic acids were prepared: N-phenyl-N-p-bromobenzohydroxamic acid, N-phenyl-N-o-bromobenzohydroxamic acid, p-methyl-N-phenyl-N-p-bromobenzohydroxamic acid and P-methyl-N-phenyl-N-o-bromobenzohydroxamic acid by the reaction of {beta}-phenylhydroxylamine and p-methyl-{beta} phenylhydroxylamine with the corresponding acid chloride. The acids were identified by their melting points, elemental analysis (nitrogen and bromine contents), infrared and ultraviolet absorption in chloroform, as well as reactions towards acidic solutions of vanadium (V) and iron (III) to give violet and blood-red coulured complexes in the chloroform layer respectively. The extractability of these acids towards chromium (VI), molybdenum (VI), iron (III), vanadium (V), copper (II) and cobalt (II) was investigated. N-phenyl-N-p-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 96.00% at 1M H{sup 2}SO{sup 4}, molybdenum (VI) 87.00% at pH 1, iron (III) 73.90% at pH 4, vanadium (V) 93.00% at pH 1, cobalt (II) 83.10 at pH 8 and copper (II) 93.80% at pH 6. N-phenyl-N-o-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 97.00% at 1M H{sup 2}SO{sup 4}, molybdenum (VI) 92.70% at pH 1, iron (III) 71.20% at pH 4, vanadium (V) 90.00% at pH 1, cobalt (II) 54.70% at pH 7 and copper (II) 86.50% at pH 5. P-methyl-N-phenyl-N-p-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 98.70% at 1M H{sup 2}SO{sup 4}, molybdenum (VI) 74.00% at pH 1, iron (III) 69.60% at pH 5, vandium (V) 76.00% at pH 1, cobalt (II) 51.20% at pH 8 and copper (II) 82.20% at pH 5. P-methyl-N-phenyl-N-o-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 51.00% at 1M H{sup 2}SO{sup 4}, molybdenum (VI) 84.70% at pH 1, iron (III) 66.00% at pH 4, vandium (V) 88.00% at pH 1, cobalt (II) 50.00% at pH 7 and copper (II) 78.6% at pH 6. Twenty four of hydroxamic acids complexes of Cr (VI), Mo (VI), V (V), Fe (III), Co (II) and Cu (II) were prepared by the

  16. Bromosubstituted aryl hydroxamic acids and their analytical application towards some transition metals

    International Nuclear Information System (INIS)

    Mohamed, Salah Elnaiem

    1997-01-01

    Four aryl substituted hydroxamic acids were prepared: N-phenyl-N-p-bromobenzohydroxamic acid, N-phenyl-N-o-bromobenzohydroxamic acid, p-methyl-N-phenyl-N-p-bromobenzohydroxamic acid and P-methyl-N-phenyl-N-o-bromobenzohydroxamic acid by the reaction of β-phenylhydroxylamine and p-methyl-β phenylhydroxylamine with the corresponding acid chloride. The acids were identified by their melting points, elemental analysis (nitrogen and bromine contents), infrared and ultraviolet absorption in chloroform, as well as reactions towards acidic solutions of vanadium (V) and iron (III) to give violet and blood-red coulured complexes in the chloroform layer respectively. The extractability of these acids towards chromium (VI), molybdenum (VI), iron (III), vanadium (V), copper (II) and cobalt (II) was investigated. N-phenyl-N-p-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 96.00% at 1M H 2 SO 4 , molybdenum (VI) 87.00% at pH 1, iron (III) 73.90% at pH 4, vanadium (V) 93.00% at pH 1, cobalt (II) 83.10 at pH 8 and copper (II) 93.80% at pH 6. N-phenyl-N-o-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 97.00% at 1M H 2 SO 4 , molybdenum (VI) 92.70% at pH 1, iron (III) 71.20% at pH 4, vanadium (V) 90.00% at pH 1, cobalt (II) 54.70% at pH 7 and copper (II) 86.50% at pH 5. P-methyl-N-phenyl-N-p-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 98.70% at 1M H 2 SO 4 , molybdenum (VI) 74.00% at pH 1, iron (III) 69.60% at pH 5, vandium (V) 76.00% at pH 1, cobalt (II) 51.20% at pH 8 and copper (II) 82.20% at pH 5. P-methyl-N-phenyl-N-o-bromobenzohydroxamic acid has a maximum extraction for chromium (VI) 51.00% at 1M H 2 SO 4 , molybdenum (VI) 84.70% at pH 1, iron (III) 66.00% at pH 4, vandium (V) 88.00% at pH 1, cobalt (II) 50.00% at pH 7 and copper (II) 78.6% at pH 6. Twenty four of hydroxamic acids complexes of Cr (VI), Mo (VI), V (V), Fe (III), Co (II) and Cu (II) were prepared by the reaction of these acids with the six

  17. Design, synthesis and structure of new potential electrochemically active boronic acid-based glucose sensors

    DEFF Research Database (Denmark)

    Norrild, Jens Chr.; Søtofte, Inger

    2002-01-01

    In the course of our investigations on new boronic acid based carbohydrate sensors three new boronic acids 3, 7 and 11 containing a ferrocene moiety were synthesised. Their design includes an intramolecular B-N bonding motif in order to facilitate binding at physiological pH. We report the synthe......In the course of our investigations on new boronic acid based carbohydrate sensors three new boronic acids 3, 7 and 11 containing a ferrocene moiety were synthesised. Their design includes an intramolecular B-N bonding motif in order to facilitate binding at physiological pH. We report...... the synthesis of the compounds and our investigations on glucose complexation as studied by C-13 NMR spectroscopy. The crystal structure of 2,4,6-tris[2-(N-ferrocenylmethyl-N-methylaminomethyl) phenyl] boroxin (13) (boroxin of boronic acid 3) (boroxin = cyclotriboroxane) was obtained and compared...... with structures obtained of 2,4,6-tris[2-(N,N-dimethylaminomethyl)phenyl]boroxin (14) and 2,2-dimethyl-1,3-diyl[2-(N,N-dimethylaminomethyl)phenyl]boronate (15). The structure of 13 shows the existence of intramolecular B-N bonds in the solid phase....

  18. Formation of aryl-chlorinated aromatic acids and precursors for chloroform in chlorination of humic acid

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Leer, E.W.B. de; Galan, L.

    1985-01-01

    The formation of chloroform when humic substances are chlorinated is well known. Other chlorinated products that may be formed are chloral, di- and trichloroacetic acid, chlorinated C-4 diacids, and α-chlorinated aliphatic acids. Several of these compounds are formed in molar yields comparable

  19. Boronic Acid-Based Approach for Separation and Immobilization of Glycoproteins and Its Application in Sensing

    Directory of Open Access Journals (Sweden)

    Lin Liu

    2013-10-01

    Full Text Available Glycoproteins influence a broad spectrum of biological processes including cell-cell interaction, host-pathogen interaction, or protection of proteins against proteolytic degradation. The analysis of their glyco-structures and concentration levels are increasingly important in diagnosis and proteomics. Boronic acids can covalently react with cis-diols in the oligosaccharide chains of glycoproteins to form five- or six-membered cyclic esters. Based on this interaction, boronic acid-based ligands and materials have attracted much attention in both chemistry and biology as the recognition motif for enrichment and chemo/biosensing of glycoproteins in recent years. In this work, we reviewed the progress in the separation, immobilization and detection of glycoproteins with boronic acid-functionalized materials and addressed its application in sensing.

  20. Boronic acid adducts of technetium dioxime (BATO) complexes derived from quinuclidine benzilate (QNB) boronic acid stereoisomers: Syntheses and studies of their binding to the muscarinic acetylcholine receptor

    International Nuclear Information System (INIS)

    Jurisson, Silvia S.; Pirro, John; DiRocco, Richard J.; Rosenspire, Karen C.; Jagoda, Elaine; Nanjappan, Palaniappa; Eckelman, William C.; Nowotnik, David P.; Nunn, Adrian D.

    1995-01-01

    We have investigated the possibility of using BATO complexes derivatized with the muscarinic acetylcholine receptor (mAChR) antagonist, quinuclidinyl benzilate (QNB), for mAChR imaging. The BATO complexes, TcCl(DMG) 3 B-QNB, were prepared using QNB derivatives containing a 4'-boronic acid substituent on one of the benzilic benzene rings (QNB-boronic acid). The QNB-boronic acid molecule has two chiral centers, and all four QNB-BATO stereoisomers were made and evaluated. When studied using in vitro receptor binding assays based on tissue from rat brain caudate-putamen (which contains primarily M 1 and M 4 mAChR) and rat heart (M 2 mAChR), the QNB-boronic acid stereoisomers had binding affinities (K A ) in the range 2 x 10 5 -1 x 10 8 , at least 10-fold lower than theK A for QNB (ca 2 x 10 9 ). The stereochemistry of both centers had some influence on the affinity constant. When the TcCl(DMG) 3 B-QNB complexes were studied, none of the stereoisomeric complexes displayed measurable specific binding (K A 6 ), but all showed high non-specific binding. In vitro autoradiography with rat brain slices confirmed the absence of specific binding in these tracers. In vivo, the 99m TcCl(DMG) 3 B-QNB complexes displayed minimal brain uptake, and modest heart uptake; the latter was unlikely to be related to uptake by the mAChR. In light of these findings, we conclude that the interaction between the TcCl(DMG) 3 B-QNB complexes and biological membranes is dominated by the hydrophobicity of the BATO moiety. The TcCl(DMG) 3 B-QNB complexes, therefore, have little potential for mAChR imaging

  1. Methanofullerene-Based Palladium Bis(amino)aryl Complexes and Applications in Lewis Acid Catalysis

    NARCIS (Netherlands)

    Koten, G. van; Meijer, M.D.; Ronde, N.; Vogt, D.; Klink, G.P.M. van

    2001-01-01

    Synthetic routes have been developed for the attachment of palladium(II) bis(amino)aryl (NCN or C6H2{CH2NMe2}2-2,6)- complexes to C60. Using diazo and Bingel addition reactions, various methanofullerene NCN-SiMe3 compounds (C60-L-NCN-SiMe3, L = C(Me), C(CO2Et)CO2CH2, and C(Me)C6H4CC) have been

  2. Sensitive Thin-Layer Chromatography Detection of Boronic Acids Using Alizarin

    NARCIS (Netherlands)

    Duval, F.L.; Beek, van T.A.; Zuilhof, H.

    2012-01-01

    A new method for the selective and sensitive detection of boronic acids on thin-layer chromatography plates is described. The plate is briefly dipped in an alizarin solution, allowed to dry in ambient air, and observed under 366 nm light. Alizarin emits a bright yellow fluorescence only in the

  3. A new boronic acid fluorescent sensor based on fluorene for monosaccharides at physiological pH.

    Science.gov (United States)

    Hosseinzadeh, Rahman; Mohadjerani, Maryam; Pooryousef, Mona; Eslami, Abbas; Emami, Saeed

    2015-06-05

    Fluorescent boronic acids are very useful fluorescent sensor for detection of biologically important saccharides. Herein we synthesized a new fluorene-based fluorescent boronic acid that shows significant fluorescence changes upon addition of saccharides at physiological pH. Upon addition of fructose, sorbitol, glucose, galactose, ribose, and maltose at different concentration to the solution of 7-(dimethylamino)-9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (7-DMAFBA, 1), significant decreases in fluorescent intensity were observed. It was found that this boronic acid has high affinity (K(a)=3582.88 M(-1)) and selectivity for fructose over glucose at pH=7.4. The sensor 1 showed a linear response toward d-fructose in the concentrations ranging from 2.5×10(-5) to 4×10(-4) mol L(-1) with the detection limit of 1.3×10(-5) mol L(-1). Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Hyaluronic acid as a potential boron carrier for BNCT: Preliminary evaluation

    International Nuclear Information System (INIS)

    Zaboronok, A.; Yamamoto, T.; Nakai, K.; Yoshida, F.; Uspenskii, S.; Selyanin, M.; Zelenetskii, A.; Matsumura, Akira

    2015-01-01

    Hyaluronic acid (HA), a nonimmunogenic, biocompatible polymer found in different biological tissues, has the potential to attach to CD44 receptors on the surface of certain cancer cells, where the receptor is overexpressed compared with normal cells. Boron–hyaluronic acid (BHA) was tested for its feasibility as a potential agent for BNCT. BHA with low-viscosity 30 kDa HA could be administered by intravenous injection. The compound showed a certain degree of cytotoxicity and accumulation in C6 rat glioma cells in vitro. Instability of the chelate bonds between boron and HA and/or insufficient specificity of CD44 receptors on C6 cells to BHA could account for the insufficient in vitro accumulation. To ensure the future eligibility of BHA for BNCT experiments, using alternative tumor cell lines and chemically securing the chelate bonds or synthesizing BHA with boron covalently attached to HA might be required. - Highlights: • Hyaluronic acid (HA) is a nonimmunogenic, biocompatible polymer. • Boron–HA (BHA) acid can contain a large number of boron atoms for BNCT. • Active targeting can be realized with CD44 and other HA receptors on tumor cells. • BHA showed a certain degree of toxicity against C6 tumor cells and V79 fibroblasts. • BHA was injected into rats via the tail vein, boron was detected in tumors in vivo.

  5. Respiratory irritation associated with inhalation of boron trifluoride and fluorosulfonic acid

    NARCIS (Netherlands)

    Rusch, G.M.; Bowden, A.M.; Muijser, H.; Arts, J.

    2008-01-01

    The objectives of this study were to examine the respiratory irritancy of boron trifluoride (BF3) and fluorosulfonic acid (FSA) following acute inhalation exposure. Testing was conducted using groups of 10 male and 10 female rats (BF3) or groups of 6 male rats (FSA). Rats were exposed for a single

  6. Silica sulfuric acid and as an efficient catalyst for the Friedlander quinoline synthesis from simple ketones and ortho - amino aryl ketones under microwave irradiation

    International Nuclear Information System (INIS)

    Zolfigol, M. A.; Salehi, P.; Shiri, M.; Faal Rastegar, T.; Ghaderi, A.

    2008-01-01

    The synthesis of quinoline derivatives via Friedlander method from ortho-amino aryl ketones in the presence of a catalytic amount of silica sulfuric acid under solvent-free condition and microwave irradiation was described. A good range of simple ketones such as cyclohexanone and deoxybenzoin were used

  7. Acetic acid-promoted condensation of o-phenylenediamine with aldehydes into 2-aryl-1-(arylmethyl-1H-benzimidazoles under microwave irradiation

    Directory of Open Access Journals (Sweden)

    DAVOOD AZARIF

    2010-09-01

    Full Text Available An efficient and simple procedure was developed for the green synthesis of various 2-aryl-1-(arylmethyl-1H-benzimidazoles in high yields by acetic acid-promoted condensation of o-phenylenediamine with aldehydes in air under microwave irradiation and transition metal catalyst-free conditions.

  8. Boron reclamation

    International Nuclear Information System (INIS)

    Smith, R.M.

    1980-07-01

    A process to recover high purity 10 B enriched crystalline boron powder from a polymeric matrix was developed on a laboratory basis and ultimately scaled up to production capacity. The process is based on controlled pyrolysis of boron-filled scrap followed by an acid leach and dry sieving operation to return the powder to the required purity and particle size specifications. Typically, the recovery rate of the crystalline powder is in excess of 98.5 percent, and some of the remaining boron is recovered in the form of boric acid. The minimum purity requirement of the recovered product is 98.6 percent total boron

  9. Towards a fragment-based approach in gelator design: halogen effects leading to thixotropic, mouldable and self-healing systems in aryl-triazolyl amino acid-based gelators!

    Science.gov (United States)

    Srivastava, Bhartendu K; Manheri, Muraleedharan K

    2017-04-18

    A simple replacement of a H atom by Br transformed non-gelating aryl triazolyl amino acid benzyl ester into a versatile gelator, which formed shape-persistent, self-healing and mouldable gels. The 'bromo-aryl benzyl ester' fragment was then transplanted into another framework, which resulted in similar solvent preference and gelation efficiency.

  10. Removal of Aqueous Boron by Using Complexation of Boric Acid with Polyols: A Raman Spectroscopic Study

    Energy Technology Data Exchange (ETDEWEB)

    Eom, Ki Heon; Jeong, Hui Cheol; An, Hye Young; Lim, Jun-Heok; Lee, Jea-Keun; Won, Yong Sun [Pukyong National University, Busan (Korea, Republic of)

    2015-12-15

    Boron is difficult to be removed from seawater by simple RO (reverse osmosis) membrane process, because the size of boric acid (B(OH){sub 3}), the major form of aqueous boron, is as small as the nominal pore size of RO membrane. Thus, the complexation of boric acid with polyols was suggested as an alternative way to increase the size of aqueous boron compounds and the complexation behavior was investigated with Raman spectroscopy. As a reference, the Raman peak for symmetric B-O stretching vibrational mode both in boric acid and borate ion (B(OH){sub 4}{sup -}) was selected. A Raman peak shift (877 cm{sup -1} →730 cm{sup -1}) was observed to confirm that boric acid in water is converted to borate ion as the pH increases, which is also correctly predicted by frequency calculation. Meanwhile, the Raman peak of borate ion (730 cm{sup -1}) did not appear as the pH increased when polyols were applied into aqueous solution of boric acid, suggesting that the boric acid forms complexing compounds by combining with polyols.

  11. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Directory of Open Access Journals (Sweden)

    Tanveer Mahamadali Shaikh

    2013-08-01

    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  12. Boronic, diboronic, and α-amino-boronic acids derived from 1-ethynyl-3, 4-dimethoxybenzene

    International Nuclear Information System (INIS)

    Nakagawa, Toshio; Mishima, Yutaka

    1985-01-01

    This work was undertaken with the intention of synthesizing (α-amino-β-(3, 4-dihydroxyphenyl) ethylboronic acid. Unfortunately, the goal could not be attained since the isolation of the target compound could not be achieved though some information suggested its existence in the final product. The methods of synthesis used in the second half of the attempted preparation are described here (compounds in the first half have been published elsewhere). In this procedure, (β-(3, 4-dimethoxyphenyl)) ethenylboronic acid is esterified and azeotropic distillation is conducted to provide diethyl (β-(3, 4-dimethoxyphenyl)) ethenylboronate. This compound is dissolved in diglyme and diborane gas is introduced. The hydroboration product is then subjected to amination with hydroxylamine-0-sulfonic acid. (β-(3, 4-dimethoxyphenyl)) ethyl-α, α-diboronic acid is obtained from the residue of acetone extraction. The acetone extract is concentrated to a solid caramel, from which (α-borono-β-(3, 4-dimethoxyphenyl)) ethylammonium tetraphenylborate is formed. Conversion from the tetraphenylborate salt to (α-amino-β-(3, 4-dimethoxyphenyl)) ethylboronic acid hydrochloride is attempted by the double decomposition RH BPh 4 + CsCl -- RH Cl + CsBPh 4 . The product is subjected to demethylation and treated with sodium tetraphenylborate to precipitate (α-borono-β-(3, 4-dihydroxyphenyl)) ethylammonium tetraphenylborate. Conversion of this to the target compound is tried by double decomposition. (Nogami, K.)

  13. Inhibition studies of soybean (Glycine max) urease with heavy metals, sodium salts of mineral acids, boric acid, and boronic acids.

    Science.gov (United States)

    Kumar, Sandeep; Kayastha, Arvind M

    2010-10-01

    Various inhibitors were tested for their inhibitory effects on soybean urease. The K(i) values for boric acid, 4-bromophenylboronic acid, butylboronic acid, and phenylboronic acid were 0.20 +/- 0.05 mM, 0.22 +/- 0.04 mM, 1.50 +/- 0.10 mM, and 2.00 +/- 0.11 mM, respectively. The inhibition was competitive type with boric acid and boronic acids. Heavy metal ions including Ag(+), Hg(2+), and Cu(2+) showed strong inhibition on soybean urease, with the silver ion being a potent inhibitor (IC(50) = 2.3 x 10(-8) mM). Time-dependent inhibition studies exhibited biphasic kinetics with all heavy metal ions. Furthermore, inhibition studies with sodium salts of mineral acids (NaF, NaCl, NaNO(3), and Na(2)SO(4)) showed that only F(-) inhibited soybean urease significantly (IC(50) = 2.9 mM). Competitive type of inhibition was observed for this anion with a K(i) value of 1.30 mM.

  14. Comparison of Nootropic and Neuroprotective Features of Aryl-Substituted Analogs of Gamma-Aminobutyric Acid.

    Science.gov (United States)

    Tyurenkov, I N; Borodkina, L E; Bagmetova, V V; Berestovitskaya, V M; Vasil'eva, O S

    2016-02-01

    GABA analogs containing phenyl (phenibut) or para-chlorophenyl (baclofen) substituents demonstrated nootropic activity in a dose of 20 mg/kg: they improved passive avoidance conditioning, decelerated its natural extinction, and exerted antiamnestic effect on the models of amnesia provoked by scopolamine or electroshock. Tolyl-containing GABA analog (tolibut, 20 mg/kg) exhibited antiamnestic activity only on the model of electroshock-induced amnesia. Baclofen and, to a lesser extent, tolibut alleviated seizures provoked by electroshock, i.e. both agents exerted anticonvulsant effect. All examined GABA aryl derivatives demonstrated neuroprotective properties on the maximum electroshock model: they shortened the duration of coma and shortened the period of spontaneous motor activity recovery. In addition, these agents decreased the severity of passive avoidance amnesia and behavioral deficit in the open field test in rats exposed to electroshock. The greatest neuroprotective properties were exhibited by phenyl-containing GABA analog phenibut.

  15. Biological evaluation of dopamine analogues containing phenylboronic acid group as new boron carriers

    International Nuclear Information System (INIS)

    Ito, Y.; Mizuno, T.; Yoshino, K.; Ban, H.S.; Nakamura, H.; Hiratsuka, J.; Ishikawa, A.; Ohki, H.

    2011-01-01

    As new BNCT reagents, we designed and synthesized dopamine analogues containing phenylboronic acid group, N-3,4-dihydroxyphenethyl-4-dihydroxyborylbenzamide (dopamine–PCBA) and N-[2-(3,4-dihydroxyphenetyl)ethyl]-3-(4-dihydroxyborylphenyl)promionamide (dopamine–CEBA). The efficacies of these compounds have not been investigated for biological samples. Therefore we have carried out experiments with cultured tumor cells and tumor-bearing mice, and evaluated possibility of these compounds as boron carriers. Dopamine–PCBA and dopamine–CEBA were synthesized by coupling between p-carboxyphenylboronic acid (PCBA) or 4-(2-carboxyethyl)benzeneboronic acid (CEBA) and 3,4-(dibenzyloxy)phenethylamine hydrochloride (DBPA-HCl) followed by catalytic hydrogenation using Pd catalyst. The effect of compounds on cell vitality was determined by MTT assay in various cells. In vivo biodistribution of compounds was determined in Balb/c and DDY mice in bearing implanted CT26 cells. These results have demonstrated that dopamine–CEBA was less toxic. - Highlights: ► Dopamine analogues containing phenylboronic acid are synthesized as BNCT reagents. ► Their cytotoxicity is almost lower than that of BSH. ► Boron uptake with dopamine–PCBA is larger than that of BSH. ► Dopamine analogs showed lesser boron accumulation property into spleen than BPA.

  16. Ratiometric Sensing of Hydrogen Peroxide Utilizing Conformational Change in Fluorescent Boronic Acid Polymers

    Directory of Open Access Journals (Sweden)

    Kan Takeshima

    2017-01-01

    Full Text Available We demonstrate that the copolymers containing boronic acid and pyrene units can be utilized for the fluorometric sensing of hydrogen peroxide (H2O2 in aqueous solutions. The copolymer exists in a relatively extended conformation in the absence of H2O2, whereas the polymer chain is contracted by the reaction of boronic acid moieties with H2O2 to form phenol groups. This conformational change induces aggregation of the originally isolated pyrene groups. As a result, relative intensity of excimer emission with respect to monomer emission increases with H2O2 concentration. Accordingly, the present methodology enables us to measure H2O2 by means of ratiometric fluorescence change in the range of 0–30 μM.

  17. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    International Nuclear Information System (INIS)

    Lee, Kwan Soo; Kim, Kee D.

    2010-01-01

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF 4 ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers

  18. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kwan Soo [KAIST, Daejeon (Korea, Republic of); Kim, Kee D. [Sangji University, Wonju (Korea, Republic of)

    2010-12-15

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF{sub 4} ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers.

  19. 2.4. The kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

    2015-01-01

    Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit. The experimental data of dependence of hydrochloric-acid decomposition of calcined boron raw material for boron oxide extraction on temperature (20-80 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction from borosilicate raw material increases from 24.1 till 86.8%. The constants of decomposition rate of boron raw material were calculated.

  20. Probing the General Time Scale Question of Boronic Acid Binding with Sugars in Aqueous Solution at Physiological pH

    Science.gov (United States)

    Ni, Nanting; Laughlin, Sarah; Wang, Yingji; Feng, You; Zheng, Yujun

    2012-01-01

    The boronic acid group is widely used in chemosensor design due to its ability to reversibly bind diol-containing compounds. The thermodynamic properties of the boronic acid-diol binding process have been investigated extensively. However, there are few studies of the kinetic properties of such binding processes. In this report, stopped-flow method was used for the first time to study the kinetic properties of the binding between three model arylboronic acids, 4-, 5-, and 8-isoquinolinylboronic acids, and various sugars. With all the boronic acid-diol pair sexamined, reactions were complete within seconds. The kon values with various sugars follow the order of D-fructose >D-tagatose>D-mannose >D-glucose. This trend tracks the thermodynamic binding affinities for these sugars and demonstrates that the “on” rate is the key factor determining the binding constant. PMID:22464680

  1. Boronic Acid functionalized core-shell polymer nanoparticles prepared by distillation precipitation polymerization for glycopeptide enrichment.

    Science.gov (United States)

    Qu, Yanyan; Liu, Jianxi; Yang, Kaiguang; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

    2012-07-16

    The boronic acid-functionalized core-shell polymer nanoparticles, poly(N,N-methylenebisacrylamide-co-methacrylic acid)@4-vinylphenylboronic acid (poly(MBA-co-MAA)@VPBA), were successfully synthesized for enriching glycosylated peptides. Such nanoparticles were composed of a hydrophilic polymer core prepared by distillation precipitation polymerization (DPP) and a boronic acid-functionalized shell designed for capturing glycopeptides. Owing to the relatively large amount of residual vinyl groups introduced by DPP on the core surface, the VPBA monomer was coated with high efficiency, working as the shell. Moreover, the overall polymerization route, especially the use of DPP, made the synthesis of nanoparticles facile and time-saving. With the poly(MBA-co-MAA)@VPBA nanoparticles, 18 glycopeptides from horseradish peroxidase (HRP) digest were captured and identified by MALDI-TOF mass spectrometric analysis, relative to eight glycopeptides enriched by using commercially available meta-aminophenylboronic acid agarose under the same conditions. When the concentration of the HRP digest was decreased to as low as 5 nmol, glycopeptides could still be selectively isolated by the prepared nanoparticles. Our results demonstrated that the synthetic poly(MBA-co-MAA)@VPBA nanoparticles might be a promising selective enrichment material for glycoproteome analysis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Identification of cinnabarinic acid as a novel endogenous aryl hydrocarbon receptor ligand that drives IL-22 production.

    Directory of Open Access Journals (Sweden)

    Margaret M Lowe

    Full Text Available The aryl hydrocarbon receptor (AHR binds to environmental toxicants including synthetic halogenated aromatic hydrocarbons and is involved in a diverse array of biological processes. Recently, the AHR was shown to control host immunity by affecting the balance between inflammatory T cells that produce IL-17 (Th17 and IL-22 versus regulatory T cells (Treg involved in tolerance. While environmental AHR ligands can mediate this effect, endogenous ligands are likely to be more relevant in host immune responses. We investigated downstream metabolites of tryptophan as potential AHR ligands because (1 tryptophan metabolites have been implicated in regulating the balance between Th17 and Treg cells and (2 many of the AHR ligands identified thus far are derivatives of tryptophan. We characterized the ability of tryptophan metabolites to bind and activate the AHR and to increase IL-22 production in human T cells. We report that the tryptophan metabolite, cinnabarinic acid (CA, is an AHR ligand that stimulates the differentiation of human and mouse T cells producing IL-22. We compare the IL-22-stimulating activity of CA to that of other tryptophan metabolites and define stimulation conditions that lead to CA production from immune cells. Our findings link tryptophan metabolism to AHR activation and define a novel endogenous AHR agonist with potentially broad biological functions.

  3. Identification of cinnabarinic acid as a novel endogenous aryl hydrocarbon receptor ligand that drives IL-22 production.

    Science.gov (United States)

    Lowe, Margaret M; Mold, Jeff E; Kanwar, Bittoo; Huang, Yong; Louie, Alexander; Pollastri, Michael P; Wang, Cuihua; Patel, Gautam; Franks, Diana G; Schlezinger, Jennifer; Sherr, David H; Silverstone, Allen E; Hahn, Mark E; McCune, Joseph M

    2014-01-01

    The aryl hydrocarbon receptor (AHR) binds to environmental toxicants including synthetic halogenated aromatic hydrocarbons and is involved in a diverse array of biological processes. Recently, the AHR was shown to control host immunity by affecting the balance between inflammatory T cells that produce IL-17 (Th17) and IL-22 versus regulatory T cells (Treg) involved in tolerance. While environmental AHR ligands can mediate this effect, endogenous ligands are likely to be more relevant in host immune responses. We investigated downstream metabolites of tryptophan as potential AHR ligands because (1) tryptophan metabolites have been implicated in regulating the balance between Th17 and Treg cells and (2) many of the AHR ligands identified thus far are derivatives of tryptophan. We characterized the ability of tryptophan metabolites to bind and activate the AHR and to increase IL-22 production in human T cells. We report that the tryptophan metabolite, cinnabarinic acid (CA), is an AHR ligand that stimulates the differentiation of human and mouse T cells producing IL-22. We compare the IL-22-stimulating activity of CA to that of other tryptophan metabolites and define stimulation conditions that lead to CA production from immune cells. Our findings link tryptophan metabolism to AHR activation and define a novel endogenous AHR agonist with potentially broad biological functions.

  4. Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

    Science.gov (United States)

    Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

    2018-02-01

    The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at

  5. Increasing human Th17 differentiation through activation of orphan nuclear receptor retinoid acid-related orphan receptor γ (RORγ) by a class of aryl amide compounds.

    Science.gov (United States)

    Zhang, Wei; Zhang, Jing; Fang, Leiping; Zhou, Ling; Wang, Shuai; Xiang, Zhijun; Li, Yuan; Wisely, Bruce; Zhang, Guifeng; An, Gang; Wang, Yonghui; Leung, Stewart; Zhong, Zhong

    2012-10-01

    In a screen for small-molecule inhibitors of retinoid acid-related orphan receptor γ (RORγ), we fortuitously discovered that a class of aryl amide compounds behaved as functional activators of the interleukin 17 (IL-17) reporter in Jurkat cells. Three of these compounds were selected for further analysis and found to activate the IL-17 reporter with potencies of ∼0.1 μM measured by EC₅₀. These compounds were shown to directly bind to RORγ by circular dichroism-based thermal stability experiments. Furthermore, they can enhance an in vitro Th17 differentiation process in human primary T cells. As RORγ remains an orphan nuclear receptor, discovery of these aryl amide compounds as functional agonists will now provide pharmacological tools for us to dissect functions of RORγ and facilitate drug discovery efforts for immune-modulating therapies.

  6. Camphor-10-sulfonic acid catalyzed condensation of 2-naphthol with aromatic/aliphatic aldehydes to 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes

    Directory of Open Access Journals (Sweden)

    Kundu Kshama

    2014-01-01

    Full Text Available (±-Camphor-10-sulfonic acid (CSA catalyzed condensation of 2-naphthol with both aliphatic/aromatic aldehydes at 80°C yielded 14-alkyl/aryl-dibenzoxanthenes as the sole product in high yields. However, the same condensation with benzaldehyde at 25°C afforded a mixture of intermediate 1,1-bis-(2-hydroxynaphthylphenylmethane and 14-phenyl-dibenzoxanthene while the condensation with aliphatic aldehydes at 25°C furnished the corresponding 14-alkyl-dibenzoxanthenes as the sole product. Moreover, condensation of 2-naphthol with aromatic/aliphatic aldehydes with low catalyst loading (2 mol% was greatly accelerated under microwave irradiation to afford the corresponding 14-aryl/alkyl-dibenzoxanthenes as the sole product in high yields.

  7. α-Selective Ni-Catalyzed Hydroalumination of Aryl- and Alkyl-Substituted Terminal Alkynes. Practical Syntheses of Internal Vinyl Aluminums, Halides or Boronates

    Science.gov (United States)

    Gao, Fang; Hoveyda, Amir H.

    2010-01-01

    Methods for Ni-catalyzed hydroalumination of terminal alkynes, leading to the formation of α-vinylaluminum isomers efficiently (>98% conv in 2–12 h) and with high selectivity (95% to >98% α), are described. Catalytic α-selective hydroalumination reactions proceed in the presence of a reagent (diisobutylaluminum hydride; dibal–H) and 3.0 mol % metal complex (Ni(dppp)Cl2) that are commercially available and inexpensive. Under the same conditions, but with Ni(PPh3)2Cl2, hydroalumination becomes highly β-selective, and, unlike uncatalyzed transformations with dibal–H, generates little or no alkynylaluminum byproducts. All hydrometallation reactions are reliable, operationally simple and practical, and afford an assortment of vinylaluminums that are otherwise not easily accessible. The derived α-vinyl halides and boronates can be synthesized through direct treatment with the appropriate electrophiles [e.g., Br2 and methoxy(pinacolato)boron, respectively]. Ni-catalyzed hydroaluminations can be performed with as little as 0.1 mol % catalyst and on gram scale with equally high efficiency and selectivity. PMID:20698643

  8. Aryl hydrocarbon receptor–ligand axis mediates pulmonary fibroblast migration and differentiation through increased arachidonic acid metabolism

    International Nuclear Information System (INIS)

    Su, Hsiang-Han; Lin, Hsin-Ting; Suen, Jau-Ling; Sheu, Chau Chyun; Yokoyama, Kazunari K.; Huang, Shau-Ku; Cheng, Chih Mei

    2016-01-01

    Pulmonary fibroblast migration and differentiation are critical events in fibrogenesis; meanwhile, fibrosis characterizes the pathology of many respiratory diseases. The role of aryl hydrocarbon receptor (AhR), a unique cellular chemical sensor, has been suggested in tissue fibrosis, but the mechanisms through which the AhR-ligand axis influences the fibrotic process remain undefined. In this study, the potential impact of the AhR-ligand axis on pulmonary fibroblast migration and differentiation was analyzed using human primary lung fibroblasts HFL-1 and CCL-202 cells. Boyden chamber-based cell migration assay showed that activated AhR in HFL-1cells significantly enhanced cell migration in response to 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD), and a known AhR antagonist, CH223191, inhibited its migratory activity. Furthermore, the calcium mobilization and subsequent upregulated expression of arachidonic acid metabolizing enzymes, including cyclooxygenase2 (COX-2) and 5-lipoxygenase (5-LOX), were observed in TCDD-treated HFL-1 cells, concomitant with elevated levels of prostaglandin E2 (PGE2) and leukotriene B4 (LTB4) secretion. Also, significantly increased expression of α-smooth muscle actin α-SMA), a fibroblast differentiation marker, was also noted in TCDD-treated HFL-1 cells (p < 0.05), resulting in a dynamic change in cytoskeleton protein levels and an increase in the nuclear translocation of the myocardin-related transcription factor. Moreover, the enhanced levels of α-SMA expression and fibroblast migration induced by TCDD, PGE2 and LTB4 were abrogated by selective inhibitors for COX-2 and 5-LOX. Knockdown of AhR by siRNA Completely diminished intracellular calcium uptake and reduced α-SMA protein verified by promoter-reporter assays and chromatin immunoprecipitation. Taken together, our results suggested the importance of the AhR-ligand axis in fibroblast migration and differentiation through its capacity in enhancing arachidonic acid metabolism.

  9. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    Directory of Open Access Journals (Sweden)

    M. Onciu

    2005-02-01

    Full Text Available Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP and pyridine (Py as bases and N-methyl-2-pyrolidinone (NMP as solvent, at reflux (180-190°C for 8-12 hours.

  10. Boron analyses in the reactor coolant system of French PWR by acid-base titration ([B]) and ICP-MS (10B atomic %): key to NPP safety

    International Nuclear Information System (INIS)

    Jouvet, Fabien; Roux, Sylvie; Carabasse, Stephanie; Felgines, Didier

    2012-09-01

    Boron is widely used by Nuclear Power Plants and especially by EDF Pressurized Water Reactors to ensure the control of the neutron rate in the reactor coolant system and, by this way, the fission reaction. The Boron analysis is thus a major factor of safety which enables operators to guarantee the permanent control of the reactor. Two kinds of analyses carried out by EDF on the Boron species, recently upgraded regarding new method validation standards and developed to enhance the measurement quality by reducing uncertainties, will be discussed in this topic: Acid-Base titration of Boron and Boron isotopic composition by Inductively Coupled Plasma Mass Spectrometer - ICP MS. (authors)

  11. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    Science.gov (United States)

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Magnetic vinylphenyl boronic acid microparticles for Cr(VI) adsorption: Kinetic, isotherm and thermodynamic studies

    International Nuclear Information System (INIS)

    Kara, Ali; Demirbel, Emel; Tekin, Nalan; Osman, Bilgen; Beşirli, Necati

    2015-01-01

    Highlights: • Cr(VI) can oxidize biological molecules and be one of the most harmful substance. • Magnetic seperation techniques are used on different applications in many fields. • Magnetic systems can be used for rapid and selective removal as a magnetic processor. • We investigate properties of both new material and other magnetic adsorbents reported in the literatures on the adsorption of Cr(VI) ions. • No researchments were reported on adsorption of Cr(VI) with magnetic vinylphenyl boronic acid microparticles. - Abstract: Magnetic vinylphenyl boronic acid microparticles, poly(ethylene glycol dimethacrylate(EG)–vinylphenyl boronic acid(VPBA)) [m-poly(EG–VPBA)], produced by suspension polymerization and characterized, was found to be an efficient solid polymer for Cr(VI) adsorption. The m-poly(EG–VPBA) microparticles were prepared by copolymerizing of ethylene glycol dimethylacrylate (EG) with 4-vinyl phenyl boronic acid (VPBA). The m-poly(EG–VPBA) microparticles were characterized by N 2 adsorption/desorption isotherms, electron spin resonance (ESR), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), elemental analysis, scanning electron microscope (SEM) and swelling studies. The m-poly(EG–VPBA) microparticles were used at adsorbent/Cr(VI) ion ratios. The influence of pH, Cr(VI) initial concentration, temperature of the removal process was investigated. The maximum removal of Cr(VI) was observed at pH 2. Langmuir isotherm and Dubinin–Radushkvich isotherm were found to better fit the experiment data rather than Fruendlich isotherm. The kinetics of the adsorption process of Cr(VI) on the m-poly(EG–VPBA) microparticles were investigated using the pseudo first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models, results showed that the pseudo-second order equation model provided the best correlation with the experimental results. The thermodynamic

  13. Boronic acid based imprinted electrochemical sensor for rutin recognition and detection.

    Science.gov (United States)

    Wang, Chunlei; Wang, Qi; Zhong, Min; Kan, Xianwen

    2016-10-21

    Multi-walled carbon nanotubes (MWNTs) and boronic acid based molecular imprinting polymer (MIP) were successively modified on a glassy carbon electrode surface to fabricate a novel electrochemical sensor for rutin recognition and detection. 3-Aminophenylboronic acid (APBA) was chosen as a monomer for the electropolymerization of MIP film in the presence of rutin. In addition to the imprinted cavities in MIP film to complement the template molecule in shape and functional groups, the high affinity between the boronic acid group of APBA and vicinal diols of rutin also enhanced the selectivity of the sensor, which made the sensor display a good selectivity to rutin. Moreover, the modified MWNTs improved the sensitivity of the sensor for rutin detection. The mole ratios of rutin and APBA, electropolymerized scan cycles and rates, and pH value of the detection solution were optimized. Under optimal conditions, the sensor was used to detect rutin in a linear range from 4.0 × 10 -7 to 1.0 × 10 -5 mol L -1 with a detection limit of 1.1 × 10 -7 mol L -1 . The sensor has also been applied to assay rutin in tablets with satisfactory results.

  14. Synthesis and Biological Activity of 2',3'-iso-Aryl-abscisic Acid Analogs.

    Science.gov (United States)

    Wan, Chuan; Wang, Mingan; Yang, Dongyan; Han, Xiaoqiang; Che, Chuanliang; Ding, Shanshan; Xiao, Yumei; Qin, Zhaohai

    2017-12-15

    2',3'- iso -Benzoabscisic acid ( iso -PhABA), an excellent selective abscisic acid (ABA) analog, was developed in our previous work. In order to find its more structure-activity information, some structural modifications were completed in this paper, including the substitution of phenyl ring and replacing the ring with heterocycles. Thus, 16 novel analogs of iso -PhABA were synthesized and screened with three bioassays, Arabidopsis and lettuce seed germination and rice seedling elongation. Some of them, i.e., 2',3'- iso -pyridoabscisic acid ( iso -PyABA) and 2',3'- iso -franoabscisic acid ( iso -FrABA), displayed good bioactivities that closed to iso -PhABA and natural (+)-ABA. Some others, for instance, substituted- iso -PhABA, exhibited certain selectivity to different physiological process when compared to iso -PhABA or (+)-ABA. These analogs not only provided new candidates of ABA-like synthetic plant growth regulators (PGRs) for practical application, but also new potential selective agonist/antagonist for probing the specific function of ABA receptors.

  15. Shoot and root responses of Trifolium vesiculosum to boron fertilization in an acidic Brazilian soil

    Directory of Open Access Journals (Sweden)

    Nerilde Favaretto

    2007-07-01

    Full Text Available To analyze the influence of boron fertilization on shoot and root growth of Trifolium vesiculosum (arrowleaf clover, an acid soil profile (60 cm depth with 67% Al saturation was recreated in a column (three layers of 20 cm each. Lime and fertilizer (P and K were incorporated into the top 20 cm. The treatments consisted of six boron rates where boric acid was mixed throughout the profile. Addition of boron to soil with low pH and high Al increased the root and shoot growth, independent of the rate applied. Boron inhibited Al toxicity, but no effect was observed in the root length when Al was not present in the soil. It was also observed that there was more root growth below the plow layer (0-20 cm, suggesting better root distribution in the soil profile which could be important for the plant growth, especially under drought conditions.Estudos têm mostrado que o boro (B afeta o crescimento das raízes em solo ácido reduzindo a toxidez do alumínio (Al. Para analisar a influência do boro no crescimento da parte aérea e raízes do Trifolium Vesiculosum (trevo vesiculoso um perfil de solo ácido (60 cm de profundidade com 67% de saturação de Al foi recriado em uma coluna (três camadas com 20 cm cada. Calcário e adubos (P e K foram incorporados na camada de 0-20 cm. Os tratamentos consistiram de seis doses de boro sendo o ácido bórico incorporado em todo o perfil. A adubação com boro em solo com baixo pH e elevado Al aumentou o crescimento da parte aérea e raízes, no entanto, independente da dose aplicada. Boro pode inibir a toxidez de Al, porém não observou-se efeito no comprimento de raízes sem a presença de Al no solo. Observou-se também um grande aumento no crescimento de raízes abaixo da camada arável (0-20 cm, fornecendo uma melhor distribuição de raízes no perfil do solo, o que pode ser importante para o crescimento da planta especialmente em condição de seca.

  16. From synthesis to function via iterative assembly of N-methyliminodiacetic acid boronate building blocks.

    Science.gov (United States)

    Li, Junqi; Grillo, Anthony S; Burke, Martin D

    2015-08-18

    The study and optimization of small molecule function is often impeded by the time-intensive and specialist-dependent process that is typically used to make such compounds. In contrast, general and automated platforms have been developed for making peptides, oligonucleotides, and increasingly oligosaccharides, where synthesis is simplified to iterative applications of the same reactions. Inspired by the way natural products are biosynthesized via the iterative assembly of a defined set of building blocks, we developed a platform for small molecule synthesis involving the iterative coupling of haloboronic acids protected as the corresponding N-methyliminodiacetic acid (MIDA) boronates. Here we summarize our efforts thus far to develop this platform into a generalized and automated approach for small molecule synthesis. We and others have employed this approach to access many polyene-based compounds, including the polyene motifs found in >75% of all polyene natural products. This platform further allowed us to derivatize amphotericin B, the powerful and resistance-evasive but also highly toxic last line of defense in treating systemic fungal infections, and thereby understand its mechanism of action. This synthesis-enabled mechanistic understanding has led us to develop less toxic derivatives currently under evaluation as improved antifungal agents. To access more Csp(3)-containing small molecules, we gained a stereocontrolled entry into chiral, non-racemic α-boryl aldehydes through the discovery of a chiral derivative of MIDA. These α-boryl aldehydes are versatile intermediates for the synthesis of many Csp(3) boronate building blocks that are otherwise difficult to access. In addition, we demonstrated the utility of these types of building blocks in accessing pharmaceutically relevant targets via an iterative Csp(3) cross-coupling cycle. We have further expanded the scope of the platform to include stereochemically complex macrocyclic and polycyclic molecules

  17. Preparation and reactivity of carboxylic acid-terminated boron-doped diamond electrodes

    International Nuclear Information System (INIS)

    Niedziolka-Joensson, Joanna; Boland, Susan; Leech, Donal; Boukherroub, Rabah; Szunerits, Sabine

    2010-01-01

    The paper reports on the formation of carboxy-terminated boron-doped diamond (BDD) electrodes. The carboxylic acid termination was prepared in a controlled way by reacting photochemically oxidized BDD with succinic anhydride. The resulting interface was readily employed for the linking of an amine-terminated ligand such as an osmium complex bearing an amine terminal group. The interfaces were characterized using X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Contact angle measurements were used to follow the changes in surface wetting properties due to surface functionalization. The chemical reactivity of the carboxyl-terminated BDD was investigated by covalent coupling of the acid groups to an amine-terminated osmium complex.

  18. Cross-Coupling Reaction of Saccharide-Based Alkenyl Boronic Acids with Aryl Halides: The Synthesis of Bergenin

    Czech Academy of Sciences Publication Activity Database

    Parkan, K.; Pohl, Radek; Kotora, M.

    2014-01-01

    Roč. 20, č. 15 (2014), s. 4414-4419 ISSN 0947-6539 Grant - others:GA ČR(CZ) GPP207/12/P713; GA ČR(CZ) GA13-15915S Institutional support: RVO:61388963 Keywords : CC coupling * glycosides * natural products * protecting groups * synthetic methods Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  19. Tannic Acid an Efficient Catalyst for the Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one Derivatives

    Directory of Open Access Journals (Sweden)

    Deepak S. Kawade

    2015-06-01

    Full Text Available Tannic acid explore a highly efficient catalytic activity for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one derivatives in excellent yields via cyclocondensation of aromatic aldehyde, β-naphthol and dimedone. Catalyst having advantages such as it is cheap and biodegradable and the protocol avoids the use of expensive catalyst and toxic solvent. We believe that this methodology is an efficient, simple, highly yielding, time saving and environmentally friendly. DOI: http://dx.doi.org/10.17807/orbital.v7i2.683

  20. Fluorescent boronic acid terminated polymer grafted silica particles synthesized via click chemistry for affinity separation of saccharides

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zhifeng, E-mail: 897061147@qq.com; Deng, Peihong; Tang, Siping; Li, Junhua

    2014-07-01

    Boronic acids are important for effective separation of biological active cis-diols. For the purpose of constructing a new type of saccharide-sensitive material which can not only provide convenient separation but also improve the access of boronic acid to guest molecules, the fluorogenic boronic acid terminated, thermo-sensitive polymers (BA-polyNIPAm) were grafted to an alkyne modified silica gel through the exploitation of click chemistry. The BA-polyNIPAm grafted silica gel (BA-polyNIPAm-SG) was characterized by FT-IR, fluorescence spectra, fluorescence microscopy, elemental analysis (EA), thermal gravimetric analysis (TGA), scanning electron microscope (SEM) and so on. BA-polyNIPAm-SG displayed affinity binding ability for saccharides under physiological pH value and allowed saccharides to be conveniently separated from solution. The maximum binding capacities for fructose and glucose are 83.2 μmol/g and 70.4 μmol/g polymer, respectively. The intensity of fluorescence emission of BA-polyNIPAm-SG increased with the increasing of fructose concentration. The present study provides a new kind of composite material which contains moveable and flexible grippers for recognizing and binding guest molecules. - Highlights: • Fluorogenic boronic acid terminated polymers were conjugated to silica particle. • The prepared material can conveniently separate saccharides from solution. • The prepared material displays increased fluorescence emission upon binding fructose.

  1. Fluorescent boronic acid terminated polymer grafted silica particles synthesized via click chemistry for affinity separation of saccharides

    International Nuclear Information System (INIS)

    Xu, Zhifeng; Deng, Peihong; Tang, Siping; Li, Junhua

    2014-01-01

    Boronic acids are important for effective separation of biological active cis-diols. For the purpose of constructing a new type of saccharide-sensitive material which can not only provide convenient separation but also improve the access of boronic acid to guest molecules, the fluorogenic boronic acid terminated, thermo-sensitive polymers (BA-polyNIPAm) were grafted to an alkyne modified silica gel through the exploitation of click chemistry. The BA-polyNIPAm grafted silica gel (BA-polyNIPAm-SG) was characterized by FT-IR, fluorescence spectra, fluorescence microscopy, elemental analysis (EA), thermal gravimetric analysis (TGA), scanning electron microscope (SEM) and so on. BA-polyNIPAm-SG displayed affinity binding ability for saccharides under physiological pH value and allowed saccharides to be conveniently separated from solution. The maximum binding capacities for fructose and glucose are 83.2 μmol/g and 70.4 μmol/g polymer, respectively. The intensity of fluorescence emission of BA-polyNIPAm-SG increased with the increasing of fructose concentration. The present study provides a new kind of composite material which contains moveable and flexible grippers for recognizing and binding guest molecules. - Highlights: • Fluorogenic boronic acid terminated polymers were conjugated to silica particle. • The prepared material can conveniently separate saccharides from solution. • The prepared material displays increased fluorescence emission upon binding fructose

  2. Hyperbranched-polyol-tethered poly (amic acid) electrospun nanofiber membrane with ultrahigh adsorption capacity for boron removal

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhe; Wu, Zhongyu; Zhang, Yufeng; Meng, Jianqiang, E-mail: jianqiang.meng@hotmail.com

    2017-04-30

    Highlights: • Electrospun nanofiber membranes were grafted with hyperbranched polyols. • The membrane had a maximum boron uptake of 5.68 mmol/g. • The membrane could adsorb 0.82 mmol/g boron from a 5 mg/L solution in 15 min. • The membrane obeyed the Langmuir and the pseudo-first-order kinetic model. • The regeneration efficiency remained over 90% after 10 cycled uses. - Abstract: The development of efficient adsorbents with high sorption capacity remains as a challenge for the removal of micropollutants occurred globally in water resources. In this work, poly (amic acid) (PAA) electrospun nanofiber membranes grafted with hyperbranched polyols were synthesized and used for boron removal. The PAA nanofiber was reacted with hyperbranched polyethylenimine (HPEI) and further with glycidol to introduce the vicinal hydroxyl groups. The chemical composition and surface characteristics of the obtained PAA-g-PG membranes were evaluated by FESEM, FTIR, XPS and water contact angles (WCA) measurements. The boron adsorption thermodynamics and kinetics were investigated systematically. The results showed that the PAA nanofiber spun from concentration of 15% had uniform morphology and narrow diameter distribution. The PAA-g-PG nanofiber membrane had a maximum boron uptake of 5.68 mmol/g and could adsorb 0.82 mmol/g boron from a 5 mg/L solution in 15 min. Both the high surface area of nanofibers and the hyperbranched structure should contribute to the high boron uptake and high adsorption rate. The nanofiber membrane obeyed the Langmuir adsorption model and the pseudo-first-order kinetic model. The regeneration efficiency of the nanofiber membrane remained 93.9% after 10 cycled uses, indicating good regenerability of the membrane.

  3. DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

    Science.gov (United States)

    Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

    2018-05-01

    The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

  4. Potent and Selective Peptidyl Boronic Acid Inhibitors of the Serine Protease Prostate-Specific Antigen

    Science.gov (United States)

    LeBeau, Aaron M.; Singh, Pratap; Isaacs, John T.; Denmeade, Samuel R.

    2012-01-01

    SUMMARY Prostate cancer cells produce high (microgram to milligram/milliliter) levels of the serine protease Prostate-Specific Antigen (PSA). PSA is enzymatically active in the extracellular fluid surrounding prostate cancers but is found at 1,000- to 10,000-fold lower concentrations in the circulation, where it is inactivated due to binding to abundant serum protease inhibitors. The exclusive presence of high levels of active PSA within prostate cancer sites makes PSA an attractive candidate for targeted imaging and therapeutics. A synthetic approach based on a peptide substrate identified first peptide aldehyde and then boronic acid inhibitors of PSA. The best of these had the sequence Cbz-Ser-Ser-Lys-Leu-(boro)Leu, with a Ki for PSA of 65 nM. The inhibitor had a 60-fold higher Ki for chymotrypsin. A validated model of PSA’s catalytic site confirmed the critical interactions between the inhibitor and residues within the PSA enzyme. PMID:18635003

  5. Enhanced dispersion of boron nitride nanosheets in aqueous media by using bile acid-based surfactants

    Science.gov (United States)

    Chae, Ari; Park, Soo-Jin; Min, Byunggak; In, Insik

    2018-01-01

    Facile noncovalent surface functionalization of hydroxylated boron nitride nanosheet (BNNS-OH) was attempted through the sonication-assisted exfoliation of h-BN in aqueous media in the presence of bile acid-based surfactants such as sodium cholic acid (SC) or sodium deoxycholic acid (SDC), resulting in SC- or SDC-BNNS-OH dispersion with high up to 2 mg ml-1 and enhanced dispersion stability due to the increased negative zeta potential. While prepared SC-BNNS-OH revealed multi-layered BNNS structures, the large lateral sizes of hundreds nanometers and clear h-BN lattice structures are very promising for the preparation and application of water-processable BNNS-based nanomaterials. It is regarded that noncovalent functionalization of BNNS-OH based on σ-π interaction between with σ-rich bile acid-based amphiphiles and π-rich BNNS is very effective to formulate multi-functional BNNS-based nanomaterials or hybrids that can be utilized in various applications where both the pristine properties of BNNS and the extra functions are simultaneously required.

  6. Determination of glycated albumin using boronic acid-derived agarose beads on paper-based devices.

    Science.gov (United States)

    Ko, Euna; Tran, Van-Khue; Geng, Yanfang; Kim, Min Ki; Jin, Ga Hyun; Son, Seong Eun; Hur, Won; Seong, Gi Hun

    2018-01-01

    Self-monitoring of glycated albumin (GA), a useful glycemic marker, is an established method for preventing diabetes complications. Here, the paper-based lateral flow assay devices were developed for the sensitive detection of GA and the total human serum albumin (tHSA) in self-monitoring diabetes patients. Boronic acid-derived agarose beads were packed into a hole on a lateral flow channel. These well-coordinated agarose beads were used to capture GA through specific cis-diol interactions and to enhance the colorimetric signals by concentrating the target molecules. The devices exhibited large dynamic ranges (from 10  μ g/ml to 10 mg/ml for GA and from 10 mg/ml to 50 mg/ml for tHSA) and low detection limits (7.1  μ g/ml for GA and 4.7 mg/ml for tHSA), which cover the range of GA concentration in healthy plasma, which is 0.21-1.65 mg/ml (0.6%-3%). In determining the unknown GA concentrations in two commercial human plasma samples, the relative percentage difference between the values found by a standard ELISA kit and those found by our developed devices was 2.62% and 8.80%, which are within an acceptable range. The measurements of GA and tHSA were completed within 20 min for the total sample-to-answer diagnosis, fulfilling the demand for rapid analysis. Furthermore, the recovery values ranged from 99.4% to 110% in device accuracy tests. These results indicate that the developed paper-based device with boronic acid-derived agarose beads is a promising platform for GA and tHSA detection as applied to self-monitoring systems.

  7. Alginic Acid-Aided Dispersion of Carbon Nanotubes, Graphene, and Boron Nitride Nanomaterials for Microbial Toxicity Testing.

    Science.gov (United States)

    Wang, Ying; Mortimer, Monika; Chang, Chong Hyun; Holden, Patricia A

    2018-01-30

    Robust evaluation of potential environmental and health risks of carbonaceous and boron nitride nanomaterials (NMs) is imperative. However, significant agglomeration of pristine carbonaceous and boron nitride NMs due to strong van der Waals forces renders them not suitable for direct toxicity testing in aqueous media. Here, the natural polysaccharide alginic acid (AA) was used as a nontoxic, environmentally relevant dispersant with defined composition to disperse seven types of carbonaceous and boron nitride NMs, including multiwall carbon nanotubes, graphene, boron nitride nanotubes, and hexagonal boron nitride flakes, with various physicochemical characteristics. AA's biocompatibility was confirmed by examining AA effects on viability and growth of two model microorganisms (the protozoan Tetrahymena thermophila and the bacterium Pseudomonas aeruginosa ). Using 400 mg·L -1 AA, comparably stable NM (200 mg·L -1 ) stock dispersions were obtained by 30-min probe ultrasonication. AA non-covalently interacted with NM surfaces and improved the dispersibility of NMs in water. The dispersion stability varied with NM morphology and size rather than chemistry. The optimized dispersion protocol established here can facilitate preparing homogeneous NM dispersions for reliable exposures during microbial toxicity testing, contributing to improved reproducibility of toxicity results.

  8. Alginic Acid-Aided Dispersion of Carbon Nanotubes, Graphene, and Boron Nitride Nanomaterials for Microbial Toxicity Testing

    Directory of Open Access Journals (Sweden)

    Ying Wang

    2018-01-01

    Full Text Available Robust evaluation of potential environmental and health risks of carbonaceous and boron nitride nanomaterials (NMs is imperative. However, significant agglomeration of pristine carbonaceous and boron nitride NMs due to strong van der Waals forces renders them not suitable for direct toxicity testing in aqueous media. Here, the natural polysaccharide alginic acid (AA was used as a nontoxic, environmentally relevant dispersant with defined composition to disperse seven types of carbonaceous and boron nitride NMs, including multiwall carbon nanotubes, graphene, boron nitride nanotubes, and hexagonal boron nitride flakes, with various physicochemical characteristics. AA’s biocompatibility was confirmed by examining AA effects on viability and growth of two model microorganisms (the protozoan Tetrahymena thermophila and the bacterium Pseudomonas aeruginosa. Using 400 mg·L−1 AA, comparably stable NM (200 mg·L−1 stock dispersions were obtained by 30-min probe ultrasonication. AA non-covalently interacted with NM surfaces and improved the dispersibility of NMs in water. The dispersion stability varied with NM morphology and size rather than chemistry. The optimized dispersion protocol established here can facilitate preparing homogeneous NM dispersions for reliable exposures during microbial toxicity testing, contributing to improved reproducibility of toxicity results.

  9. A Novel Fiber Optic Surface Plasmon Resonance Biosensors with Special Boronic Acid Derivative to Detect Glycoprotein

    Directory of Open Access Journals (Sweden)

    Yang Zhang

    2017-10-01

    Full Text Available We proposed and demonstrated a novel tilted fiber Bragg grating (TFBG-based surface plasmon resonance (SPR label-free biosensor via a special boronic acid derivative to detect glycoprotein with high sensitivity and selectivity. TFBG, as an effective sensing element for optical sensing in near-infrared wavelengths, possess the unique capability of easily exciting the SPR effect on fiber surface which coated with a nano-scale metal layer. SPR properties can be accurately detected by measuring the variation of transmitted spectra at optical communication wavelengths. In our experiment, a 10° TFBG coated with a 50 nm gold film was manufactured to stimulate SPR on a sensor surface. To detect glycoprotein selectively, the sensor was immobilized using designed phenylboronic acid as the recognition molecule, which can covalently bond with 1,2- or 1,3-diols to form five- or six-membered cyclic complexes for attaching diol-containing biomolecules and proteins. The phenylboronic acid was synthetized with long alkyl groups offering more flexible space, which was able to improve the capability of binding glycoprotein. The proposed TFBG-SPR sensors exhibit good selectivity and repeatability with a protein concentration sensitivity up to 2.867 dB/ (mg/mL and a limit of detection (LOD of 15.56 nM.

  10. Cross-Linked Dependency of Boronic Acid-Conjugated Chitosan Nanoparticles by Diols for Sustained Insulin Release

    Directory of Open Access Journals (Sweden)

    Nabil A. Siddiqui

    2016-10-01

    Full Text Available Boronic acids have been widely investigated for their potential use as glucose sensors in glucose responsive polymeric insulin delivery systems. Interactions between cyclic diols and boronic acids, anchored to polymeric delivery systems, may result in swelling of the delivery system, releasing the drug. In this study, 4-formylphenylboronic acid conjugated chitosan was formulated into insulin containing nanoparticles via polyelectrolyte complexation. The nanoparticles had an average diameter of 140 ± 12.8 nm, polydispersity index of 0.17 ± 0.1, zeta potential of +19.1 ± 0.69 mV, encapsulation efficiency of 81% ± 1.2%, and an insulin loading capacity of 46% ± 1.8% w/w. Changes in size of the nanoparticles and release of insulin were type of sugar- and concentration-dependent. High concentration of diols resulted in a sustained release of insulin due to crosslink formation with boronic acid moieties within the nanoparticles. The formulation has potential to be developed into a self-regulated insulin delivery system for the treatment of diabetes.

  11. Development of Quantitative Structure-Property Relationship Models for Self-Emulsifying Drug Delivery System of 2-Aryl Propionic Acid NSAIDs

    Directory of Open Access Journals (Sweden)

    Chen-Wen Li

    2011-01-01

    Full Text Available We developed the quantative structure-property relationships (QSPRs models to correlate the molecular structures of surfactant, cosurfactant, oil, and drug with the solubility of poorly water-soluble 2-aryl propionic acid nonsteroidal anti-inflammatory drugs (2-APA-NSAIDs in self-emulsifying drug delivery systems (SEDDSs. The compositions were encoded with electronic, geometrical, topological, and quantum chemical descriptors. To obtain reliable predictions, we used multiple linear regression (MLR and artificial neural network (ANN methods for model development. The obtained equations were validated using a test set of 42 formulations and showed a great predictive power, and linear models were found to be better than nonlinear ones. The obtained QSPR models would greatly facilitate fast screening for the optimal formulations of SEDDS at the early stage of drug development and minimize experimental effort.

  12. Boronic acid recognition of non-interacting carbohydrates for biomedical applications: increasing fluorescence signals of minimally interacting aldoses and sucralose.

    Science.gov (United States)

    Resendez, Angel; Halim, Md Abdul; Singh, Jasmeet; Webb, Dominic-Luc; Singaram, Bakthan

    2017-11-22

    To address carbohydrates that are commonly used in biomedical applications with low binding affinities for boronic acid based detection systems, two chemical modification methods were utilized to increase sensitivity. Modified carbohydrates were analyzed using a two component fluorescent probe based on boronic acid-appended viologen-HPTS (4,4'-o-BBV). Carbohydrates normally giving poor signals (fucose, l-rhamnose, xylose) were subjected to sodium borohydride (NaBH 4 ) reduction in ambient conditions for 1 h yielding the corresponding sugar alcohols from fucose, l-rhamnose and xylose in essentially quantitative yields. Compared to original aldoses, apparent binding affinities were increased 4-25-fold. The chlorinated sweetener and colon permeability marker sucralose (Splenda), otherwise undetectable by boronic acids, was dechlorinated to a detectable derivative by reactive oxygen and hydroxide intermediates by the Fenton reaction or by H 2 O 2 and UV light. This method is specific to sucralose as other common sugars, such as sucrose, do not contain any carbon-chlorine bonds. Significant fluorescence response was obtained for chemically modified sucralose with the 4,4'-o-BBV-HPTS probe system. This proof of principle can be applied to biomedical applications, such as gut permeability, malabsorption, etc.

  13. Adsorption of nucleic acid bases and amino acids on single-walled carbon and boron nitride nanotubes: a first-principles study.

    Science.gov (United States)

    Zheng, Jiaxin; Song, Wei; Wang, Lu; Lu, Jing; Luo, Guangfu; Zhou, Jing; Qin, Rui; Li, Hong; Gao, Zhengxiang; Lai, Lin; Li, Guangping; Mei, Wai Ning

    2009-11-01

    We study the adsorptions of nucleic acid bases adenine (A), cytosine (C), guanine (G), thymine (T), and uracil (U) and four amino acids phenylalanine, tyrosine, tryptophan, alanine on the single-walled carbon nanotubes (SWCNTs) and boron nitride nanotubes (SWBNNTs) by using density functional theory. We find that the aromatic content plays a critical role in the adsorption. The adsorptions of nucleic acid bases and amino acids on the (7, 7) SWBNNT are stronger than those on the (7, 7) SWCNT. Oxidative treatment of SWCNTs favors the adsorption of biomolecules on nanotubes.

  14. Simultaneous Chronoamperometric Sensing of Ascorbic Acid and Acetaminophen at a Boron-Doped Diamond Electrode

    Directory of Open Access Journals (Sweden)

    Ciprian Radovan

    2008-06-01

    Full Text Available Cyclic voltammetry (CV and chronoamperometry (CA have been used to sense and determine simultaneously L-ascorbic acid (AA and acetaminophen (AC at a boron-doped diamond electrode (BDDE in a Britton-Robinson buffer solution. The calibration plots of anodic current peak versus concentration obtained from CV and CA data for both investigated compounds in single and di-component solutions over the concentration range 0.01 mM – 0.1 mM proved to be linear, with very good correlation parameters. Sensitivity values and RSD of 2-3% were obtained for various situations, involving both individual and simultaneous presence of AA and AC. The chronoamperometric technique associated with standard addition in sequential one step and/or two successive and continuous chronoamperograms at two characteristic potential levels represented a feasible option for the simultaneous determination of AA and AC in real sample systems such as pharmaceutical formulations. The average values indicated by the supplier were confirmed to a very close approximation from chronoamperomgrams by using several additions with the application of suitable current correction factors.

  15. Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

    Science.gov (United States)

    Alver, Özgur; Kaya, Mehmet Fatih

    2014-11-01

    Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.

  16. Hypochlorous acid turn-on boron dipyrromethene probe based on oxidation of methyl phenyl sulfide

    International Nuclear Information System (INIS)

    Liu, Shi-Rong; Vedamalai, Mani; Wu, Shu-Pao

    2013-01-01

    Graphical abstract: -- Highlights: •A BODIPY-based green fluorescent probe for sensing HOCl was developed. •The probe utilizes HOCl-promoted oxidation of methyl phenyl sulfide to produce a proportional fluorescence response to the concentration of HOCl. •Confocal fluorescence microscopy imaging of RAW264.7 cells demonstrated that the HCS probe might have application in the investigation of HOCl roles in biological systems. -- Abstract: A boron dipyrromethene (BODIPY)-based fluorometric probe, HCS, has been successfully developed for the highly sensitive and selective detection of hypochlorous acid (HOCl). The probe is based on the specific HOCl-promoted oxidation of methyl phenyl sulfide. The reaction is accompanied by a 160-fold increase in the fluorescent quantum yield (from 0.003 to 0.480). The fluorescent turn-on mechanism is accomplished by suppression of photoinduced electron transfer (PET) from the methyl phenyl sulfide group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCS shows a good linearity in the HOCl concentration range 1–10 μM. The detection limit is 23.7 nM (S/N = 3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrates that the HCS probe could be an efficient fluorescent detector for HOCl in living cells

  17. Hypochlorous acid turn-on boron dipyrromethene probe based on oxidation of methyl phenyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shi-Rong; Vedamalai, Mani; Wu, Shu-Pao, E-mail: spwu@mail.nctu.edu.tw

    2013-10-24

    Graphical abstract: -- Highlights: •A BODIPY-based green fluorescent probe for sensing HOCl was developed. •The probe utilizes HOCl-promoted oxidation of methyl phenyl sulfide to produce a proportional fluorescence response to the concentration of HOCl. •Confocal fluorescence microscopy imaging of RAW264.7 cells demonstrated that the HCS probe might have application in the investigation of HOCl roles in biological systems. -- Abstract: A boron dipyrromethene (BODIPY)-based fluorometric probe, HCS, has been successfully developed for the highly sensitive and selective detection of hypochlorous acid (HOCl). The probe is based on the specific HOCl-promoted oxidation of methyl phenyl sulfide. The reaction is accompanied by a 160-fold increase in the fluorescent quantum yield (from 0.003 to 0.480). The fluorescent turn-on mechanism is accomplished by suppression of photoinduced electron transfer (PET) from the methyl phenyl sulfide group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCS shows a good linearity in the HOCl concentration range 1–10 μM. The detection limit is 23.7 nM (S/N = 3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrates that the HCS probe could be an efficient fluorescent detector for HOCl in living cells.

  18. Boron-containing acids: preliminary evaluation of acute toxicity and access to the brain determined by Raman scattering spectroscopy.

    Science.gov (United States)

    Soriano-Ursúa, Marvin A; Farfán-García, Eunice D; López-Cabrera, Yessica; Querejeta, Enrique; Trujillo-Ferrara, José G

    2014-01-01

    Boron-containing compounds (BCCs), particularly boron containing acids (BCAs), have become attractive moieties or molecules in drug development. It has been suggested that when functional groups with boron atoms are added to well-known drugs, the latter are conferred with greater potency and efficacy in relation to their target receptors. However, the use of BCAs in drug development is limited due to the lack of a toxicological profile. Consequently, the aim of the present study was to evaluate the acute toxicity of boric and boronic acids. Thus, a determination was made of the lethal dose (LD50) of test compounds in male CD1 mice, as well as the effective dose required to negatively affect spontaneous motor activity and to produce notable behavioral abnormalities. After treatment of animals at different doses, macroscopic observations were made from a necropsy, and Raman scattering spectroscopic studies were carried out on brain tissue samples. In general, the results show that most of the tested BCAs have very low toxicity, evidenced by the high doses required to induce notable toxic effects (greater than 100 mg/kg of body weight for all compounds, except for 3-thyenilboronic acid). Such toxic effects, presumably mediated by action on the CNS, include eye damage, gastrointestinal effects (e.g., gastric-gut dilatation and fecal retention), sedation, hypnosis and/or trembling. This preliminary toxicological profile suggests that BCAs can be considered potential therapeutic agents or moieties to be added to other compounds in the development of new drugs. Future studies are required to explore possible chronic toxicity of BCCs. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

    Directory of Open Access Journals (Sweden)

    Volodymyr V. Tkachenko

    2014-12-01

    Full Text Available The switchable three-component reactions of 5-amino-3-methylisoxazole, salicylaldehyde and N-aryl-3-oxobutanamides under different conditions were studied and discussed. The unexpected influence of the aryl substituent in N-aryl-3-oxobutanamides on the behavior of the reaction was discovered. The key influence of ultrasonication and Lewis acid catalysts led to an established protocol to selectively obtain two or three types of heterocyclic scaffolds depending on the substituent in the N-aryl moiety.

  20. Reconstitution of Vanadium Haloperoxidase's Catalytic Activity by Boric Acid-Towards a Potential Biocatalytic Role of Boron.

    Science.gov (United States)

    Natalio, Filipe; Wiese, Stefanie; Brandt, Wolfgang; Wessjohann, Ludger

    2017-04-11

    Boron's unusual properties inspired major advances in chemistry. In nature, the existence and importance of boron has been fairly explored (e.g. bacterial signaling, plant development) but its role as biological catalyst was never reported. Here, we show that boric acid [B(OH) 3 ] can restore chloroperoxidase activity of Curvularia inaequalis recombinant apo-haloperoxidase's (HPO) in the presence of hydrogen peroxide and chloride ions. Molecular modeling and semi-empirical PM7 calculations support a thermodynamically highly favored (bio)catalytic mechanism similarly to vanadium haloperoxidases (V-HPO) in which [B(OH) 3 ] is assumedly located in apo-HPO's active site and a monoperoxyborate [B(OH) 3 (OOH) - ] intermediate is formed and stabilized by interaction with specific active site amino acids leading ultimately to the formation of HOCl. Thus, B(OH) 3 -HPO provides the first evidence towards the future exploitation of boron's role in biological systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Abscisic acid and transpiration rate are involved in the response to boron toxicity in Arabidopsis plants.

    Science.gov (United States)

    Macho-Rivero, Miguel Ángel; Camacho-Cristóbal, Juan José; Herrera-Rodríguez, María Begoña; Müller, Maren; Munné-Bosch, Sergi; González-Fontes, Agustín

    2017-05-01

    Boron (B) is an essential microelement for vascular plant development, but its toxicity is a major problem affecting crop yields in arid and semi-arid areas of the world. In the literature, several genes involved in abscisic acid (ABA) signalling and responses are upregulated in Arabidopsis roots after treatment with excess B. It is known that the AtNCED3 gene, which encodes a crucial enzyme for ABA biosynthesis, plays a key role in the plant response to drought stress. In this study, root AtNCED3 expression and shoot ABA content were rapidly increased in wild-type plants upon B-toxicity treatment. The Arabidopsis ABA-deficient nced3-2 mutant had higher transpiration rate, stomatal conductance and accumulated more B in their shoots than wild-type plants, facts that were associated with the lower levels of ABA in this mutant. However, in wild-type plants, B toxicity caused a significant reduction in stomatal conductance, resulting in a decreased transpiration rate. This response could be a mechanism to limit the transport of excess B from the roots to the leaves under B toxicity. In agreement with the higher transpiration rate of the nced3-2 mutant, this genotype showed an increased leaf B concentration and damage upon exposure to 5 mM B. Under B toxicity, ABA application decreased B accumulation in wild-type and nced3-2 plants. In summary, this work shows that excess B applied to the roots leads to rapid changes in AtNCED3 expression and gas exchange parameters that would contribute to restrain the B entry into the leaves, this effect being mediated by ABA. © 2016 Scandinavian Plant Physiology Society.

  2. Doxorubicin delivery to 3D multicellular spheroids and tumors based on boronic acid-rich chitosan nanoparticles.

    Science.gov (United States)

    Wang, Xin; Zhen, Xu; Wang, Jing; Zhang, Jialiang; Wu, Wei; Jiang, Xiqun

    2013-06-01

    Boronic acid-rich chitosan-poly(N-3-acrylamidophenylboronic acid) nanoparticles (CS-PAPBA NPs) with the tunable size were successfully prepared by polymerizing N-3-acrylamidophenylboronic acid in the presence of chitosan in an aqueous solution. The CS-PAPBA NPs were then functionalized by a tumor-penetrating peptide iRGD and loading doxorubicin (DOX). The interaction between boronic acid groups of hydrophobic PAPBA and the amino groups of hydrophilic chitosan inside the nanoparticles was examined by solid-state NMR measurement. The size and morphology of nanoparticles were characterized by dynamic light scattering and electron microscopy. The cellular uptake, tumor penetration, biodistribution and antitumor activity of the nanoparticles were evaluated by using three-dimensional (3-D) multicellular spheroids (MCs) as the in vitro model and H22 tumor-bearing mice as the in vivo model. It was found that the iRGD-conjugated nanoparticles significantly improved the efficiency of DOX penetration in MCs, compared with free DOX and non-conjugated nanoparticles, resulting in the efficient cell killing in the MCs. In vivo antitumor activity examination indicated that iRGD-conjugated CS-PAPBA nanoparticles promoted the accumulation of nanoparticles in tumor tissue and enhanced their penetration in tumor areas, both of which improved the efficiency of DOX-loaded nanoparticles in restraining tumor growth and prolonging the life time of H22 tumor-bearing mice. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Synthesis of PBAD-lipiodol nanoparticles for combination treatment with boric acid in boron neutron capture therapy for hepatoma in-vitro

    International Nuclear Information System (INIS)

    Chou, F.I.; Chung, H.P.; Liu, H.M.; Wen, H.W.; Chi, C.W.; Lin, Shanyang; Lui, W.Y.; Kai, J.J.

    2006-01-01

    This study attempted to increase BNCT efficiency for hepatoma by a combined treatment of phenylboric acid derivative entrapped lipiodol nanoparticles (PBAD-L nanoparticles) with boric acid. The size of PBAD-L nanoparticles were 400-750 nm at the boron concentrations of 0.3-2.7 mg/ml. After 24 hours the boron concentration in PBAD-L nanoparticles treated human hepatoma HepG2 cells was 112 ppm, while that in rat liver Clone 9 cells was 52 ppm. With the use of 25 μg B/ml boric acid, after 6 hours the boron concentration in HepG2 and Clone 9 cells were 75 ppm and 40 ppm, respectively. In a combined treatment, boron concentration in HepG2 cells which were treated with PBAD-L nanoparticles for 18 hours and then combined with boric acid for 6 hours was 158 ppm. After neutron irradiation, the surviving fraction of HepG2 cells treated with PBAD-L nanoparticles was 12.6%, while that in the ones with a combined treatment was 1.3%. In conclusion, the combined treatment provided a higher boron concentration in HepG2 cells than treatments with either PBAD-L nanoparticles or boric acid, resulting in a higher therapeutic efficacy of BNCT in hepatoma cells. (author)

  4. Study of the interaction of boron-containing amino acids for the neutron capture therapy with biologically interesting compounds by using 'three-spot zone electrophoresis'

    International Nuclear Information System (INIS)

    Kitaoka, Yoshinori; Kobayashi, Mitsue; Morimoto, Tsuguhiro; Kirihata, Mitsunori; Ichimoto, Itsuo.

    1995-01-01

    As the boron carriers for boron neutron capture therapy, p-borono phenylalanine (BPA) is the boron compound which has been clinically used together with sodium borocaptate. It was found by the electrophoresis behavior that the BPA interacted with organic carboxylic acids in its dissolved state. In this paper, the electrophoresis behavior of general amino acids as seen in three-spot zone electrophoresis and the peculiar interaction of the amino acids having dihydroxyboryl radical are described. Zone electrophoresis has been developed as separation means, and three-spot process excludes the errors due to accidental factors as far as possible. The behaviors of zone electrophoresis of ordinary neutral amino acids, orthoboric acid and p-BPA are reported. For utilizing the features of boron neutron capture therapy, it is necessary to develop the carrier which is singularly taken into cancer cells. There is not a good method for discriminating normal cells and cancer cells. As for the administration of BPA to patients, its solubility is insufficient, therefore, its fructose complex has been used. The research on the biochemical peculiarity of boron is important. (K.I.)

  5. One-pot synthesis of biocompatible boronic acid-functionalized poly(methyl methacrylate) nanoparticles at sub-100 nm scale for glucose sensing

    Energy Technology Data Exchange (ETDEWEB)

    Sakalak, Huseyin [Selcuk University, Metallurgy and Materials Engineering (Turkey); Ulasan, Mehmet; Yavuz, Emine [Selcuk University, Advanced Technology Research and Application Center (Turkey); Camli, Sevket Tolga, E-mail: tolgacamli@gmail.com [Biyotez Machinery Chemistry R& D Co. Ltd. (Turkey); Yavuz, Mustafa Selman, E-mail: selmanyavuz@selcuk.edu.tr [Selcuk University, Metallurgy and Materials Engineering (Turkey)

    2014-12-15

    Poly(methyl methacrylate) nanoparticles containing 4-vinylphenyl boronic acid were synthesized in one pot by surfactant-free emulsion polymerization. The nanoparticles were characterized by scanning electron microscopy and dynamic light scattering. Boron content in the nanoparticles was confirmed by electron-dispersive X-ray spectroscopy. In polymerization process, several co-monomer ratios were studied in order to obtain optimum nanoparticle size. Average hydrodynamic diameter and polydispersity index of nanoparticles versus variation of acetone percentage in the solvent mixture and total monomer concentration were investigated. The effect of boronic acid concentration in the monomer mixture on nanoparticle size and size distribution was also reported. Without further functionalization to the nanoparticles, the catechol dye, alizarin red S, was bound to boronic acid-containing nanoparticles. These nanoparticles behave as a nanosensor by which glucose or fructose can be easily detected. Dye-containing nanoparticles were undertaken displacement reaction by glucose or fructose. The glucose or fructose content was also monitored by UV–Visible spectrophotometer. Furthermore, cytotoxicity studies of boronic acid-carrying poly(methyl methacrylate) nanoparticles were carried out in 3T3 cells, which showed no toxicity effect on the cells.

  6. One-pot synthesis of biocompatible boronic acid-functionalized poly(methyl methacrylate) nanoparticles at sub-100 nm scale for glucose sensing

    International Nuclear Information System (INIS)

    Sakalak, Huseyin; Ulasan, Mehmet; Yavuz, Emine; Camli, Sevket Tolga; Yavuz, Mustafa Selman

    2014-01-01

    Poly(methyl methacrylate) nanoparticles containing 4-vinylphenyl boronic acid were synthesized in one pot by surfactant-free emulsion polymerization. The nanoparticles were characterized by scanning electron microscopy and dynamic light scattering. Boron content in the nanoparticles was confirmed by electron-dispersive X-ray spectroscopy. In polymerization process, several co-monomer ratios were studied in order to obtain optimum nanoparticle size. Average hydrodynamic diameter and polydispersity index of nanoparticles versus variation of acetone percentage in the solvent mixture and total monomer concentration were investigated. The effect of boronic acid concentration in the monomer mixture on nanoparticle size and size distribution was also reported. Without further functionalization to the nanoparticles, the catechol dye, alizarin red S, was bound to boronic acid-containing nanoparticles. These nanoparticles behave as a nanosensor by which glucose or fructose can be easily detected. Dye-containing nanoparticles were undertaken displacement reaction by glucose or fructose. The glucose or fructose content was also monitored by UV–Visible spectrophotometer. Furthermore, cytotoxicity studies of boronic acid-carrying poly(methyl methacrylate) nanoparticles were carried out in 3T3 cells, which showed no toxicity effect on the cells

  7. Spontaneous arylation of activated carbon from aminobenzene organic acids as source of diazonium ions in mild conditions

    International Nuclear Information System (INIS)

    Lebègue, Estelle; Brousse, Thierry; Gaubicher, Joël; Cougnon, Charles

    2013-01-01

    Activated carbon products modified with benzoic, benzenesulfonic and benzylphosphonic acid groups were prepared by spontaneous reduction of aryldiazonium ions in situ generated in water from the corresponding aminobenzene organic acids without addition of an external acid. Electrochemistry and NMR studies show that the advancement of the diazotization reaction depends both on the acidity and the electronic effect of the organic acid substituent, giving a mixture of diazonium, amine and triazene functionalities. Carbon products prepared by reaction of activated carbon Norit with 4-aminobenzenecarboxylic acid, 4-aminobenzenesulfonic acid and (4-aminobenzyl)phosphonic acid were analyzed by chemical elemental analysis and X-ray photoelectron spectroscopy experiments. Results show that this strategy is well suited for the chemical functionalization, giving a maximized grafting yield due to a chemical cooperation of amine and diazonium functionalities

  8. Design, synthesis and docking studies of novel dipeptidyl boronic acid proteasome inhibitors constructed from αα- and αβ-amino acids.

    Science.gov (United States)

    Shi, Jingmiao; Lei, Meng; Wu, Wenkui; Feng, Huayun; Wang, Jia; Chen, Shanshan; Zhu, Yongqiang; Hu, Shihe; Liu, Zhaogang; Jiang, Cheng

    2016-04-15

    A series of novel dipeptidyl boronic acid proteasome inhibitors constructed from αα- and αβ-amino acids were designed and synthesized. Their structures were elucidated by (1)H NMR, (13)C NMR, LC-MS and HRMS. These compounds were evaluated for their β5 subunit inhibitory activities of human proteasome. The results showed that dipeptidyl boronic acid inhibitors composed of αα-amino acids were as active as bortezomib. Interestingly, the activities of those derived from αβ-amino acids lost completely. Of all the inhibitors, compound 22 (IC50=4.82 nM) was the most potent for the inhibition of proteasome activity. Compound 22 was also the most active against three MM cell lines with IC50 values less than 5 nM in inhibiting cell growth assays. Molecular docking studies displayed that 22 fitted very well in the β5 subunit active pocket of proteasome. Copyright © 2016. Published by Elsevier Ltd.

  9. Structure and luminescent property of complexes of aryl carboxylic acid-functionalized polystyrene with Eu(III) and Tb(III) ions.

    Science.gov (United States)

    Gao, Baojiao; Shi, Nan; Qiao, Zongwen

    2015-11-05

    Via polymer reactions, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polystyrene (PS), respectively, and two aryl carboxylic acid-functionalized polystyrenes, PSNA and PSBA, were obtained. Using PSNA and PSBA as macromolecule ligands and Eu(3+) and Tb(3+) ions as central ions, various luminescent binary polymer-rare earth complexes were prepared. At the same time, with 1,10-phenanthroline (Phen) and 4,4'-bipyridine (Bipy) as small-molecule co-ligands, various ternary polymer-rare earth complexes were also prepared. On the basis of characterizing PSNA, PSBA and complexes, the relationship between structure and luminescent property for these prepared complexes were mainly investigated. The study results show that the macromolecule ligands PSNA and PSBA, or the bonded NA and BA ligands, can strongly sensitize the fluorescence emissions of Eu(3+) ion or Tb(3+) ion, but the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions, namely it is strongly dependent on the matching degree of energy levels. The fluorescence emission of the binary complex PS-(NA)3-Eu(III) is stronger than that PS-(BA)3-Eu(III), indicating ligand NA has stronger sensitization action for Eu(3+) ion than ligand BA; the binary complex PS-(BA)3-Tb(III) emit strong characteristic fluorescence of Tb(3+) ion, displaying that ligand BA can strongly sensitize Tb(3+) ion, whereas the binary complex PS-(NA)3-Tb(III) nearly does not emit the characteristic fluorescence of Tb(3+) ion, showing that ligand NA does not sensitize Tb(3+) ion. The fluorescence intensity of the ternary complexes is much stronger than that of the binary complexes in the same series. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-01-01

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel

  11. 2-([1,2,4]triazolo[1,5-c]quinazolin-2-yl-)alkyl-(alkaryl-, aryl-)-amines and their derivatives. (3Н-quinazolin-4-yliden)hydrazides (1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)alkyl-(alkaryl-, aryl-)carboxylic acids: features of synthesis, modification and ant

    OpenAIRE

    Yu. V. Martynenko; M. S. Kazunin; E. А. Selivanova; S. I. Kovalenko

    2016-01-01

    The combination of different «pharmacophore» components in one structure connected via «linker» functional groups is one of the major and justified approaches for the synthesis of new biologically active substances. In this area (3Н-quinazoline-4-yliden)hydrazides (1,3-dioxo-1,3-dihydro-2H-іsoindol-2-yl-)alkyl-(aralkyl-, aryl-)carboxylic acids are the most interesting compounds. They contain quinazoline and іsoindole fragments united through аlkyl, аlkaryl and аryl groups and furthermore can ...

  12. A sensing approach for dopamine determination by boronic acid-functionalized molecularly imprinted graphene quantum dots composite

    Science.gov (United States)

    Zhou, Xi; Gao, Xuexia; Song, Fengyan; Wang, Chunpeng; Chu, Fuxiang; Wu, Shishan

    2017-11-01

    A novel fluorescence sensor was developed for dopamine (DA) determination based on molecularly imprinted graphene quantum dots and poly(indolylboronic acid) composite (MIPs@ PIn-BAc/GQDs). When the DA is added to the system, it leads to an aggregation and fluorescence quenching of the MIPs@ PIn-BAc/GQDs because of the covalent binding between the catechol group of DA and boronic acid. Such fluorescence behaviors are used for well testing DA in a range from 5 × 10-9 to 1.2 × 10-6 M with the detection limit of 2.5 × 10-9 M. Furthermore, the prepared sensors could well against the interferences from various biomolecules and be successfully used for the assay of DA in human biological samples, exhibiting excellent specificity. It is believed that the prepared MIPs@ PIn-BAc/GQDs hold great promise as a practical platform that can monitor DA level change.

  13. 2-([1,2,4]triazolo[1,5-c]quinazolin-2-yl-alkyl-(alkaryl-, aryl--amines and their derivatives. (3Н-quinazolin-4-ylidenhydrazides (1,3-dioxo-1,3-dihydro-2H-isoindol-2-ylalkyl-(alkaryl-, aryl-carboxylic acids: features of synthesis, modification and ant

    Directory of Open Access Journals (Sweden)

    Yu. V. Martynenko

    2016-08-01

    Full Text Available The combination of different «pharmacophore» components in one structure connected via «linker» functional groups is one of the major and justified approaches for the synthesis of new biologically active substances. In this area (3Н-quinazoline-4-ylidenhydrazides (1,3-dioxo-1,3-dihydro-2H-іsoindol-2-yl-alkyl-(aralkyl-, aryl-carboxylic acids are the most interesting compounds. They contain quinazoline and іsoindole fragments united through аlkyl, аlkaryl and аryl groups and furthermore can be used for the synthesis of new heterocycles. Aim: The purpose of this work is to find antimicrobial and antifungal agents among (3H-quinazolin-4-ylidenehydrazides (1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl-alkyl-(alkaryl-, aryl-carboxylic acids and their fused derivatives and to establish physical-chemical properties of these compounds and to correlate «structure – activity relationship» for structure optimization. Methods and results. The study of microbiological activity was conducted by disco-diffusion method on Mueller-Hinton agar on the following strains of microorganisms: gram-positive cocci (Staphylococcus aureus ATCC 25923, Enterococcus aeruginosa, E. faecalis ATCC 29212, gram-negative bacteria (Pseudomonas aeruginosa PSS27853, Escherichia coli ATCC 25922, facultative anaerobic gram-negative bacteria (Klebsiella pneumoniaе and fungi (Candida albicans ATCC 885653. Conclusion. The protected aminoacids were used to synthesize unknown (3H-quinazolin-4-ylidenehydrazides (1,3-dioxo-1,3-dihydroisoindolo-2-yl-alkyl-(alkaryl-, aryl-carboxylic acids in the reactions of nucleophilic substitution for the first time. While new [1,2,4]triazolo[1,5-c]quinazolin-2-yl-alkyl-(alkaryl-, aryl-- isoindol-1,3(2H-diones were received by heterocyclization of the last. Structure and identity have been confirmed by elemental analysis, physical and chemical methods (1H NMR spectroscopy, mass-spectrometry. Analysis of the results of microbiological study shows, that

  14. Preparation of dual-responsive hybrid fluorescent nano probe based on graphene oxide and boronic acid/BODIPY-conjugated polymer for cell imaging

    Energy Technology Data Exchange (ETDEWEB)

    Khoerunnisa [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Kang, Eun Bi [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Mazrad, Zihnil Adha Islamy [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Lee, Gibaek [Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); In, Insik [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Polymer Science and Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Park, Sung Young, E-mail: parkchem@ut.ac.kr [Department of IT Convergence, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea National University of Transportation, Chungju 380–702 (Korea, Republic of)

    2017-02-01

    Here, we report a pH- and thermo-responsive fluorescent nanomaterial of functionalized reduced graphene oxide (rGO) with cross-linked polymer produced via catechol-boronate diol binding mechanism. When conjugated with the hydrophobic dye boron dipyrromethane (BODIPY), this material can act as a dual-responsive nanoplatform for cells imaging. 2-Chloro-3′,4′-dihydroxyacetophenone (CCDP)-quaternized-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [C-PDN] was cross-linked with BODIPY and 4-chlorophenyl boronic acid (BA)-quaternized-poly(ethylene glycol)-g-poly(dimethylaminoethyl methacrylate-co-N-isopropylacrylamide) [BB-PPDN]. The GO was then reduced by the catechol group in the cross-linked polymer to synthesize rGO nanoparticles, which able to stabilize the quenching mechanism. This nanoplatform exhibits intense fluorescence at acidic pH and low fluorescence at physiological pH. Confocal laser scanning microscopy (CLSM) images shows bright fluorescence at lysosomal pH and total quench at physiological pH. Therefore, we have successfully developed a promising sensitive bio-imaging probe for identifying cancer cells. - Graphical abstract: [BB-PPDN]-[C-PDN]/rGO nanoparticles with boronic acid-catechol cis-diol binding mechanism toward change in pH demonstrated good biocompatibility and effective quenching for cancer cell detection. - Highlights: • Dual responsive (pH- and thermo) fluorescent nano probe was proposed for cells imaging. • The mechanism was based on cis-diol binding mechanism of boronic acid and catechol. • Reduced graphene oxide was used as quencher on nano-platform. • Detection was controlled dependent on pH based on diol compound of boron chemistry.

  15. Selective on-line detection of boronic acids and derivatives in high-performance liquid chromatography eluates by post-column reaction with alizarin

    NARCIS (Netherlands)

    Duval, F.L.; Wardani, P.A.; Zuilhof, H.; Beek, van T.A.

    2015-01-01

    An on-line high-performance liquid chromatography (HPLC) method for the rapid and selective detection of boronic acids in complex mixtures was developed. After optimization experiments at an HPLC flow rate of 0.40 mL/min, the HPLC-separated analytes were mixed post-column with a solution of 75 µM

  16. Diphenylarsinic acid, a chemical warfare-related neurotoxicant, promotes liver carcinogenesis via activation of aryl hydrocarbon receptor signaling and consequent induction of oxidative DAN damage in rats

    International Nuclear Information System (INIS)

    Wei, Min; Yamada, Takanori; Yamano, Shotaro; Kato, Minoru; Kakehashi, Anna; Fujioka, Masaki; Tago, Yoshiyuki; Kitano, Mistuaki; Wanibuchi, Hideki

    2013-01-01

    Diphenylarsinic acid (DPAA), a chemical warfare-related neurotoxic organic arsenical, is present in the groundwater and soil in some regions of Japan due to illegal dumping after World War II. Inorganic arsenic is carcinogenic in humans and its organic arsenic metabolites are carcinogenic in animal studies, raising serious concerns about the carcinogenicity of DPAA. However, the carcinogenic potential of DPAA has not yet been evaluated. In the present study we found that DPAA significantly enhanced the development of diethylnitrosamine-induced preneoplastic lesions in the liver in a medium-term rat liver carcinogenesis assay. Evaluation of the expression of cytochrome P450 (CYP) enzymes in the liver revealed that DPAA induced the expression of CYP1B1, but not any other CYP1, CYP2, or CYP3 enzymes, suggesting that CYP1B1 might be the enzyme responsible for the metabolic activation of DPAA. We also found increased oxidative DNA damage, possibly due to elevated CYP1B1 expression. Induction of CYP1B1 has generally been linked with the activation of AhR, and we found that DPAA activates the aryl hydrocarbon receptor (AhR). Importantly, the promotion effect of DPAA was observed only at a dose that activated the AhR, suggesting that activation of AhR and consequent induction of AhR target genes and oxidative DNA damage plays a vital role in the promotion effects of DPAA. The present study provides, for the first time, evidence regarding the carcinogenicity of DPAA and indicates the necessity of comprehensive evaluation of its carcinogenic potential using long-term carcinogenicity studies. - Highlights: • DPAA, an environmental neurotoxicant, promotes liver carcinogenesis in rats. • DPAA is an activator of AhR signaling pathway. • DPAA promoted oxidative DNA damage in rat livers. • AhR target gene CYP 1B1 might be involved in the metabolism of DPAA

  17. Diphenylarsinic acid, a chemical warfare-related neurotoxicant, promotes liver carcinogenesis via activation of aryl hydrocarbon receptor signaling and consequent induction of oxidative DAN damage in rats

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Min; Yamada, Takanori; Yamano, Shotaro; Kato, Minoru; Kakehashi, Anna; Fujioka, Masaki; Tago, Yoshiyuki; Kitano, Mistuaki; Wanibuchi, Hideki, E-mail: wani@med.osaka-cu.ac.jp

    2013-11-15

    Diphenylarsinic acid (DPAA), a chemical warfare-related neurotoxic organic arsenical, is present in the groundwater and soil in some regions of Japan due to illegal dumping after World War II. Inorganic arsenic is carcinogenic in humans and its organic arsenic metabolites are carcinogenic in animal studies, raising serious concerns about the carcinogenicity of DPAA. However, the carcinogenic potential of DPAA has not yet been evaluated. In the present study we found that DPAA significantly enhanced the development of diethylnitrosamine-induced preneoplastic lesions in the liver in a medium-term rat liver carcinogenesis assay. Evaluation of the expression of cytochrome P450 (CYP) enzymes in the liver revealed that DPAA induced the expression of CYP1B1, but not any other CYP1, CYP2, or CYP3 enzymes, suggesting that CYP1B1 might be the enzyme responsible for the metabolic activation of DPAA. We also found increased oxidative DNA damage, possibly due to elevated CYP1B1 expression. Induction of CYP1B1 has generally been linked with the activation of AhR, and we found that DPAA activates the aryl hydrocarbon receptor (AhR). Importantly, the promotion effect of DPAA was observed only at a dose that activated the AhR, suggesting that activation of AhR and consequent induction of AhR target genes and oxidative DNA damage plays a vital role in the promotion effects of DPAA. The present study provides, for the first time, evidence regarding the carcinogenicity of DPAA and indicates the necessity of comprehensive evaluation of its carcinogenic potential using long-term carcinogenicity studies. - Highlights: • DPAA, an environmental neurotoxicant, promotes liver carcinogenesis in rats. • DPAA is an activator of AhR signaling pathway. • DPAA promoted oxidative DNA damage in rat livers. • AhR target gene CYP 1B1 might be involved in the metabolism of DPAA.

  18. Binary boronic acid-functionalized attapulgite with high adsorption capacity for selective capture of nucleosides at acidic pH values

    International Nuclear Information System (INIS)

    Li, Huihui; Zhu, Shuqiang; Cheng, Ting; Wang, Shuxia; Zhu, Bin; Liu, Xiaoyan; Zhang, Haixia

    2016-01-01

    Boronate affinity materials have been widely used for selective capture of cis-diols such as nucleosides. Adsorbents with features of low binding pH and high adsorption capacity are highly desired. However, most reported materials only possess one of the two features. We have synthesized a 1,3,5-triazine-containing binary boronic acid by reacting cyanuric chloride with 3-amino phenylboronic acid, and the product was then grafted onto attapulgite (a fibrous aluminum-magnesium silicate). The resulting functionalized attapulgite exhibit low binding pH (5.0) and display high adsorption capacity (19.5 ± 1.1 mg⋅g"−"1 for adenosine). The material exhibits high selectivity for cis-diols even in the presence of a 1000-fold excess of interferences. It was applied to the selective extraction of nucleosides from human urine. Typical features of the method include (a) limits of detection in the range from 4 to 17 ng⋅mL"−"1, (b) limits of quantification between 13 and 57 ng⋅mL"−"1, (c) relative standard deviations of ≤9.1 %, and (d) recoveries of nucleosides from spiked human urine between 85.0 and 112.9 %. In our perception, the material and method offer a promising strategy for selective capture of cis-diols in the areas of proteomics, metabolomics and glycomics. (author)

  19. Docking Studies, Synthesis and Biological Evaluation of β-aryl-β-hydroxy Propanoic Acids for Anti-inflammatory Activity.

    Science.gov (United States)

    Savic, Jelena; Dilber, Sanda; Milenkovic, Marina; Kotur-Stevuljevic, Jelena; Markovic, Bojan; Vladimirov, Sote; Brboric, Jasmina

    2017-01-01

    Nonsteriodal anti-inflammatory drugs (NSAIDs) are numerous and widely used for more than 60 years, but there is still a strong need for developing novel selective NSAIDs. The need is justified by the fact that nonselective NSAIDs can produce serious gastric side effects and that some of the selective NSAID are withdrawn due to their cardiotoxic side effects. Eight β-hydroxy-β-arylpropanoic acids, which belong to the arylpropanoic acid class of compounds, structurally similar to some nonsteroidal anti-inflammatory drugs (NSAIDs), were docked into 3D catalytic site of both cyclooxygenase-1 (COX-1) and cyclooxygenase-2 (COX-2). Seven out of those eight acids were synthesized using already published modification of Reformatsky reaction additionally optimized by increasing temperature. Synthesized compounds were tested in vivo in order to elucidate anti-inflammatory activity, gastric tolerability and impact on liver function of rats. Results of docking studies have indicated that all compounds have potential to selectively inhibit COX-2 isoform, but that the compounds containing polar substituents on phenyl ring are better inhibitors. Results of carrageenan-induced rat paw oedema test have shown that all compounds exhibit dose dependence and good gastric tolerability and none of the tested compounds have shown negative effect on liver function compared to ibuprofen. The compound containing polar nitro group in para position has shown the best docking results, anti-inflammatory activity, low hepatotoxicity and good gastric tolerability. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  20. Determination of boron as boric acid by automatic potentiometric titration using Gran plots [in pressurized water reactor coolant

    International Nuclear Information System (INIS)

    Midgley, D.; Gatford, C.

    1989-11-01

    Boron in PWR primary coolant and related waters may be determined as boric acid by titration with sodium hydroxide, using a glass electrode as a pH indicator. Earlier work has shown that this analysis can conveniently be carried out automatically with adequate precision and accuracy for routine use, although bias became apparent at the lowest concentrations tested. The latest titrators enable the titration data to be transformed mathematically to give two linear segments, before and after the end-point (Gran plots). The results are as precise as those from other titration methods (in which the end-point is found from the point of inflexion of a plot of pH against volume of titrant), but the bias at low concentrations is much reduced. This is achieved without extra time or involvement of the operator. (author)

  1. Direct catalytic trifluoromethylthiolation of boronic acids and alkynes employing electrophilic shelf-stable N-(trifluoromethylthio)phthalimide.

    Science.gov (United States)

    Pluta, Roman; Nikolaienko, Pavlo; Rueping, Magnus

    2014-02-03

    A new and safe method for the synthesis of N-(trifluoromethylthio)phthalimide, a convenient and shelf-stable reagent for the direct trifluoromethylthiolation, has been developed. N-(Trifluoromethylthio)phthalimide can be used as an electrophilic source of F3 CS(+) and reacts readily with boronic acids and alkynes under copper catalysis. The utility of CF3 S-containing molecules as biologically active agents, the mild reaction conditions employed, and the high tolerance of functional groups demonstrate the potential of this new methodology to be widely applied in organic synthesis as well as industrial pharmaceutical and agrochemical research and development. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Boronic acid-modified lipid nanocapsules: a novel platform for the highly efficient inhibition of hepatitis C viral entry

    Science.gov (United States)

    Khanal, Manakamana; Barras, Alexandre; Vausselin, Thibaut; Fénéant, Lucie; Boukherroub, Rabah; Siriwardena, Aloysius; Dubuisson, Jean; Szunerits, Sabine

    2015-01-01

    The search for viral entry inhibitors that selectively target viral envelope glycoproteins has attracted increasing interest in recent years. Amongst the handful of molecules reported to show activity as hepatitis C virus (HCV) entry inhibitors are a variety of glycan-binding proteins including the lectins, cyanovirin-N (CV-N) and griffithsin. We recently demonstrated that boronic acid-modified nanoparticles are able to reduce HCV entry through a similar mechanism to that of lectins. A major obstacle to any further development of these nanostructures as viral entry inhibitors is their only moderate maximal inhibition potential. In the present study, we report that lipid nanocapsules (LNCs), surface-functionalized with amphiphilic boronic acid (BA) through their post-insertion into the semi-rigid shell of the LNCs, are indeed far superior as HCV entry inhibitors when compared with previously reported nanostructures. These 2nd generation particles (BA-LNCs) are shown to prevent HCV infection in the micromolar range (IC50 = 5.4 μM of BA moieties), whereas the corresponding BA monomers show no significant effects even at the highest analyzed concentration (20 μM). The new BA-LNCs are the most promising boronolectin-based HCV entry inhibitors reported to date and are thus observed to show great promise in the development of a pseudolectin-based therapeutic agent.The search for viral entry inhibitors that selectively target viral envelope glycoproteins has attracted increasing interest in recent years. Amongst the handful of molecules reported to show activity as hepatitis C virus (HCV) entry inhibitors are a variety of glycan-binding proteins including the lectins, cyanovirin-N (CV-N) and griffithsin. We recently demonstrated that boronic acid-modified nanoparticles are able to reduce HCV entry through a similar mechanism to that of lectins. A major obstacle to any further development of these nanostructures as viral entry inhibitors is their only moderate maximal

  3. Electrochemical incineration of chloromethylphenoxy herbicides in acid medium by anodic oxidation with boron-doped diamond electrode

    International Nuclear Information System (INIS)

    Boye, Birame; Brillas, Enric; Marselli, Beatrice; Michaud, Pierre-Alain; Comninellis, Christos; Farnia, Giuseppe; Sandona, Giancarlo

    2006-01-01

    The electrochemical degradation of saturated solutions of herbicides 4-chloro-2-methylphenoxyacetic acid, 2-(4-chlorophenoxy)-2-methylpropionic acid and 2-(4-chloro-2-methylphenoxy)propionic acid in 1 M HClO 4 on a boron-doped diamond (BDD) thin film anode has been studied by chronoamperometry, cyclic voltammetry and bulk electrolysis. At low anodic potentials polymeric products are formed causing the fouling and deactivation of BDD. This is reactivated at high potentials when water decomposes producing hydroxyl radical as strong oxidant of organics. Electrolyses in a batch recirculation system at constant current density ≥8 mA cm -2 yielded overall decontamination of all saturated solution. The effect of current density and herbicide concentration on the degradation rate of each compound, the specific charge required for its total mineralization and instantaneous current efficiency have been investigated. Experimental results have been compared with those predicted by a theoretical model based on a fast anodic oxidation of initial herbicides, showing that at 30 mA cm -2 their degradation processes are completely controlled by mass transfer. Kinetic analysis of the change of herbicide concentration with time during electrolysis, determined by high-performance liquid chromatography, revealed that all compounds follow a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids have been identified using this technique and a general pathway for the electrochemical incineration of all herbicides on BDD is proposed

  4. Improved biological processes for the production of aryl sulfates

    DEFF Research Database (Denmark)

    2017-01-01

    The present invention generally relates to the field of biotechnology as it applies to the production of aryl sulfates using recombinant host cells. More particularly, the present invention pertains to recombinant host cells comprising (e.g., expressing) a polypeptide having aryl sulfotransferase...... activity, wherein said recombinant host cells have been modified to have an increased uptake of sulfate compared to identical host cells that does not carry said modification. Further provided are processes for the production of aryl sulfates, such as zosteric acid, employing such recombinant host cells....

  5. Enrichment of boron 10

    International Nuclear Information System (INIS)

    Coutinho, C.M.M.; Rodrigues Filho, J.S.R.; Umeda, K.; Echternacht, M.V.

    1990-01-01

    A isotopic separation pilot plant with five ion exchange columns interconnected in series were designed and built in the IEN. The columns are charged with a strong anionic resin in its alkaline form. The boric acid solution is introduced in the separation columns until it reaches a absorbing zone length which is sufficient to obtain the desired boron-10 isotopic concentration. The boric acid absorbing zone movement is provided by the injection of a diluted hydrochloric acid solution, which replace the boric acid throughout the columns. The absorbing zone equilibrium length is proportional to its total length. The enriched boron-10 and the depleted boron are located in the final boundary and in the initial position of the absorbing zones, respectively. (author)

  6. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    Directory of Open Access Journals (Sweden)

    Sanna L. Diemer

    2015-09-01

    Full Text Available Dynamic combinatorial chemistry has emerged as a promising tool for the discovery of complex receptors in supramolecular chemistry. At the heart of dynamic combinatorial chemistry are the reversible reactions that enable the exchange of building blocks between library members in dynamic combinatorial libraries (DCLs ensuring thermodynamic control over the system. If more than one reversible reaction operates in a single dynamic combinatorial library, the complexity of the system increases dramatically, and so does its possible applications. One can imagine two reversible reactions that operate simultaneously or two reversible reactions that operate independently. Both these scenarios have advantages and disadvantages. In this contribution, we show how disulfide exchange and boronic ester transesterification can function simultaneous in dynamic combinatorial libraries under appropriate conditions. We describe the detailed studies necessary to establish suitable reaction conditions and highlight the analytical techniques appropriate to study this type of system.

  7. Synthetic approach of norbadione A: new preparation of alcohols from sulfones and boron compounds

    International Nuclear Information System (INIS)

    Billaud, C.

    2005-12-01

    The synthetic approach of norbadione A, a pigment from mushrooms related to pulvinic acids, was studied. This compound has the property to complex caesium and has shown an antioxidant activity. The first strategy, based on a double Suzuki-Miyaura coupling between a naphtho-lactone with two boron functions and two pulvinic moieties with a triflate was unsuccessful and has shown a deactivating effect of the lactone. Modifications aimed to inhibit the electro-attracting character of the lactone permitted to obtain a bis(coupled) product with a poor yield. A second approach based on a the cyclization of enol aryl-acetates was studied in order to build the pulvinic moiety in several steps. The important reaction of introduction of an alkyl-acetate from a triflate was realised by a palladium-mediated coupling. The cyclization attempts carried out using a naphthalenic compound allowed us to isolate a monocyclised product. A parallel study was to first build a tetronic moiety and then to construct the exocyclic double bond by a method developed in the laboratory for the preparation of an iodated pulvinic compound. Finally, a new preparation of alcohols from sulfones and boron compounds was developed. Two known reactions in the chemistry of boron were combined. The first one is the reaction between anions of sulfones and tri-alkyl-boranes, the second one is a thermal isomerization which places the boron atom in a terminal position. A new preparation of primary alcohols was thus carried out. (author)

  8. Inhibition of bacterial DD-peptidases (penicillin-binding proteins) in membranes and in vivo by peptidoglycan-mimetic boronic acids.

    Science.gov (United States)

    Dzhekieva, Liudmila; Kumar, Ish; Pratt, R F

    2012-04-03

    The DD-peptidases or penicillin-binding proteins (PBPs) catalyze the final steps of bacterial peptidoglycan biosynthesis and are inhibited by the β-lactam antibiotics. There is at present a question of whether the active site structure and activity of these enzymes is the same in the solubilized (truncated) DD-peptidase constructs employed in crystallographic and kinetics studies as in membrane-bound holoenzymes. Recent experiments with peptidoglycan-mimetic boronic acids have suggested that these transition state analogue-generating inhibitors may be able to induce reactive conformations of these enzymes and thus inhibit strongly. We have now, therefore, measured the dissociation constants of peptidoglycan-mimetic boronic acids from Escherichia coli and Bacillus subtilis PBPs in membrane preparations and, in the former case, in vivo, by means of competition experiments with the fluorescent penicillin Bocillin Fl. The experiments showed that the boronic acids bound measurably (K(i) DD-peptidase inhibitors are more or less effective in vivo than in homogeneous solution.

  9. Direct N9-arylation of purines with aryl halides

    DEFF Research Database (Denmark)

    Larsen, Anders Foller; Ulven, Trond

    2014-01-01

    An efficient method for N-arylation of purines is reported. The N-arylation is catalysed by Cu(i) and 4,7-bis(2-hydroxyethylamino)-1,10-phenanthroline (BHPhen) in aqueous DMF or ethanol. The reaction generally proceeds with high selectivity for the N(9)-position.......An efficient method for N-arylation of purines is reported. The N-arylation is catalysed by Cu(i) and 4,7-bis(2-hydroxyethylamino)-1,10-phenanthroline (BHPhen) in aqueous DMF or ethanol. The reaction generally proceeds with high selectivity for the N(9)-position....

  10. Boron-Doped Diamond (BDD) Coatings Protect Underlying Silicon in Aqueous Acidic Media–Application to the Hydrogen Evolution Reaction

    International Nuclear Information System (INIS)

    Halima, A.F.; Rana, U.A.; MacFarlane, D.R.

    2014-01-01

    Abstract: Silicon has potential application as a functional semiconductor electrode in proposed solar water splitting cells. It is abundant and has excellent photovoltaic attributes, however it is extremely susceptible to corrosion, even in the dark, resulting in the formation of an electrochemically passive oxide upon interaction with aqueous media. This work investigates the potential for conductive, inert and transparent boron doped diamond (BDD) coatings to protect p-type Silicon (p-Si). The stability and electrochemical performance of p-Si and p-Si|BDD were investigated using voltammetric techniques in 1 M H 2 SO 4 , before and after long-term exposure to the acidic medium (up to 280 hours) under no applied potential bias. Unprotected Si degraded very rapidly whilst BDD was shown to protect the underlying Si, as evident from I-V curves that indicated no increased resistance across the Si-diamond interface. Furthermore, BDD supported facile proton reduction at significantly lower onset potential for the hydrogen evolution reaction (up to -500 mV vs. SCE) compared with bare Si cathode (-850 mV vs. SCE). The activity of the BDD electrode/electrolyte interface was further improved by coating with platinum catalyst particles, to produce a p-Si|BDD|Pt strucure, which reduced the HER onset to nearly zero overpotential. Tafel analysis indicated that desirable electrochemical activity and stability were achieved for p-Si|BDD|Pt, making this a promising electrode for application in water splitting cells

  11. Voltammetric determination of mixtures of caffeine and chlorogenic acid in beverage samples using a boron-doped diamond electrode.

    Science.gov (United States)

    Yardım, Yavuz; Keskin, Ertugrul; Şentürk, Zühre

    2013-11-15

    Herein, a boron-doped diamond (BDD) electrode that is anodically pretreated was used for the simultaneous determination of caffeine (CAF) and chlorogenic acid (CGA) by cyclic and adsorptive stripping voltammetry. The dependence of peak current and potential on pH, scan rate, accumulation parameters and other experimental variables were studied. By using square-wave stripping mode after 60 s accumulation under open-circuit voltage, the BDD electrode was able to separate the oxidation peak potentials of CAF and CGA present in binary mixtures by about 0.4V in Britton-Robinson buffer at pH 1.0. The limits of detection were 0.107 µg mL(-1) (5.51×10(-7) M) for CAF, and 0.448 µg mL(-1) (1.26×10(-6) M) for CGA. The practical applicability of this methodology was tested in commercially available beverage samples. © 2013 Elsevier B.V. All rights reserved.

  12. Enhanced selectivity of boron doped diamond electrodes for the detection of dopamine and ascorbic acid by increasing the film thickness

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Yao; Long, Hangyu [School of Material Science and Engineering, Central South University, Changsha 410083 (China); Ma, Li, E-mail: marycsupm@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Wei, Quiping, E-mail: qiupwei@csu.edu.cn [School of Material Science and Engineering, Central South University, Changsha 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Li, Site [School of Material Science and Engineering, Central South University, Changsha 410083 (China); Yu, Zhiming [School of Material Science and Engineering, Central South University, Changsha 410083 (China); State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Hu, Jingyuan [School of Material Science and Engineering, Central South University, Changsha 410083 (China); Liu, Peizhi [Key laboratory of interface science and engineering in advanced materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024,PR China (China); Wang, Yijia [School of Material Science and Engineering, Central South University, Changsha 410083 (China); Meng, Lingcong [Department of Chemistry, University of Warwick, Coventry, West Midlands CV4 7AL (United Kingdom)

    2016-12-30

    Highlights: • BDD electrodes with different thickness have been fabricated. • BDD electrodes are used for simultaneous detection of DA and AA. • Anodic pretreatment enhance the separation of DA and AA oxidation peak potential. • Thicker BDD electrode show better performance for DA detection coexisting with AA. - Abstract: In this paper, boron doped diamond (BDD) with different thickness were prepared by hot filament chemical vapor deposition. The performance of BDD electrodes for detecting dopamine (DA) and ascorbic acid (AA) were investigated. Scanning electron microscopy and Raman spectra reveal the grain size increases and the film quality improves with the increase of film thickness. Electrochemical test show that the transfer coefficient in [Fe{sub 3} (CN) {sub 6}]{sup 3−/4−} redox system increases with the increase of the film thickness. The results of selectivity and sensitivity for DA mixed with AA detection show that 8h-BDD and 12h-BDD electrodes possess well selective separated oxidation peaks of DA and AA, and the 12h-BDD electrode exhibits optimal sensitivity until the DA concentration drops to 1 μ M.

  13. Highly sensitive detection of influenza virus by boron-doped diamond electrode terminated with sialic acid-mimic peptide.

    Science.gov (United States)

    Matsubara, Teruhiko; Ujie, Michiko; Yamamoto, Takashi; Akahori, Miku; Einaga, Yasuaki; Sato, Toshinori

    2016-08-09

    The progression of influenza varies according to age and the presence of an underlying disease; appropriate treatment is therefore required to prevent severe disease. Anti-influenza therapy, such as with neuraminidase inhibitors, is effective, but diagnosis at an early phase of infection before viral propagation is critical. Here, we show that several dozen plaque-forming units (pfu) of influenza virus (IFV) can be detected using a boron-doped diamond (BDD) electrode terminated with a sialic acid-mimic peptide. The peptide was used instead of the sialyloligosaccharide receptor, which is the common receptor of influenza A and B viruses required during the early phase of infection, to capture IFV particles. The peptide, which was previously identified by phage-display technology, was immobilized by click chemistry on the BDD electrode, which has excellent electrochemical characteristics such as low background current and weak adsorption of biomolecules. Electrochemical impedance spectroscopy revealed that H1N1 and H3N2 IFVs were detectable in the range of 20-500 pfu by using the peptide-terminated BDD electrode. Our results demonstrate that the BDD device integrated with the receptor-mimic peptide has high sensitivity for detection of a low number of virus particles in the early phase of infection.

  14. Efficient one-pot, four-component synthesis of N,N-dibenzyl-N-{1-[5-(3-aryl-1,3,4-oxadiazol-2-yl]cyclobutyl}amine derivatives from the reaction of (isocyanoiminotriphenylphosphorane, dibenzylamine, an aromatic carboxylic acid and cyclobutanone

    Directory of Open Access Journals (Sweden)

    Shajari Nahid

    2012-01-01

    Full Text Available Four-component reaction of cyclobutanone, dibenzylamine and (Nisocyanimino triphenylphosphorane in the presence of aromatic carboxylic acids proceed smoothly at room temperature and under neutral conditions to afford N,N-dibenzyl-N-{1-[5-(3-aryl-1,3,4-oxadiazol-2-yl]cyclobutyl}amine derivatives in high yields.

  15. Protein Complexation and pH Dependent Release Using Boronic Acid Containing PEG-Polypeptide Copolymers.

    Science.gov (United States)

    Negri, Graciela E; Deming, Timothy J

    2017-01-01

    New poly(L-lysine)-b-poly(ethylene glycol) copolypeptides have been prepared, where the side-chain amine groups of lysine residues are modified to contain ortho-amine substituted phenylboronic acid, i.e., Wulff-type phenylboronic acid (WBA), groups to improve their pH responsive, carbohydrate binding properties. These block copolymers form nanoscale complexes with glycosylated proteins that are stable at physiological pH, yet dissociate and release the glycoproteins under acidic conditions, similar to those found in endosomal and lysosomal compartments within cells. These results suggest that WBA modified polypeptide copolymers are promising for further development as degradable carriers for intracellular protein delivery. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The role of calcium, silicon and salicylic acid treatment in protection of canola plants against boron toxicity stress.

    Science.gov (United States)

    Metwally, Ashraf M; Radi, Abeer A; El-Shazoly, Rasha M; Hamada, Afaf M

    2018-01-22

    Boron (B) toxicity often limits crop yield and the quality of production in agricultural areas. Here, we investigated the effects of calcium (Ca), silicon (Si) and salicylic acid (SA) on development of B toxicity, B allocation in canola (Brassica napus cultivar Sarw 4) and its role in non-enzymatic antioxidants in relation to yield of this cultivar under B toxicity. Canola seedlings were subjected to four B levels induced by boric acid in the absence or presence of Ca, Si and SA. The results showed that Ca, Si and SA addition ameliorated the inhibition in canola growth, water content (WC), and improved siliqua number, siliqua weight and seed index. The B content in shoots and roots and total B accumulation in the whole plant were increased in control plants under B-toxicity-stress, and these parameters were significantly decreased by addition of Ca, Si and SA. The shoot ascorbate pool (ascorbate, AsA, and dehydroascorbate, DHA), α-tocopherol and phenolics (free and bound) were increased under B toxicity, and were significantly decreased in most cases by addition of Ca, Si and SA, except α-tocopherol, which increased at low B levels (0, 25 and 50 mg kg soil -1 ). The glutathione content did not obviously change by B stress, while added Ca, Si and SA inhibited its accumulation under B stress. In addition, B toxicity reduced the shoot flavonoids content; however, this reduction was not alleviated by the use of Ca, Si and SA treatments. It could be concluded that growth and yield of canola plants grown under high B concentration improved after external application of Ca, Si or SA.

  17. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian

    2016-04-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

  18. Conformationally locked aryl C-nucleosides: synthesis of phosphoramidite monomers and incorporation into single-stranded DNA and LNA (locked nucleic acid)

    DEFF Research Database (Denmark)

    Babu, B. Ravindra; Prasad, Ashok K.; Trikha, Smriti

    2002-01-01

    . The phosphoramidite approach was used for automated incorporation of the LNA-type beta-configured C-aryl monomers 17a-17e into short DNA and 2'-OMe-RNA/LNA strands. It is shown that universal hybridization can be obtained with a conformationally restricted monomer as demonstrated most convincingly for the pyrene LNA...... monomer 17d, both in a DNA context and in an RNA-like context. Increased binding affinity of oligonucleotide probes for universal hybridization can be induced by combining the pyrene LNA monomer 17d with affinity-enhancing 2'-OMe-RNA/LNA monomers....

  19. Unprecedentedly mild direct Pd-catalyzed arylation of oxazolo[4,5-b]pyridine

    DEFF Research Database (Denmark)

    Zhuravlev, Fedor

    2006-01-01

    Pd-catalyzed C-2 arylation of oxazolo[4,5-b]pyridine proceeds efficiently at 30 degrees C and tolerates a variety of aryl halides, including derivatized amino acids for which no racemization was observed during the reaction. Experimental evidence for facile deprotonation of oxazolo[4,5-b...

  20. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    Energy Technology Data Exchange (ETDEWEB)

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  1. EFFECTS.OF BORIC ACID ON THE CURE OF BORON-FILLED Y-3602 SILICONE GUM

    Energy Technology Data Exchange (ETDEWEB)

    Leichliter, G E

    1974-10-01

    The first two phases of a program designed to determine the effects of boric acid on the cure of Y-3602 silicone gum were conducted to evaluate extraction solvents and extraction time. The standard production formulation of B10-filled Y-3602 silicone gum was used in these evaluations. Results showed that the best solvent for reproducibility and high amine content was chloroform. The second phase indicated that extraction was essentially complete at the end of 4 hours.

  2. Catalytic conversion of cellulose to fuels and chemicals using boronic acids

    Science.gov (United States)

    Raines, Ronald; Caes, Benjamin; Palte, Michael

    2015-10-20

    Methods and catalyst compositions for formation of furans from carbohydrates. A carbohydrate substrate is heating in the presence of a 2-substituted phenylboronic acid (or salt or hydrate thereof) and optionally a magnesium or calcium halide salt. The reaction is carried out in a polar aprotic solvent other than an ionic liquid, an ionic liquid or a mixture thereof. Additional of a selected amount of water to the reaction can enhance the yield of furans.

  3. PEG1000-Based Dicationic Acidic Ionic Liquid Catalyzed One-Pot Synthesis of 4-Aryl-3-Methyl-1-Phenyl-1H-Benzo[h]pyrazolo [3,4-b]quinoline-5,10-Diones via Multicomponent Reactions

    Directory of Open Access Journals (Sweden)

    Yi-Ming Ren

    2015-09-01

    Full Text Available A novel and green approach for efficient and rapid synthesis of 4-aryl-3-methyl-1-phenyl-1H-benzo[h]pyrazolo[3,4-b]quinoline-5,10-diones has been accomplished by the one-pot condensation reaction of aromatic aldehydes, 3-methyl-1-phenyl-1H-pyrazol-5-amine and 2-hydroxynaphthalene-1,4-dione using PEG1000-based dicationic acidic ionic liquid (PEG1000-DAIL as a catalyst was reported. Recycling studies have shown that the PEG1000-DAIL can be readily recovered and reused several times without significant loss of activity. The key advantages are the short reaction time, high yields, simple workup, and recovered catalyst.

  4. Formation of an adduct by clenbuterol, a beta-adrenoceptor agonist drug, and serum albumin in human saliva at the acidic pH of the stomach: evidence for an aryl radical-based process.

    Science.gov (United States)

    Pietraforte, D; Brambilla, G; Camerini, S; Scorza, G; Peri, L; Loizzo, A; Crescenzi, M; Minetti, M

    2008-07-15

    Clenbuterol (CLB) is an antiasthmatic drug used also illegally as a lean muscle mass enhancer in both humans and animals. CLB and amine-related drugs in general are nitrosatable, thus raising concerns regarding possible genotoxic/carcinogenic activity. Oral administration of CLB raises the issue of its possible transformation by salivary nitrite at the acidic pH of gastric juice. In acidic human saliva CLB was rapidly transformed to the CLB arenediazonium ion. This suggests a reaction of CLB with salivary nitrite, as confirmed in aerobic HNO(2) solution by a drastic decrease in nitric oxide, nitrite, and nitrate. In human saliva, both glutathione and ascorbic acid were able to inhibit CLB arenediazonium formation and to react with preformed CLB arenediazonium. The effect of ascorbic acid is particularly pertinent because this vitamin is actively concentrated within the gastric juice. EPR spin trapping experiments showed that preformed CLB arenediazonium ion was reduced to the aryl radical by ascorbic acid, glutathione, and serum albumin, the major protein of saliva. As demonstrated by anti-CLB antibodies and MS, the CLB-albumin interaction leads to the formation of a covalent drug-protein adduct, with a preference for Tyr-rich regions. This study highlights the possible hazards associated with the use/abuse of this drug.

  5. Boronic acid functionalized silica microparticles for isolation of flavonoids from Hypericum perforatum

    Directory of Open Access Journals (Sweden)

    Onur Çetinkaya

    2017-10-01

    Full Text Available We have selectively separated cis- and/or vicinal-diol-containing flavonoids from Hypericum perfaratum (HP by adsorption/desorption using aminophenylboronic acid (APBA functionalized uniform (1.6 μm silica microparticles (BASPs synthesized via the Stöber method. Silica particles were alkylated by its terminal –OH with 3-aminopropyl trimethoxysilane (APTS, glutaraldehyde (GA and APBA. The results from model adsorption studies indicated that these microparticles selectively adsorbed quercetin and rutin but partially apigenin. The antioxidant and antiradical activities of the desorption solution were slightly higher than that of the post-adsorption solution. These results indicated that the BASP selectively adsorbed the cis- and/or vicinal antioxidant and antiradical flavonoids.

  6. Boron-Doped Carbon Nano-/Microballs from Orthoboric Acid-Starch: Preparation, Characterization, and Lithium Ion Storage Properties

    Directory of Open Access Journals (Sweden)

    Xinhua Lu

    2018-01-01

    Full Text Available A boron-doped carbon nano-/microballs (BC was successfully obtained via a two-step procedure including hydrothermal reaction (180°C and carbonization (800°C with cheap starch and H3BO3 as the carbon and boron source. As a new kind of boron-doped carbon, BC contained 2.03 at% B-content and presented the morphology as almost perfect nano-/microballs with different sizes ranging from 500 nm to 5 μm. Besides that, due to the electron deficient boron, BC was explored as anode material and presented good lithium storage performance. At a current density of 0.2 C, the first reversible specific discharge capacity of BC electrode reached as high as 964.2 mAh g–1 and kept at 699 mAh g–1 till the 11th cycle. BC also exhibited good cycle ability with a specific capacity of 356 mAh g–1 after 79 cycles at a current density of 0.5 C. This work proved to be an effective approach for boron-doped carbon nanostructures which has potential usage for lithium storage material.

  7. Boron supplementation in broiler diets

    Directory of Open Access Journals (Sweden)

    EJ Fassani

    2004-12-01

    Full Text Available Boron supplementation in broiler feed is not a routine practice. However, some reports suggest a positive effect of boron on performance. This study assessed the effects of boron supplementation on broiler performance. Diets were based on maize and soybean meal, using boric acid P.A. as boron source. Six supplementation levels (0, 30, 60, 90, 120 and 150 ppm were evaluated using 1,440 one-day old males housed at a density of 30 chickens in each of 48 experimental plots of 3m². A completely randomized block design was used with 8 replicates. Feed intake, weight gain and feed conversion were assessed in the periods from 1 to 7 days, 1 to 21 days and 1 to 42 days of age, and viability was evaluated for the total 42-day rearing period. No performance variable was affected by boron supplementation (p>0.05 in the period from 1 to 7 days. The regression analysis indicated an ideal level of 37.4 ppm of boron for weight gain from 1 to 21 days (p0.05, although feed intake was reduced linearly with increased boron levels (p0.05. Ash and calcium percentages in the tibias of broilers and viability in the total rearing period were not affected by boron supplementation (p>0.05.

  8. Crystal structures of Leishmania mexicana arginase complexed with α,α-disubstituted boronic amino-acid inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Hai, Yang; Christianson, David W.

    2016-03-16

    Leishmaniaarginase is a potential drug target for the treatment of leishmaniasis because this binuclear manganese metalloenzyme initiatesde novopolyamine biosynthesis by catalyzing the hydrolysis of L-arginine to generate L-ornithine and urea. The product L-ornithine subsequently undergoes decarboxylation to yield putrescine, which in turn is utilized for spermidine biosynthesis. Polyamines such as spermidine are essential for the growth and survival of the parasite, so inhibition of enzymes in the polyamine-biosynthetic pathway comprises an effective strategy for treating parasitic infections. To this end, two X-ray crystal structures ofL. mexicanaarginase complexed with α,α-disubstituted boronic amino-acid inhibitors based on the molecular scaffold of 2-(S)-amino-6-boronohexanoic acid are now reported. Structural comparisons with human and parasitic arginase complexes reveal interesting differences in the binding modes of the additional α-substituents,i.e.the D side chains, of these inhibitors. Subtle differences in the three-dimensional contours of the outer active-site rims among arginases from different species lead to different conformations of the D side chains and thus different inhibitor-affinity trends. The structures suggest that it is possible to maintain affinity while fine-tuning intermolecular interactions of the D side chain of α,α-disubstituted boronic amino-acid inhibitors in the search for isozyme-specific and species-specific arginase inhibitors.

  9. A ditopic fluorescence sensor for saccharides and mercury based on a boronic-acid receptor and desulfurisation reaction.

    Science.gov (United States)

    Xing, Zhitao; Wang, Hui-Chen; Cheng, Yixiang; James, Tony D; Zhu, Chengjian

    2011-11-04

    Two boron-contained fluorescent sensors, 1 and 2, based on coumarin have been prepared. The fluorescence response of the two systems was investigated with addition of saccharide and mercury ions. Sensor 2 behaves as a bifunctional fluorescent switch with chemical inputs of D-fructose and mercury ions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Aryl substitution of pentacenes

    Directory of Open Access Journals (Sweden)

    Andreas R. Waterloo

    2014-07-01

    Full Text Available A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films, thermoanalytical methods (DSC and TGA, cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives. X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices.

  11. Aryl substitution of pentacenes

    Science.gov (United States)

    Waterloo, Andreas R; Sale, Anna-Chiara; Lehnherr, Dan; Hampel, Frank

    2014-01-01

    Summary A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films), thermoanalytical methods (DSC and TGA), cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives). X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices. PMID:25161729

  12. Investigation into ramie whisker reinforced arylated soy protein composites

    CSIR Research Space (South Africa)

    Kumar, R

    2010-03-01

    Full Text Available isolate (SPI). Thiodiglycol was used as a plasticizer for the preparation of SW composites. The SW composites were arylated with 2,2-diphenyl-2-hydroxyethanoic acid through the process of “dip-coating” and coded as SW-B. In this paper, the characterization...

  13. Reaction of aryl diazonium tetrafluoro borates with allyl methacrylate in the presence of rhodanide-anion

    International Nuclear Information System (INIS)

    Grishchuk, B.D.; Baranovskij, V.S.; Simchak, R.V.; Tulajdan, G.N.; Gorbovoj, P.M.

    2006-01-01

    Reaction of aryl diazonium tetrafluoro borates (I) with allyl ester of methacrylic acid in the water-acetone (1:5) medium is studied by means of IR spectroscopy and 1 H NMR. It is established that (I) reacts with aryl methacrylate in the presence of rhodanide-anion and catalytic quantities of copper salts with the formation of allyl esters of 2-thiocyanato-2-methyl-3-aryl propionic acids with the yield of 32-56%. Allyl fragment of biunsaturated compound shows no reaction under the tested conditions [ru

  14. Aryl hydrocarbon receptor-dependent up-regulation of the heterodimeric amino acid transporter LAT1 (SLC7A5)/CD98hc (SLC3A2) by diesel exhaust particle extract in human bronchial epithelial cells

    Energy Technology Data Exchange (ETDEWEB)

    Le Vee, Marc; Jouan, Elodie; Lecureur, Valérie [Institut de Recherches en Santé, Environnement et Travail (IRSET), UMR INSERM U1085, Faculté de Pharmacie, 2 Avenue du Pr Léon Bernard, 35043 Rennes (France); Fardel, Olivier, E-mail: olivier.fardel@univ-rennes1.fr [Institut de Recherches en Santé, Environnement et Travail (IRSET), UMR INSERM U1085, Faculté de Pharmacie, 2 Avenue du Pr Léon Bernard, 35043 Rennes (France); Pôle Biologie, Centre Hospitalier Universitaire, 2 rue Henri Le Guilloux, 35033 Rennes (France)

    2016-01-01

    The heterodimeric L-type amino acid transporter (LAT) 1/CD98hc is overexpressed in lung cancers with a poor prognosis factor. Factors that contribute to LAT1/CD98hc overexpression in lung cells remain however to be determined, but the implication of atmospheric pollution can be suspected. The present study was therefore designed to analyze the effects of diesel exhaust particle (DEP) extract (DEPe) on LAT1/CD98hc expression in bronchial epithelial BEAS-2B cells. Exposure to DEPe up-regulated LAT1 and CD98hc mRNA levels in a concentration-dependent manner, with DEPe EC{sub 50} values (around 0.2 μg/mL) relevant to environmental situations. DEPe concomitantly induced LAT1/CD98hc protein expression and LAT1-mediated leucine accumulation in BEAS-2B cells. Inhibition of the aryl hydrocarbon receptor (AhR) pathway through the use of a chemical AhR antagonist or the siRNA-mediated silencing of AhR expression was next found to prevent DEPe-mediated induction of LAT1/CD98hc, indicating that this regulation depends on AhR, known to be activated by major chemical DEP components like polycyclic aromatic hydrocarbons. DEPe exposure was finally shown to induce mRNA expression and activity of matrix metalloproteinase (MMP)-2 in BEAS-2B cells, in a CD98hc/focal adhesion kinase (FAK)/extracellular regulated kinase (ERK) manner, thus suggesting that DEPe-mediated induction of CD98hc triggers activation of the integrin/FAK/ERK signaling pathway known to be involved in MMP-2 regulation. Taken together, these data demonstrate that exposure to DEPe induces functional overexpression of the amino acid transporter LAT1/CD98hc in lung cells. Such a regulation may participate to pulmonary carcinogenic effects of DEPs, owing to the well-documented contribution of LAT1 and CD98hc to cancer development. - Highlights: • The amino acid transporter LAT1/CD98hc is up-regulated in DEPe-treated lung cells. • The aryl hydrocarbon receptor is involved in DEPe-triggered induction of LAT1/CD98hc.

  15. Synthesis, characterization and fuel cell performance tests of boric acid and boron phosphate doped, sulphonated and phosphonated poly(vinyl alcohol) based composite membranes

    Science.gov (United States)

    Şahin, Alpay; Ar, İrfan

    2015-08-01

    The aim of this study is to synthesize a composite membrane having high proton conductivity, ion exchange capacity and chemical stability. In order to achieve this aim, poly(vinyl alcohol) (PVA) based composite membranes are synthesized by using classic sol-gel method. Boric acid (H3BO3) and boron phosphate (BPO4) are added to the membrane matrix in different ratios in order to enhance the membrane properties. Characterization tests, i.e; FT-IR analysis, mechanical strength tests, water hold-up capacities, swelling properties, ion exchange capacities, proton conductivities and fuel cell performance tests of synthesized membranes are carried out. As a result of performance experiments highest performance values are obtained for the membrane containing 15% boron phosphate at 0.6 V and 750 mA/cm2. Water hold-up capacity, swelling ratio, ion exchange capacity and proton conductivity of this membrane are found as 56%, 8%, 1.36 meq/g and 0.37 S/cm, respectively. These values are close to the values obtained ones for perfluorosulphonic acid membranes. Therefore this membrane can be regarded as a promising candidate for usage in fuel cells.

  16. Crystal Structures of KPC-2[beta]-Lactamase in Complex with 3-Nitrophenyl Boronic Acid and the Penam Sulfone PSR-3-226

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Wei; Bethel, Christopher R.; Papp-Wallace, Krisztina M.; Pagadala, Sundar Ram Reddy; Nottingham, Micheal; Fernandez, Daniel; Buynak, John D.; Bonomo, Robert A.; van den Akker, Focco (Case Western); (Stokes); (SMU)

    2012-08-01

    Class A carbapenemases are a major threat to the potency of carbapenem antibiotics. A widespread carbapenemase, KPC-2, is not easily inhibited by {beta}-lactamase inhibitors (i.e., clavulanic acid, sulbactam, and tazobactam). To explore different mechanisms of inhibition of KPC-2, we determined the crystal structures of KPC-2 with two {beta}-lactamase inhibitors that follow different inactivation pathways and kinetics. The first complex is that of a small boronic acid compound, 3-nitrophenyl boronic acid (3-NPBA), bound to KPC-2 with 1.62-{angstrom} resolution. 3-NPBA demonstrated a Km value of 1.0 {+-} 0.1 {micro}M (mean {+-} standard error) for KPC-2 and blocks the active site by making a reversible covalent interaction with the catalytic S70 residue. The two boron hydroxyl atoms of 3-NPBA are positioned in the oxyanion hole and the deacylation water pocket, respectively. In addition, the aromatic ring of 3-NPBA provides an edge-to-face interaction with W105 in the active site. The structure of KPC-2 with the penam sulfone PSR-3-226 was determined at 1.26-{angstrom} resolution. PSR-3-226 displayed a K{sub m} value of 3.8 {+-} 0.4 {micro}M for KPC-2, and the inactivation rate constant (kinact) was 0.034 {+-} 0.003 s{sup -1}. When covalently bound to S70, PSR-3-226 forms a trans-enamine intermediate in the KPC-2 active site. The predominant active site interactions are generated via the carbonyl oxygen, which resides in the oxyanion hole, and the carboxyl moiety of PSR-3-226, which interacts with N132, N170, and E166. 3-NPBA and PSR-3-226 are the first {beta}-lactamase inhibitors to be trapped as an acyl-enzyme complex with KPC-2. The structural and inhibitory insights gained here could aid in the design of potent KPC-2 inhibitors.

  17. Identification of amino acid residues in the ligand-binding domain of the aryl hydrocarbon receptor causing the species-specific response to omeprazole: possible determinants for binding putative endogenous ligands.

    Science.gov (United States)

    Shiizaki, Kazuhiro; Ohsako, Seiichiroh; Kawanishi, Masanobu; Yagi, Takashi

    2014-02-01

    Omeprazole (OME) induces the expression of genes encoding drug-metabolizing enzymes, such as CYP1A1, via activation of the aryl hydrocarbon receptor (AhR) both in vivo and in vitro. However, the precise mechanism of OME-mediated AhR activation is still under investigation. While elucidating species-specific susceptibility to dioxin, we found that OME-mediated AhR activation was mammalian species specific. Moreover, we previously reported that OME has inhibitory activity toward CYP1A1 enzymes. From these observations, we speculated that OME-mediated AhR target gene transcription is due to AhR activation by increasing amounts of putative AhR ligands in serum by inhibition of CYP1A1 activity. We compared the amino acid sequences of OME-sensitive rabbit AhR and nonsensitive mouse AhR to identify the residues responsible for the species-specific response. Chimeric AhRs were constructed by exchanging domains between mouse and rabbit AhRs to define the region required for the response to OME. OME-mediated transactivation was observed only with the chimeric AhR that included the ligand-binding domain (LBD) of the rabbit AhR. Site-directed mutagenesis revealed three amino acids (M328, T353, and F367) in the rabbit AhR that were responsible for OME-mediated transactivation. Replacing these residues with those of the mouse AhR abolished the response of the rabbit AhR. In contrast, substitutions of these amino acids with those of the rabbit AhR altered nonsensitive mouse AhR to become sensitive to OME. These results suggest that OME-mediated AhR activation requires a specific structure within LBD that is probably essential for binding with enigmatic endogenous ligands.

  18. Microwave-assisted synthesis of α-aryl malonates: Key intermediates for the

    Directory of Open Access Journals (Sweden)

    Mohamed A. Ibrahim

    2016-11-01

    Full Text Available We disclose a new microwave-assisted protocol for the effective α-arylation of diethyl malonate. The coupling of aryl halides with diethyl malonate proceeds smoothly in short reaction time in the presence of a catalytic amount of Cu(OTf2, 2-picolinic acid and Cs2CO3 in toluene using microwave irradiation. The resulting α-aryl malonates are then used as key intermediates for synthesis of variety of heterocyclic compounds, including benzodiazepines, isoquinolines and pyrrolopyridine scaffolds.

  19. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction...... tolerates a variety of functional groups, including ether, amide, alcohol, aldehyde, ketone, ester, cyano, carboxylic acid, and nitro groups. Ortho-substituted arylating agents afforded moderate yields in some cases, though good to high yields were obtained with o-iodotoluene, iodovanillin, and 1...

  20. Boron-containing thioureas for neutron capture therapy

    International Nuclear Information System (INIS)

    Ketz, H.

    1993-01-01

    Melanin is produced in large amounts in malignant melanotic melanomas. Because thiourea compounds are covalently incorporated into melanin during its biosynthesis, the preparation of boronated thiourea-derivatives is of particular interest for the BNCT (Boron Neutron Capture Therapy). Accumulation of boron in tumors by means of boronated thiourea-derivatives may therefore provide levels of 10 B which are useful for BNCT. In BNCT the tumor containing the boron compound is irradiated with epithermal neutrons to generate He- and Li-nuclei from the 10 B which can then destroy the tumor cells. Because of the short ranges of these particles (approximately one cell diameter) the damage will be almost exclusively confined to the tumor leaving normal tissue unharmed. High accumulation of 2-mercapto-1-methylimidazole (methimazole) in melanotic melanomas has been described in the literature. Boronated derivatives of methimazole were therefore synthesized. Boron was in the form of a boronic acid, a nido-carbonate and a mercaptoundeca hydro-closo-dodecaborate (BSH). The synthesis of the boron cluster derivatives of methimazole (nido-carborate- and BSH-derivatives) with 9 resp. 12 boron atoms in the molecule were expected to achieve higher concentrations of boron in the tumor than in the case of the boronic acid compound with its single boron atom. (orig.) [de

  1. Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

    Directory of Open Access Journals (Sweden)

    Andrea Caporale

    2014-02-01

    Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

  2. An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

    Science.gov (United States)

    Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

    2018-05-01

    This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

  3. A ratiometric fluorescent probe based on boron dipyrromethene and rhodamine Förster resonance energy transfer platform for hypochlorous acid and its application in living cells

    International Nuclear Information System (INIS)

    Liu, Ying; Zhao, Zhi-Min; Miao, Jun-Ying; Zhao, Bao-Xiang

    2016-01-01

    We have developed a ratiometric fluorescent probe BRT based on boron dipyrromethene (BODIPY) and rhodamine-thiohydrazide Förster resonance energy transfer (FRET) platform for sensing hypochlorous acid (HOCl) with high selectivity and sensitivity. The probe can detect HOCl in 15 s with the detection limit of 38 nM. Upon mixing with HOCl the fluorescence colour of probe BRT changed from green to orange. Moreover, probe BRT was applied to successfully monitor HOCl in living RAW 264.7 cells. - Highlights: • A probe based on BODIPY and rhodamine was developed for sensing HOCl. • The probe could sense HOCl in a ratiometric manner based on the FRET platform in PBS buffer solution. • The probe can detect HOCl in 15 s accompanied with a fluorescence colour change. • This probe was successfully used to monitor HOCl in living RAW 264.7 cells.

  4. Amine and Titanium (IV Chloride, Boron (III Chloride or Zirconium (IV Chloride-Promoted Baylis-Hillman Reactions

    Directory of Open Access Journals (Sweden)

    Shi-Cong Cui

    2001-10-01

    Full Text Available The Baylis-Hillman reactions of various aryl aldehydes with methyl vinyl ketone at temperatures below -20oC using Lewis acids such as titanium (IV chloride, boron (III chloride or zirconium (IV chloride in the presence of a catalytic amount of selected amines used as a Lewis bases afford the chlorinated compounds 1 as the major product in very high yields. Acrylonitrile can also undergo the same reaction to give the corresponding chlorinated product in moderate yield. A plausible reaction mechanism is proposed. However, if the reaction was carried out at room temperature (ca. 20oC, then the Z-configuration of the elimination product 3, derived from 1, was formed as the major product.

  5. Synthesis and preliminary evaluation of antinociceptive activity of novel isoxazolyl-aryl-hydrazones

    International Nuclear Information System (INIS)

    Reis, Silvio Leandro Goncalves Bomfim; Almeida, Valderes Moraes de; Almeida, Gleybson Correia de; Boaviagem, Karinna Moura; Mendes, Charles Christophe du Barriere; Faria, Antonio Rodolfo de; Goes, Alexandre Jose da Silva; Magalhaes, Laudelina Rodrigues; Silva, Teresinha Goncalves da

    2011-01-01

    New 2-isoxazoline aldehydes were synthesized, in good yields, from cycloadduct of the 1,3-dipolar cycloaddition reaction between endocyclic enecarbamate and carboethoxyformonitrile oxide (CEFNO). Condensation of these 2-isoxazoline aldehydes with several phenyl-hydrazines produced new isoxazolyl-aryl-hydrazones, which showed low toxicity and excellent antinociceptive activity, when compared to dipyrone. The antinociceptive activity of isoxazolyl-aryl-hydrazones was performed using the acetic acid-induced mice abdominal constrictions test. (author)

  6. Boron removal in radioactive liquid waste by forward osmosis membrane

    Energy Technology Data Exchange (ETDEWEB)

    Doo Seong Hwang; Hei Min Choi; Kune Woo Lee; Jei Kwon Moon [KAERI, Daejeon (Korea, Republic of)

    2013-07-01

    This study investigated the treatment of boric acid contained in liquid radioactive waste using a forward osmosis membrane. The boron permeation through the membrane depends on the type of membrane, membrane orientation, pH of the feed solution, salt and boron concentration in the feed solution, and osmotic pressure of the draw solution. The boron flux begins to decline from pH 7 and increases with an increase of the osmotic driving force. The boron flux decreases slightly with the salt concentration, but is not heavily influenced by a low salt concentration. The boron flux increases linearly with the concentration of boron. No element except for boron was permeated through the FO membrane in the multi-component system. The maximum boron flux is obtained in an active layer facing a draw solution orientation of the CTA-ES membrane under conditions of less than pH 7 and high osmotic pressure. (authors)

  7. Sulfonic acid functionalized boron nitride nanomaterials as a microwave-assisted efficient and highly biologically active one-pot synthesis of piperazinyl-quinolinyl fused Benzo[c]acridine derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Murugesan, Arul; Gengan, R.M., E-mail: genganrm@dut.ac.za; Krishnan, Anand

    2017-02-15

    Boron nitride nano material based solid acid catalyst was found to be an efficient and reusable sulfonic acid catalyst for the synthesis of one-pot Knoevenagel and Michael type reactions in 3, 3-dimethyl-9-(2-(4-methylpiperazin-1-yl) quinolin-3-yl)-3, 4, 9, 10-tetrahydroacridin-1(2H)-one derivatives under microwave irradiation conditions. The catalyst was prepared by mixing boron nitrile and (3-mercaptopropyl) trimethoxysilane. This is simple and safe method for the preparation of solid acid catalysts. The morphological properties of catalyst determined by using FT-IR, XRD, TEM, SEM and Raman spectroscopy. The synthesised catalyst was employed in Knoevenagel and Michael type reactions to synthesise novel piperazinyl-quinolinyl based acridine derivatives. Furthermore the newly-synthesised compounds have been used for molecular docking in DNA binding studies. The method developed in this study has the advantages of good yield, simplicity coupled with safety and short reaction time. Most importantly it was found that the solid acid catalyst can be recycled with only 5% loss of activity. - Highlights: • One-pot Synthesis of Knoevenagel and Michel type reactions. • Synthesis of Sulfonic acid Functionalized Boron nitride nano materials. • Synthesis of piperazinyl-quinolinyl fused Benzo[c]acridine derivatives under Microwave irradiation. • Molecular docking studies were performed on piperazinyl-quinolinyl acridine derivatives using DNA.

  8. Conformationally constrained dipeptide surrogates with aromatic side-chains: synthesis of 4-aryl indolizidin-9-one amino acids by conjugate addition to a common alpha,omega-diaminoazelate enone intermediate.

    Science.gov (United States)

    Cluzeau, Jérôme; Lubell, William D

    2004-03-05

    Four methyl 9-oxo-8-(N-(Boc)-amino)-4-phenyl-1-azabicyclo[4.3.0]nonane carboxylates (11, 4-Ph-I(9)aa-OMe) were synthesized from (2S,8S,5E)-di-tert-butyl-4-oxo-5-ene-2,8-bis[N-(PhF)amino]azelate [(5E)-7, PhF = 9-(9-phenylfluorenyl)] via a seven-step process featuring a conjugate addition/reductive amination/lactam cyclization sequence. Various nucleophiles were used in the conjugate addition reactions on enone (5E)-7 as a general route for making alpha,omega-diaminoazelates possessing different substituents in good yield albeit low diastereoselectivity except in the case of aryl Grignard reagents (9/1 to 15/1 drs). 6-Phenylazelates (6S)-8d and (6R)-8d were separated by chromatography and diastereoselective precipitation and independently transformed into 4-Ph-I(9)aa-OMe. From (6S)-8d, (2S,4R,6R,8S)-4-Ph-I(9)aa-OMe 11 was prepared selectively in 51% yield. Reductive amination of (6R)-8d provided the desired pipecolates 9 along with desamino compound 10, which was minimized by performing the hydrogenation in the presence of ammonium acetate. Subsequent ester exchange, lactam cyclization, and amine protection provided three products (2R,4S,6S,8R)-, (2R,4S,6S,8S)-, and (2S,4S,6R,8S)-4-Ph-I(9)aa-OMe 11 in 10, 6, and 6% yields, respectively, from (6R)-8d. Ester hydrolysis of (2S,4R,6R,8S)-11 furnished 4-phenyl indolizidin-9-one N-(Boc)amino acid 3 as a novel constrained Ala-Phe dipeptide surrogate for studying conformation-activity relationships of biologically active peptides.

  9. The determination of boron and carbon in reactor grade boron carbide

    International Nuclear Information System (INIS)

    Crossley, D.; Wood, A.J.; McInnes, C.A.J.; Jones, I.G.

    1978-09-01

    The sealed tube method of dissolution at high temperature and pressure has been successfully applied in the analysis of reactor grade boron carbide for the determination of boron. A 50 mg sample of boron carbide is completely dissolved by heating with concentrated nitric acid in a sealed tube at 300 0 C. The boron content of the resultant sample solution is determined by the mannitol potentiometric titration method. The precision of the method for the determination of 2.5 mg of boron using the Harwell automatic potentiometric titrator is 0.2% (coefficient of variation). The carbon content of a boron carbide sample is determined by combustion of the sample at 1050 0 C in a stream of oxygen using vanadium pentoxide to ensure the complete oxidation of the sample. The carbon dioxide produced from the sample is measured manometrically and the precision of the method for the determination of 4 mg of carbon is 0.4% (coefficient of variation). (author)

  10. Insights into the Mechanisms Underlying Boron Homeostasis in Plants

    Directory of Open Access Journals (Sweden)

    Akira Yoshinari

    2017-11-01

    Full Text Available Boron is an essential element for plants but is toxic in excess. Therefore, plants must adapt to both limiting and excess boron conditions for normal growth. Boron transport in plants is primarily based on three transport mechanisms across the plasma membrane: passive diffusion of boric acid, facilitated diffusion of boric acid via channels, and export of borate anion via transporters. Under boron -limiting conditions, boric acid channels and borate exporters function in the uptake and translocation of boron to support growth of various plant species. In Arabidopsis thaliana, NIP5;1 and BOR1 are located in the plasma membrane and polarized toward soil and stele, respectively, in various root cells, for efficient transport of boron from the soil to the stele. Importantly, sufficient levels of boron induce downregulation of NIP5;1 and BOR1 through mRNA degradation and proteolysis through endocytosis, respectively. In addition, borate exporters, such as Arabidopsis BOR4 and barley Bot1, function in boron exclusion from tissues and cells under conditions of excess boron. Thus, plants actively regulate intracellular localization and abundance of transport proteins to maintain boron homeostasis. In this review, the physiological roles and regulatory mechanisms of intracellular localization and abundance of boron transport proteins are discussed.

  11. Synthesis of quaternary aryl phosphonium salts: photoredox-mediated phosphine arylation.

    Science.gov (United States)

    Fearnley, A F; An, J; Jackson, M; Lindovska, P; Denton, R M

    2016-04-11

    We report a synthesis method for the construction of quaternary aryl phoshonium salts at ambient temperature. The regiospecific reaction involves the coupling of phosphines with aryl radicals derived from diaryliodonium salts under photoredox conditions.

  12. Utilization of Boron Compounds for the Modification of Suberoyl Anilide Hydroxamic Acid as Inhibitor of Histone Deacetylase Class II Homo sapiens

    Science.gov (United States)

    Bakri, Ridla; Parikesit, Arli Aditya; Satriyanto, Cipta Prio; Kerami, Djati; Tambunan, Usman Sumo Friend

    2014-01-01

    Histone deacetylase (HDAC) has a critical function in regulating gene expression. The inhibition of HDAC has developed as an interesting anticancer research area that targets biological processes such as cell cycle, apoptosis, and cell differentiation. In this study, an HDAC inhibitor that is available commercially, suberoyl anilide hydroxamic acid (SAHA), has been modified to improve its efficacy and reduce the side effects of the compound. Hydrophobic cap and zinc-binding group of these compounds were substituted with boron-based compounds, whereas the linker region was substituted with p-aminobenzoic acid. The molecular docking analysis resulted in 8 ligands with ΔG binding value more negative than the standards, SAHA and trichostatin A (TSA). That ligands were analyzed based on the nature of QSAR, pharmacological properties, and ADME-Tox. It is conducted to obtain a potent inhibitor of HDAC class II Homo sapiens. The screening process result gave one best ligand, Nova2 (513246-99-6), which was then further studied by molecular dynamics simulations. PMID:25214833

  13. Enhanced electrochemical response in oxidative differential pulse voltammetry of dopamine in the presence of ascorbic acid at carboxyl-terminated boron-doped diamond electrodes

    International Nuclear Information System (INIS)

    Kondo, Takeshi; Niwano, Yu; Tamura, Akira; Imai, Junichi; Honda, Kensuke; Einaga, Yasuaki; Tryk, Donald A.; Fujishima, Akira; Kawai, Takeshi

    2009-01-01

    The differential pulse voltammetric (DPV) peak for dopamine (DA) oxidation was found to be highly amplified by the addition of ascorbic acid (AA) when carboxyl-terminated boron-doped diamond (BDD) electrodes were used as the working electrode. The DP voltammogram for a solution containing DA and AA obtained using a 4-pentenoic acid-modified BDD (4PA-BDD) electrode showed well-separated oxidation peaks for DA and AA at 0.4 and 0.6 V vs. Ag/AgCl, respectively. In addition, as the DA concentration increased at constant AA concentration, a simultaneous increase in the DA peak current density and decrease in the AA peak current density were observed. The slope of the calibration curve for the [DA] range of 1-10 μM in the presence of AA (500 μM) was seven times larger than that obtained in the absence of AA. Such an enhancement was found to be more efficient at 4PA-BDD than at oxidized-BDD, partly due to simple electrostatic effects and partly due to suppression of the polymerization of DA oxidation products by the terminal carboxyl groups. The enhanced detection method using a carboxyl-terminated BDD electrode should be an effective analytical tool, especially for determining low concentrations of DA in the presence of high concentrations of AA

  14. Enhanced electrochemical response in oxidative differential pulse voltammetry of dopamine in the presence of ascorbic acid at carboxyl-terminated boron-doped diamond electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, Takeshi [Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan)], E-mail: t.kondo@ci.kagu.tus.ac.jp; Niwano, Yu; Tamura, Akira; Imai, Junichi [Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan); Honda, Kensuke [Department of Chemistry and Earth Sciences, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi-shi, Yamaguchi 753-8521 (Japan); Einaga, Yasuaki [Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Yokohama 223-0012 (Japan); Tryk, Donald A. [Fuel Cell Nanomaterials Center, University of Yamanashi, Takeda 4-3-11, Kofu, Yamanashi 400-8511 (Japan); Fujishima, Akira [Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu-ku, Kawasaki, Kanagawa 213-0012 (Japan); Kawai, Takeshi [Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 (Japan)

    2009-03-01

    The differential pulse voltammetric (DPV) peak for dopamine (DA) oxidation was found to be highly amplified by the addition of ascorbic acid (AA) when carboxyl-terminated boron-doped diamond (BDD) electrodes were used as the working electrode. The DP voltammogram for a solution containing DA and AA obtained using a 4-pentenoic acid-modified BDD (4PA-BDD) electrode showed well-separated oxidation peaks for DA and AA at 0.4 and 0.6 V vs. Ag/AgCl, respectively. In addition, as the DA concentration increased at constant AA concentration, a simultaneous increase in the DA peak current density and decrease in the AA peak current density were observed. The slope of the calibration curve for the [DA] range of 1-10 {mu}M in the presence of AA (500 {mu}M) was seven times larger than that obtained in the absence of AA. Such an enhancement was found to be more efficient at 4PA-BDD than at oxidized-BDD, partly due to simple electrostatic effects and partly due to suppression of the polymerization of DA oxidation products by the terminal carboxyl groups. The enhanced detection method using a carboxyl-terminated BDD electrode should be an effective analytical tool, especially for determining low concentrations of DA in the presence of high concentrations of AA.

  15. Photolytic inhibition and labeling of proteins with aryl diazonium compounds

    International Nuclear Information System (INIS)

    Tometsko, A.M.; Turula, J.; Comstock, J.

    1978-01-01

    In the course of preparing aryl azide derivatives for use as photoprobes, we have observed significant light sensitivity in the precursor aryl diazonium compounds. The photosensitive properties of this class of compounds are of interest since they will seek out cationic binding sites in biological targets, and can be employed to inhibit complementary targets at acid pH. The relationship between photolytic change in the structure of diazonium compounds and the corresponding change in function of a biological target are presented. Experiments are described in which the dark and light sensitive properties of a model diazonium compound, diazobenzene sulfonate (DBS), were determined. The ultraviolet spectra were used to evaluate the dark stability and light sensitivity og DBS. Chymotrypsin and trypsin served as functioning targets for further evaluation of the photochemical properties. Both enzymes are stable to the probe in the dark at acid pH. A rapid loss of enzyme activity was observed following flash photolysis of DBS-enzyme solutions. Photolytic incorporation of radioactive DBS into chymotrypsin was observed. Aryl diazonium salts can be employed to probe the availability of complementary sites in biological targets at different acid pH values. (Author)

  16. Boron isotopic enrichment by displacement chromatography

    International Nuclear Information System (INIS)

    Mohapatra, K.K.; Bose, Arun

    2014-01-01

    10 B enriched boron is used in applications requiring high volumetric neutron absorption (absorption cross section- 3837 barn for thermal and 1 barn for 1 MeV fast neutron). It is used in fast breeder reactor (as control rod material), in neutron counter, in Boron Neutron Capture Therapy etc. Owing to very small separation factor, boron isotopic enrichment is a complex process requiring large number of separation stages. Heavy Water Board has ventured in industrial scale production of 10 B enriched boron using Exchange Distillation Process as well as Ion Displacement Chromatography Process. Ion Displacement Chromatography process is used in Boron Enrichment Plant at HWP, Manuguru. It is based on isotopic exchange between borate ions (B(OH) 4 - ) on anion exchange resin and boric acid passing through resin. The isotopic exchange takes place due to difference in zero point energy of 10 B and 11 B

  17. XPS analysis of boron doped heterofullerenes

    Energy Technology Data Exchange (ETDEWEB)

    Schnyder, B; Koetz, R [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Muhr, H J; Nesper, R [ETH Zurich, Zurich (Switzerland)

    1997-06-01

    Boron heterofullerenes were generated through arc-evaporation of doped graphite rods in a helium atmosphere. According to mass spectrometric analysis only mono-substituted fullerenes like C{sub 59}B, C{sub 69}B and higher homologues together with a large fraction of higher undoped fullerenes were extracted and enriched when pyridine was used as the solvent. XPS analysis of the extracts indicated the presence of two boron species with significantly different binding energies. One peak was assigned to borid acid. The second one corresponds to boron in the fullerene cage, which is mainly C{sub 59}B, according to the mass spectrum. This boron is in a somewhat higher oxidation state than that of ordinary boron-carbon compounds. The reported synthesis and extraction procedure opens a viable route for production of macroscopic amounts of these compounds. (author) 2 figs., 1 tab., 7 refs.

  18. The Aggregation of Boron on the Tissues of Gold Fish (Carassius auratus Linnaeus, 1758

    Directory of Open Access Journals (Sweden)

    Tuncer Okan Genç

    2015-03-01

    Full Text Available In this study, it was aimed to determine the water-borne and food-borne boron accumulation in the liver and muscle tissues of Gold Fish (Carassius auratus Linnaeus, 1758. For each treatment, 12 individuals were. The water-borne boron treatments were applied as boron acid concentration of 1 mg/L, 10 mg/L and 20 mg/L in the aquarium water, while the food-borne boron treatments were prepared food contained the defined levels of boron (1 mg/kg, 5 mg/kg and 10 mg/kg as boric acid. The boron levels in the tissues were determined by an ICP-MS procedure. The maximum boron concentration was found in the 20mg/L water borne boron treatment in the liver tissue (1.78±0.02 mg/kg. In the water-borne boron treatments, the maximum Transfer Factor (TF was found in the 20mg/L boron concentration, and TF values were increased when the boron concentrations were decreasing. In the 1 mg/kg food-borne boron treatment, TF was found as 0, and increasing concentration of boron in the food caused an increase in TF reached about 0.06. This study suggested that the target organ for boron accumulation is the liver rather than the muscles and the accumulation of food-borne boron is lower when comparing water-borne boron.

  19. Evolutionary divergence of plant borate exporters and critical amino acid residues for the polar localization and boron-dependent vacuolar sorting of AtBOR1

    KAUST Repository

    Wakuta, Shinji

    2015-01-24

    Boron (B) is an essential micronutrient for plants but is toxic when accumulated in excess. The plant BOR family encodes plasma membrane-localized borate exporters (BORs) that control translocation and homeostasis of B under a wide range of conditions. In this study, we examined the evolutionary divergence of BORs among terrestrial plants and showed that the lycophyte Selaginella moellendorffii and angiosperms have evolved two types of BOR (clades I and II). Clade I includes AtBOR1 and homologs previously shown to be involved in efficient transport of B under conditions of limited B availability. AtBOR1 shows polar localization in the plasma membrane and high-B-induced vacuolar sorting, important features for efficient B transport under low-B conditions, and rapid down-regulation to avoid B toxicity. Clade II includes AtBOR4 and barley Bot1 involved in B exclusion for high-B tolerance. We showed, using yeast complementation and B transport assays, that three genes in S. moellendorffii, SmBOR1 in clade I and SmBOR3 and SmBOR4 in clade II, encode functional BORs. Furthermore, amino acid sequence alignments identified an acidic di-leucine motif unique in clade I BORs. Mutational analysis of AtBOR1 revealed that the acidic di-leucine motif is required for the polarity and high-B-induced vacuolar sorting of AtBOR1. Our data clearly indicated that the common ancestor of vascular plants had already acquired two types of BOR for low- and high-B tolerance, and that the BOR family evolved to establish B tolerance in each lineage by adapting to their environments. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists.

  20. Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

    Science.gov (United States)

    Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

    2014-12-19

    A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

  1. Enhancing the electrochemical oxidation of acid-yellow 36 azo dye using boron-doped diamond electrodes by addition of ferrous ion

    International Nuclear Information System (INIS)

    Villanueva-Rodriguez, M.; Hernandez-Ramirez, A.; Peralta-Hernandez, J.M.; Bandala, Erick R.; Quiroz-Alfaro, Marco A.

    2009-01-01

    This work shows preliminary results on the electrochemical oxidation process (EOP) using boron-doped diamond (BDD) electrode for acidic yellow 36 oxidation, a common azo dye used in textile industry. The study is centred in the synergetic effect of ferrous ions and hydroxyl free radicals for improving discoloration of azo dye. The assays were carried out in a typical glass cell under potentiostatic conditions. On experimental conditions, the EOP was able to partially remove the dye from the reaction mixture. The reaction rate increased significantly by addition of Fe 2+ (1 mM as ferrous sulphate) to the system and by (assumed) generation of ferrate ion [Fe(VI)] over BDD electrode. Ferrate is considered as a highly oxidizing reagent capable of removing the colorant from the reaction mixture, in synergistic action with the hydroxyl radicals produced on the BDD surface. Further increases in the Fe 2+ concentration lead to depletion of the reaction rate probably due to the hydroxyl radical scavenging effect of Fe 2+ excess in the system.

  2. A novel biosensor based on boronic acid functionalized metal-organic frameworks for the determination of hydrogen peroxide released from living cells.

    Science.gov (United States)

    Dai, Hongxia; Lü, Wenjuan; Zuo, Xianwei; Zhu, Qian; Pan, Congjie; Niu, Xiaoying; Liu, Juanjuan; Chen, HongLi; Chen, Xingguo

    2017-09-15

    In this work, we report a durable and sensitive H 2 O 2 biosensor based on boronic acid functionalized metal-organic frameworks (denoted as MIL-100(Cr)-B) as an efficient immobilization matrix of horseradish peroxidase (HRP). MIL-100(Cr)-B features a hierarchical porous structure, extremely high surface area, and sufficient recognition sites, which can significantly increase HRP loading and prevent them from leakage and deactivation. The H 2 O 2 biosensor can be easily achieved without any complex processing. Meanwhile, the immobilized HRP exhibited enhanced stability and remarkable catalytic activity towards H 2 O 2 reduction. Under optimal conditions, the biosensor showed a fast response time (less than 4s) to H 2 O 2 in a wide linear range of 0.5-3000μM with a low detection limit of 0.1μM, as well as good anti-interference ability and long-term storage stability. These excellent performances substantially enable the proposed biosensor to be used for the real-time detection of H 2 O 2 released from living cells with satisfactory results, thus showing the potential application in the study of H 2 O 2 -involved dynamic pathological and physiological process. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. A simple chip free-flow electrophoresis for monosaccharide sensing via supermolecule interaction of boronic acid functionalized quencher and fluorescent dye.

    Science.gov (United States)

    Yin, Xiao-Yang; Dong, Jing-Yu; Wang, Hou-Yu; Li, Si; Fan, Liu-Yin; Cao, Cheng-Xi

    2013-08-01

    Here, a simple micro free-flow electrophoresis (μFFE) was developed for fluorescence sensing of monosaccharide via supermolecule interaction of synthesized boronic acid functionalized benzyl viologen (ο-BBV) and fluorescent dye. The μFFE contained two open electrode cavities and an ion-exchange membrane was sandwiched between two polymethylmethacrylate plates. The experiments demonstrated the following merits of developed μFFE: (i) up to 90.5% of voltage efficiency due to high conductivity of ion-exchange membrane; (ii) a strong ability against influence of bubble produced in two electrodes due to open design of electrode cavities; and (iii) reusable and washable separation chamber (45 mm × 17 mm × 100 μm, 77 μL) avoiding the discard of μFFE due to blockage of solute precipitation in chamber. Remarkably, the μFFE was first designed for the sensing of monosaccharide via the supermolecule interaction of synthesized ο-BBV, fluorescent dye, and monosaccharide. Under the optimized conditions, the minimum concentration of monosaccharide that could be detected was 1 × 10(-11) M. Finally, the developed device was used for the detection of 0.3 mM glucose spiked in human urine. All of the results demonstrated the feasibility of monosaccharide detection via the μFFE. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Polycomplexes of Hyaluronic Acid and Borates in a Solid State and Solution: Synthesis, Characterization and Perspectives of Application in Boron Neutron Capture Therapy

    Directory of Open Access Journals (Sweden)

    Alexander N. Zelenetskii

    2018-02-01

    Full Text Available In this report, we propose a new polyborate fragment synthesis strategy along the whole chain of the polysaccharide hyaluronic acid (HA to produce boron neutron capture therapy (BNCT compounds. Under high pressure and deformatory solid-state conditions, polymolecular system formation takes place due to association of phase-specific transition components into a more or less distinct microscopic organization. Fourier transform infrared (FTIR spectroscopy shows that HA and polyborates form a network of cyclic polychelate complexes. HA acts as a multidentate ligand using carboxylic and hydroxyl proton donor groups to link oxygen atoms in B–O–B bonds and borate-anions B–O(−: O–H···O, O–H···(−O. With free electron pairs in heteroatoms –O(:···B, –N(:···B, HA can act simultaneously as an electron donor. Nuclear magnetic resonance (NMR with 13C and 1H reveals a preserved complex interaction after both solubilizing and attenuating the HA-polyborate system. Stability of the product in water, low cost, ease of synthesis and scalability of manufacturing indicate that HA-polyborate complexes might have advantages over current chemotherapeutic approaches in creating therapeutic agents for BNCT.

  5. Nucleophilic 18F-Labeling of Spirocyclic Iodonium Ylide or Boronic Pinacol Ester Precursors - Advantages and Disadvantages

    DEFF Research Database (Denmark)

    Petersen, Ida Nymann; Kristensen, Jesper Langgaard; Herth, Matthias Manfred

    2017-01-01

    The field of labeling electron-rich aryl compounds with nucleophilic [18F]fluoride has recently expanded with radiofluorination strategies that apply boronic esters or spirocyclic iodonium ylides as precursors. Herein, we present a direct comparison of these strategies by using nine chemically di...

  6. Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

    Science.gov (United States)

    Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

    2014-02-18

    The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

  7. Evolutionary divergence of plant borate exporters and critical amino acid residues for the polar localization and boron-dependent vacuolar sorting of AtBOR1

    KAUST Repository

    Wakuta, Shinji; Mineta, Katsuhiko; Amano, Taro; Toyoda, Atsushi; Fujiwara, Toru; Naito, Satoshi; Takano, Junpei

    2015-01-01

    Boron (B) is an essential micronutrient for plants but is toxic when accumulated in excess. The plant BOR family encodes plasma membrane-localized borate exporters (BORs) that control translocation and homeostasis of B under a wide range

  8. Aspects of the chemistry of boron

    International Nuclear Information System (INIS)

    Moellinger, H.

    1976-01-01

    Crystal phases of elementary boron are reviewed as well as boron-sulphur, boron-selenum, boron-tellurium, and boron-nitrogen compounds, carboranes, and boron-carbohydrate complexes. A boron cadastre of rivers and lakes serves to illustrate the role of boron in environmental protection. Technically relevant boron compounds and their uses are mentioned. (orig.) 891 HK/orig. 892 MB [de

  9. Synthesis and evaluation of boronated folates for BNCT

    International Nuclear Information System (INIS)

    Shukla, S.; Sekido, M.; Guo, W.; Mueller, R.; Sudimack, J.; Lee, R.J.; Tjarks, W.; Adams, D.M.; Barth, R.F.

    2000-01-01

    To study the possible utilization of folic acid as the 10 B carrier for BNCT, folic acid conjugated boron containing liposomes and starburst dendrimers were prepared. In both systems folic acid was used as the recognition part and polyethylene glycol (PEG) as the spacer. In vitro studies were carried out using folate receptor overexpressing 24JK-FBP and KB cells. The results indicated that these boronated folic acid conjugates were incorporated into the tumor cells via receptor-mediated endocytosis. (author)

  10. A direct method to visualise the aryl acylamidase activity on cholinesterases in polyacrylamide gels

    Directory of Open Access Journals (Sweden)

    Boopathy Rathanam

    2000-12-01

    Full Text Available Abstract Background In vertebrates, two types of cholinesterases exist, acetylcholinesterase and butyrylcholinesterase. The function of acetylcholinesterase is to hydrolyse acetylcholine, thereby terminating the neurotransmission at cholinergic synapse, while the precise physiological function of butyrylcholinesterase has not been identified. The presence of cholinesterases in tissues that are not cholinergically innervated indicate that cholinesterases may have functions unrelated to neurotransmission. Furthermore, cholinesterases display a genuine aryl acylamidase activity apart from their predominant acylcholine hydrolase activity. The physiological significance of this aryl acylamidase activity is also not known. The study on the aryl acylamidase has been, in part hampered by the lack of a specific method to visualise this activity. We have developed a method to visualise the aryl acylamidase activity on cholinesterase in polyacrylamide gels. Results The o-nitroaniline liberated from o-nitroacetanilide by the action of aryl acylamidase activity on cholinesterases, in the presence of nitrous acid formed a diazonium compound. This compound gave an azo dye complex with N-(1-napthyl-ethylenediamine, which appeared as purple bands in polyacrylamide gels. Treating the stained gels with trichloroacetic acid followed by Tris-HCl buffer helped in fixation of the stain in the gels. By using specific inhibitors for acetylcholinesterase and butyrylcholinesterase, respectively, differential staining for the aryl acylamidase activities on butyrylcholinesterase and acetylcholinesterase in a sample containing both these enzymes has been demonstrated. A linear relationship between the intensity of colour developed and activity of the enzyme was obtained. Conclusions A novel method to visualise the aryl acylamidase activity on cholinesterases in polyacrylamide gels has been developed.

  11. Design and stereoselective synthesis of a C-aryl furanoside as a conformationally constrained CHIR-090 analogue

    DEFF Research Database (Denmark)

    Oddo, Alberto; Holl, Ralph

    2012-01-01

    The UDP-3-O-[(R)-3-hydroxymyristoyl]-N-acetylglucosamine deacetylase (LpxC) is a promising target for the development of novel antibiotic substances against multidrug-resistant Gram-negative bacteria. The C-aryl glycoside 3 was designed as conformationally constrained analogue of the potent LpxC-......, and esterification. A Sonogashira reaction of the aryl iodide 11 led to the alkyne 17 which was transformed with H(2)NOH into the hydroxamic acid 3....

  12. Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids.

    Science.gov (United States)

    Martín-Sómer, Ana; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2015-01-21

    The intrinsic acidity of CH2[double bond, length as m-dash]CHXH2, HC[triple bond, length as m-dash]CXH2 (X = N, P, As, Sb) derivatives and of their complexes with BeH2 and BH3 has been investigated by means of high-level density functional theory and molecular orbital ab initio calculations, using as a reference the ethyl saturated analogues. The acidity of the free systems steadily increases down the group for the three series of derivatives, ethyl, vinyl and ethynyl. The association with both beryllium dihydride and borane leads to a very significant acidity enhancement, being larger for BeH2 than for BH3 complexes. This acidity enhancement, for the unsaturated compounds, is accompanied by a change in the acidity trends down the group, which do not steadily decrease but present a minimum value for both the vinyl- and the ethynyl-phosphine. When the molecule acting as the Lewis acid is beryllium dihydride, the π-type complexes in which the BeH2 molecules interact with the double or triple bond are found, in some cases, to be more stable, in terms of free energies, than the conventional complexes in which the attachment takes place at the heteroatom, X. The most important finding, however, is that P, As, and Sb ethynyl complexes with BeH2 do not behave as P, As, or Sb Brønsted acids, but unexpectedly as Be acids.

  13. Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

    Science.gov (United States)

    Hari, Durga Prasad; Schroll, Peter; König, Burkhard

    2012-02-15

    Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

  14. Structure and reactivity of boron-ate complexes derived from primary and secondary boronic esters.

    Science.gov (United States)

    Feeney, Kathryn; Berionni, Guillaume; Mayr, Herbert; Aggarwal, Varinder K

    2015-06-05

    Boron-ate complexes derived from primary and secondary boronic esters and aryllithiums have been isolated, and the kinetics of their reactions with carbenium ions studied. The second-order rate constants have been used to derive nucleophilicity parameters for the boron-ate complexes, revealing that nucleophilicity increased with (i) electron-donating aromatics on boron, (ii) neopentyl glycol over pinacol boronic esters, and (iii) 12-crown-4 ether.

  15. Synthesis and characterization of ammonium phosphate fertilizers with boron

    Directory of Open Access Journals (Sweden)

    ANGELA MAGDA

    2010-07-01

    Full Text Available The concentration of boron, an essential micronutrient for plants, presents a narrow range between deficiency and toxicity. In order to provide the boron requirement for plants, and to avoid toxicity problems, boron compounds are mixed with basic fertilizers. Sodium borate pentahydrate was used as a boron source. Ammonium orthophosphates fertilizers with boron were prepared by neutralizing phosphoric acid with ammonia and addition of variable amounts of sodium tetraborate pentahydrate to the reaction mixture at a NH3:H3PO4 molar ratio of 1.5. The fertilizers obtained with boron contents ranging from 0.05 to 1 % (w/w were fully characterized by chemical analysis, thermal analysis, X-ray diffraction and infrared spectrophotometry. The studies showed that up to 500 °C, regardless of the boron content, no significant changes concerning thermal stability and nutritional properties occurred. Above 500 °C, an increase of thermal stability with an increase of the boron content was observed. X-Ray diffraction of a heat-treated sample containing 5 % (w/w boron indicated the appearance of boron orthophosphate, BPO4, as a new crystalline phase, and the disappearance of the previous structures above 500 °C, which explains the increase in thermal stability.

  16. Rapid small intestinal permeability assay based on riboflavin and lactulose detected by bis-boronic acid appended benzyl viologens.

    Science.gov (United States)

    Resendez, Angel; Abdul Halim, Md; Landhage, Caroline M; Hellström, Per M; Singaram, Bakthan; Webb, Dominic-Luc

    2015-01-15

    Although organoboronic acids are efficient high-throughput sugar sensors, they have not been pursued for gut permeability studies. A modification of the lactulose/mannitol assay is described by which small intestinal permeability is assessed at the time of urine collection using a lactulose/riboflavin ratio. Volunteers ingested 50mg riboflavin and either 5 g mannitol or 10 g lactulose. Urine was collected for 6 hrs. Riboflavin was assayed by autofluorescence. Riboflavin was removed by C18 solid phase extraction. Lactulose and mannitol were then assayed using 1,1'-bis(2-boronobenzyl)-4,4'-bipyridinium (4,4'oBBV) coupled to the fluorophore HPTS. The temporal profile over 6 hrs for riboflavin paralleled mannitol. Riboflavin recovery in urine was 11.1 ± 1.9 % (mean ± SEM, n=7), similar to mannitol. There was selective binding of 4,4'oBBV to lactulose, likely involving cooperativity between the fructose and galactose moieties. Lower limits of detection and quantification were 90 and 364 μM. The lactulose assay was insensitive to other permeability probes (e.g., sucrose, sucralose) while tolerating glucose or lactose. This assay can be adapted to automated systems. Stability of 4,4'oBBV exceeds 4 years. Riboflavin measured by autofluorescence combined with lactulose measured with 4,4'oBBV represents a useful new chemistry for rapid measurement of intestinal permeability with excellent stability, cost and throughput benefits. Copyright © 2014. Published by Elsevier B.V.

  17. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    Science.gov (United States)

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

  18. Boron-containing thioureas for neutron capture therapy. Borhaltige Thioharnstoffe fuer die Neutroneneinfangtherapie

    Energy Technology Data Exchange (ETDEWEB)

    Ketz, H.

    1993-10-21

    Melanin is produced in large amounts in malignant melanotic melanomas. Because thiourea compounds are covalently incorporated into melanin during its biosynthesis, the preparation of boronated thiourea-derivatives is of particular interest for the BNCT (Boron Neutron Capture Therapy). Accumulation of boron in tumors by means of boronated thiourea-derivatives may therefore provide levels of [sup 10]B which are useful for BNCT. In BNCT the tumor containing the boron compound is irradiated with epithermal neutrons to generate He- and Li-nuclei from the [sup 10]B which can then destroy the tumor cells. Because of the short ranges of these particles (approximately one cell diameter) the damage will be almost exclusively confined to the tumor leaving normal tissue unharmed. High accumulation of 2-mercapto-1-methylimidazole (methimazole) in melanotic melanomas has been described in the literature. Boronated derivatives of methimazole were therefore synthesized. Boron was in the form of a boronic acid, a nido-carbonate and a mercaptoundeca hydro-closo-dodecaborate (BSH). The synthesis of the boron cluster derivatives of methimazole (nido-carborate- and BSH-derivatives) with 9 resp. 12 boron atoms in the molecule were expected to achieve higher concentrations of boron in the tumor than in the case of the boronic acid compound with its single boron atom. (orig.)

  19. Application of electrochemical advanced oxidation processes with a boron-doped diamond anode to degrade acidic solutions of Reactive Blue 15 (Turqueoise Blue) dye

    International Nuclear Information System (INIS)

    Solano, Aline Maria Sales; Martínez-Huitle, Carlos Alberto; Garcia-Segura, Sergi; El-Ghenymy, Abdellatif

    2016-01-01

    Highlights: • Degradation of Reactive Blue 15 solution at pH 3.0 by electrochemical oxidation, electro-Fenton and photoelectro-Fenton. • Hard destruction of the dye and its products by BDD(·OH) and much more rapidly by ·OH. • 94% mineralization by the most powerful photoelectro-Fenton at 66.7 mA cm"−"2, with acetic acid accumulation. • 25 aromatics and heteroaromatics, 30 hydroxylated derivatives and 4 carboxylic acids as products. • Release of Cl"−, SO_4"2"− and pre-eminently NO_3"− during dye mineralization. - Abstract: The degradation of the copper-phthalocyanine dye Reactive Blue 15 dye in sulfate medium has been comparatively studied by electrochemical oxidation with electrogenerated H_2O_2 (EO-H_2O_2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments with 100 cm"3 solutions of 0.203 mmol dm"−"3 dye were performed with a stirred tank reactor containing a boron-doped diamond (BDD) anode and an air-diffusion cathode for continuous H_2O_2 production. Experimental conditions of pH 3.0 and 0.50 mmol dm"−"3 Fe"2"+ as catalyst were found optimal for the EF process by the predominant oxidation with hydroxyl radicals formed in the bulk from Fenton’s reaction between added Fe"2"+ and generated H_2O_2. The kinetics of Reactive Blue 15 abatement was followed by reversed-phase HPLC and always obeyed a pseudo-first-order reaction. The decolorization rate in EO-H_2O_2 was much lower than dye decay due to the formation of large quantities of colored intermediates under the action of hydroxyl radicals generated at the BDD anode from water oxidation. In contrast, the color and dye removals were much more rapid in EF and PEF by the most efficient oxidation of hydroxyl radicals produced from Fenton’s reaction. PEF was the most powerful treatment owing to the photolytic action of UVA irradiation, yielding 94% mineralization after 360 min at 66.7 mA cm"−"2. The effect of current density over the performance of all methods was examined. LC

  20. Highly Efficient Synthesis of 2-Aryl-3-methoxyacrylates via Suzuki-Miyaura Coupling Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyung Ho; Lee, Chun Ho; Song, Young Seob; Park, No Kyun; Kim, Bum Tae; Heo, Jung Nyoung [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of)

    2006-02-15

    We have developed a highly efficient and convergent synthesis of 2-aryl-3-methoxyacrylates via the Suzuki-Miyaura coupling reaction of α-iodo-β-methoxy-acrylate with arylboronic acids. The biological activities of 2-aryl-3-methoxyacrylate derivatives will be reported in due course. The Suzuki-Miyaura coupling reaction provides a convenient access to the carbon-carbon bond formation with high efficiency. Recently, a number of 2-aryl-3-methoxy-acrylates served as a key scaffold for the development of biologically active pharmaceuticals and agrochemicals. Especially, the discovery of the naturally-occurring fungicides, such as strobilurin A and oudemansin A, possessing a β-methoxyacrylate moiety was immediately seized great attention by industrial research groups to open a new era of the strobilurin family including azoxy-strobin and picoxystrobin.

  1. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  2. Tandem trifluoromethylthiolation/aryl migration of aryl alkynoates to trifluoromethylthiolated alkenes.

    Science.gov (United States)

    Li, Huan; Liu, Shuai; Huang, Yangen; Xu, Xiu-Hua; Qing, Feng-Ling

    2017-09-12

    A trifluoromethylthiolation initiated aryl migration of aryl alkynoates was disclosed. This protocol employs AgSCF 3 as the SCF 3 source and MeCN as both the solvent and the hydrogen source. This provides a new access to trifluoromethylthiolated alkenes from readily available substrates and reagents.

  3. Boron Removal in Radioactive Liquid Waste by Forward Osmosis Membrane

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Dooseong; Choi, Hei Min; Lee, Kune Woo; Moon Jeikwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-05-15

    These wastes contain about 0.3-0.8 wt% boric acid and have been concentrated through an evaporation treatment. Boric acid tends to crystallize owing to its solubility, and to plug the evaporator. The volume reduction obtained through evaporation is limited by the amount of boric acid in the waste. As an emerging technology, forward osmosis (FO) has attracted growing interest in wastewater treatment and desalination. FO is a membrane process in which water flows across a semi-permeable membrane from a feed solution of lower osmotic pressure to a draw solution of higher osmotic pressure. However, very few studies on the removal of boron by FO have been performed. The objective of this study is to evaluate the possibility of boron separation in radioactive liquid waste by FO. In this study, the performance of FO was investigated to separate boron in the simulated liquid waste under the factors such as pH, osmotic pressure, ionic strength of the solution, and membrane characteristic. The boron separation in radioactive borate liquid waste was investigated with an FO membrane. When the feed solution containing boron is treated by the FO membrane, the boron permeation depends on the type of membrane, membrane orientation, pH of the feed solution, salt and boron concentration in the feed solution, and osmotic pressure of the draw solution. The boron flux begins to decline from pH 7, and increases with an increase in the osmotic driving force. The boron flux of the CTA-ES and ALFD membrane orientation is higher than those of the CTA-NW and ALFF orientation, respectively. The boron permeation rate is constant regardless of the osmotic pressure and membrane orientation. The boron flux decreases slightly with the salt concentration, but it is not heavily influenced at a low salt concentration.

  4. Boron Removal in Radioactive Liquid Waste by Forward Osmosis Membrane

    International Nuclear Information System (INIS)

    Hwang, Dooseong; Choi, Hei Min; Lee, Kune Woo; Moon Jeikwon

    2014-01-01

    These wastes contain about 0.3-0.8 wt% boric acid and have been concentrated through an evaporation treatment. Boric acid tends to crystallize owing to its solubility, and to plug the evaporator. The volume reduction obtained through evaporation is limited by the amount of boric acid in the waste. As an emerging technology, forward osmosis (FO) has attracted growing interest in wastewater treatment and desalination. FO is a membrane process in which water flows across a semi-permeable membrane from a feed solution of lower osmotic pressure to a draw solution of higher osmotic pressure. However, very few studies on the removal of boron by FO have been performed. The objective of this study is to evaluate the possibility of boron separation in radioactive liquid waste by FO. In this study, the performance of FO was investigated to separate boron in the simulated liquid waste under the factors such as pH, osmotic pressure, ionic strength of the solution, and membrane characteristic. The boron separation in radioactive borate liquid waste was investigated with an FO membrane. When the feed solution containing boron is treated by the FO membrane, the boron permeation depends on the type of membrane, membrane orientation, pH of the feed solution, salt and boron concentration in the feed solution, and osmotic pressure of the draw solution. The boron flux begins to decline from pH 7, and increases with an increase in the osmotic driving force. The boron flux of the CTA-ES and ALFD membrane orientation is higher than those of the CTA-NW and ALFF orientation, respectively. The boron permeation rate is constant regardless of the osmotic pressure and membrane orientation. The boron flux decreases slightly with the salt concentration, but it is not heavily influenced at a low salt concentration

  5. The photocatalyzed Meerwein arylation: classic reaction of aryl diazonium salts in a new light.

    Science.gov (United States)

    Hari, Durga Prasad; König, Burkhard

    2013-04-26

    The use of diazonium salts for aryl radical generation and C-H arylation processes has been known since 1896 when Pschorr first used the reaction for intramolecular cyclizations. Meerwein developed it further in the early 1900s into a general arylation method. However, this reaction could not compete with the transition-metal-mediated formation of C(sp(2))-C(sp(2)) bonds. The replacement of the copper catalyst with iron and titanium compounds improved the situation, but the use of photocatalysis to induce the one-electron reduction and activation of the diazonium salts is even more advantageous. The first photocatalyzed Pschorr cyclization was published in 1984, and just last year a series of papers described applications of photocatalytic Meerwein arylations leading to aryl-alkene coupling products. In this Minireview we summarize the origins of this reaction and its scope and applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. An overview the boron dilution issue in PWRs

    International Nuclear Information System (INIS)

    Hyvaerinen, J.

    1994-01-01

    The presentation is an overview of boron (boric acid) dilution in pressurized water reactors (PWRs). Boric acid has been widely used in PWRs as a dissolved poison, as one of the main reactivity controlling means, for a long time, from nearly but not quite from the beginning of the design, construction and operation of PWRs in the present-day sense. The specific safety issue, namely the risk of uncontrolled reactivity insertion due to inadvertent boron dilution, is discussed first, followed by a brief look on the history of boron usage in PWRs. A discussion of boron dilution phenomenology is presented next in general terms. Some particular concerns that boron dilution phenomena arouse in the minds of a regulator will also be presented before concluding with a brief look on the future of dissolved poisons. (11 refs.)

  7. Boron-based nanostructures: Synthesis, functionalization, and characterization

    Science.gov (United States)

    Bedasso, Eyrusalam Kifyalew

    Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any

  8. A highly selective turn-on fluorescent probe for hypochlorous acid based on hypochlorous acid-induced oxidative intramolecular cyclization of boron dipyrromethene-hydrazone

    International Nuclear Information System (INIS)

    Chen, Wei-Chieh; Venkatesan, Parthiban; Wu, Shu-Pao

    2015-01-01

    Highlights: • A BODIPY-based fluorescent probe for sensing HOCl was developed. • The probe utilizes the HOCl-promoted cyclization in response to the amount of HOCl. • The probe might have application in the investigation of HOCl in biological systems. - Abstract: A BODIPY-based fluorescent probe, HBP, was developed for the detection of hypochlorous acid based on the specific hypochlorous acid-promoted oxidative intramolecular cyclization of heterocyclic hydrazone in response to the amount of HOCl. The reaction is accompanied by a 41-fold increase in the fluorescent quantum yield (from 0.004 to 0.164). The fluorescence intensity of the reaction between HOCl and HBP is linear in the HOCl concentration range of 1–8 μM with a detection limit of 2.4 nM (S/N = 3). Confocal fluorescence microscopy imaging using RAW264.7 cells showed that the new probe HBP could be used as an effective fluorescent probe for detecting HOCl in living cells

  9. A highly selective turn-on fluorescent probe for hypochlorous acid based on hypochlorous acid-induced oxidative intramolecular cyclization of boron dipyrromethene-hydrazone

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Chieh; Venkatesan, Parthiban; Wu, Shu-Pao, E-mail: spwu@mail.nctu.edu.tw

    2015-07-02

    Highlights: • A BODIPY-based fluorescent probe for sensing HOCl was developed. • The probe utilizes the HOCl-promoted cyclization in response to the amount of HOCl. • The probe might have application in the investigation of HOCl in biological systems. - Abstract: A BODIPY-based fluorescent probe, HBP, was developed for the detection of hypochlorous acid based on the specific hypochlorous acid-promoted oxidative intramolecular cyclization of heterocyclic hydrazone in response to the amount of HOCl. The reaction is accompanied by a 41-fold increase in the fluorescent quantum yield (from 0.004 to 0.164). The fluorescence intensity of the reaction between HOCl and HBP is linear in the HOCl concentration range of 1–8 μM with a detection limit of 2.4 nM (S/N = 3). Confocal fluorescence microscopy imaging using RAW264.7 cells showed that the new probe HBP could be used as an effective fluorescent probe for detecting HOCl in living cells.

  10. Photocatalytic Arylation of Alkenes, Alkynes and Enones with Diazonium Salts

    OpenAIRE

    Schroll, Peter; Hari, Durga Prasad; König, Burkhard

    2012-01-01

    Teaching old dogs new tricks: Visible light photoredox catalysis improves the classic Meerwein arylation protocol significantly and allows the light-controlled arylation of alkenes, alkynes and enones by diazonium salts.

  11. Ligand-Enabled Reactivity and Selectivity in a Synthetically Versatile Aryl C–H Olefination*

    Science.gov (United States)

    Wang, Dong-Hui; Engle, Keary M.; Shi, Bing-Feng; Yu, Jin-Quan

    2010-01-01

    The Mizoroki–Heck reaction, which couples aryl halides with olefins, has been widely used to stitch together the carbogenic cores of numerous complex organic molecules. Given that the position-selective introduction of a halide onto an arene is not always straightforward, direct olefination of aryl C–H bonds would obviate the inefficiencies associated with generating halide precursors or their equivalents; however, methods for carrying out such a reaction have suffered from narrow substrate scope and low positional selectivity. Here we report an operationally simple, atom-economical, carboxylate-directed Pd(II)-catalyzed C–H olefination reaction with phenylacetic acid and 3-phenylpropionic acid substrates, using oxygen at atmospheric pressure as the oxidant. The positional selectivity can be tuned by introducing amino acid derivatives as ligands. We demonstrate the versatility of the method through direct elaboration of commercial drug scaffolds and efficient synthesis of 2-tetralone and naphthoic acid natural product cores. PMID:19965380

  12. Development of effective methods for determination of boron in soils and soil solutions

    Directory of Open Access Journals (Sweden)

    Мaruan Tanasheva

    2012-12-01

    Full Text Available This paper is related to serious ecological problem in agriculture: soil degradation in rice fields in South Kazakhstan and in particular, to boron toxicity in rice, which resulted in reduced crop yields. The following abiotic factors were studied to determine the ability of boron to accumulate in rice fields: soil type, soil properties like salinity and acidity', season (level of precipitation, water logging /water shortage. The results shows that the severity of boron excess for fertility of rice crop which depends on boron ionic composition in soil. Adverse impact of both boron deficiency and boron excess are discussed. The necessity of boron fertilizers is shown for soils with high boron mobility.

  13. Differentiation in boron distribution in adult male and female rats' normal brain: A BNCT approach

    International Nuclear Information System (INIS)

    Goodarzi, Samereh; Pazirandeh, Ali; Jameie, Seyed Behnamedin; Baghban Khojasteh, Nasrin

    2012-01-01

    Boron distribution in adult male and female rats' normal brain after boron carrier injection (0.005 g Boric Acid+0.005 g Borax+10 ml distilled water, pH: 7.4) was studied in this research. Coronal sections of control and trial animal tissue samples were irradiated with thermal neutrons. Using alpha autoradiography, significant differences in boron concentration were seen in forebrain, midbrain and hindbrain sections of male and female animal groups with the highest value, four hours after boron compound injection. - Highlights: ► Boron distribution in male and female rats' normal brain was studied in this research. ► Coronal sections of animal tissue samples were irradiated with thermal neutrons. ► Alpha and Lithium tracks were counted using alpha autoradiography. ► Different boron concentration was seen in brain sections of male and female rats. ► The highest boron concentration was seen in 4 h after boron compound injection.

  14. Photometric and emission-spectrometric determination of boron in steels

    International Nuclear Information System (INIS)

    Thierig, D.

    1982-01-01

    A method for the photometric determination of boron in unalloyed and alloyed steels is described, in which Curcumine is used as reagent. A separation of boron is not necessary. Limit of detection: 0.0003% B. The decomposition of boron nitride in the steel is achieved by heating the whole sample in fuming sulphuric acid/phosphoric acid. For the emission spectrometric investigation of solid steel samples and for the spectrochemical analysis of solutions with plasma excitation working parameters are given and possibilities of interferences are demonstrated. (orig.) [de

  15. Biological processes for the production of aryl sulfates

    DEFF Research Database (Denmark)

    2016-01-01

    The present invention generally relates to the field of biotechnology as it applies to the production of aryl sulfates using polypeptides or recombinant cells comprising said polypeptides. More particularly, the present invention pertains to polypeptides having aryl sulfotransferase activity......, recombinant host cells expressing same and processes for the production of aryl sulfates employing these polypeptides or recombinant host cells....

  16. Designing your boron-charging system

    International Nuclear Information System (INIS)

    Miller, J.

    1979-01-01

    High-pressure positive-displacement pumps used in the boron-charging setups of pressurized-water (PWR) nuclear plants because of their inherently high efficiencies over a wide range of pressures and speeds are described. Hydrogen-saturated water containing 4-12% boric acid is fed to the pump from a volume-control tank under a gas blanket. Complicated piping and the pulsation difficulties associated with reciprocating pumps make hydrogen-saturated boron-charging systems a challenge to the designer. The article describes the unusual hydraulics of the systems to help assure a trouble-free design

  17. Electronic structure and tautomerism of aryl ketones

    International Nuclear Information System (INIS)

    Novak, Igor; Klasinc, Leo; Šket, Boris; McGlynn, S.P.

    2015-01-01

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed

  18. Electronic structure and tautomerism of aryl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Igor, E-mail: inovak@csu.edu.au [Charles Sturt University, POB 883, Orange, NSW 2800 (Australia); Klasinc, Leo, E-mail: klasinc@irb.hr [Physical Chemistry Department, Ruđer Bošković Institute, HR-10002 Zagreb (Croatia); Šket, Boris, E-mail: Boris.Sket@fkkt.uni-lj.si [Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 (Slovenia); McGlynn, S.P., E-mail: sean.mcglynn@chemgate.chem.lsu.edu [Louisiana State University, Baton Rouge, LA 70803 (United States)

    2015-07-15

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed.

  19. Foliar fertilizations with boron and growth regulators on lettuce (Lactuca sativa L.) cv floresta culture

    International Nuclear Information System (INIS)

    Masunaga, S.I.; Chueire, F.B.; Teixeira, N.T.

    1989-01-01

    The experiment was realized to verify the possibility of applying Boron as foliar fertilization with growth regulators: indol acetic acid, giberellic acid, ethephon and cycocel. The other objective was to compare the foliar and soil fertilization, with Boron, on the lettuce culture. The results showed that there wasn't difference of production between the treatments. Meanwhile the application of growth regulator modified the Boron grade in the leaves. (author) [pt

  20. Oxidation of boron carbide at high temperatures

    International Nuclear Information System (INIS)

    Steinbrueck, Martin

    2005-01-01

    The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

  1. Fracture toughness of borides formed on boronized ductile iron

    International Nuclear Information System (INIS)

    Sen, Ugur; Sen, Saduman; Koksal, Sakip; Yilmaz, Fevzi

    2005-01-01

    In this study, fracture toughness properties of boronized ductile iron were investigated. Boronizing was realized in a salt bath consisting of borax, boric acid and ferro-silicon. Boronizing heat treatment was carried out between 850 and 950 deg. C under the atmospheric pressure for 2-8 h. Borides e.g. FeB, Fe 2 B formed on ductile iron was verified by X-ray diffraction (XRD) analysis, SEM and optical microscope. Experimental results revealed that longer boronizing time resulted in thicker boride layers. Optical microscope cross-sectional observation of borided layers showed dentricular morphology. Both microhardness and fracture toughness of borided surfaces were measured via Vickers indenter. The harnesses of borides formed on the ductile iron were in the range of 1160-2140 HV 0.1 and fracture toughness were in the range of 2.19-4.47 MPa m 1/2 depending on boronizing time and temperature

  2. Boron tolerance in NS wheat lines

    Directory of Open Access Journals (Sweden)

    Brdar Milka

    2006-01-01

    Full Text Available Boron is an essential micronutrient for higher plants. Present in excessive amounts boron becomes toxic and can limit plant growth and yield. Suppression of root growth is one of the symptoms of boron toxicity in wheat. This study was undertaken to investigate the response of 10 perspective NS lines of wheat to high concentrations of boron. Analysis of root growth was done on young plants, germinated and grown in the presence of different concentrations of boric acid (0, 50,100 and 150 mg/1. Significant differences occurred between analyzed genotypes and treatments regarding root length. Average suppression of root growth was between 11,6 and 34,2%, for line NS 252/02 are even noted 61,4% longer roots at treatments in relation to the control. Lines with mean suppression of root growth less than 20% (NS 101/02, NS 138/01, NS 53/03 and NS 73/02 may be considered as boron tolerant. Spearmans coefficients showed high level of agreement regarding rang of root length for genotypes treated with 100 and 150 mg H3BO3/l.

  3. Pulverization of boron element and proportions of boron carbide in boron

    International Nuclear Information System (INIS)

    Lang, F.M.; Finck, C.

    1956-01-01

    It is possible to reduce boron element into fine powder by means of a mortar and pestle made of sintered boron carbide, the ratio of boron carbide introduced being less than one per cent. Boron element at our disposal is made of sharp edged, dark brown, little grains of average size greater than 5 μ. Grain sizes smaller than 1μ are required for applying thin layers of such boron. (author) [fr

  4. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    OpenAIRE

    B. F. Mirjalili; A. Bamoniri; L. Zamani

    2013-01-01

    Nano-silica supported titanium tetrachloride (TiCl4.SiO2) was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  5. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    Directory of Open Access Journals (Sweden)

    B. F. Mirjalili

    2013-12-01

    Full Text Available Nano-silica supported titanium tetrachloride (TiCl4.SiO2 was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  6. Synthesis and preliminary evaluation of antinociceptive activity of novel isoxazolyl-aryl-hydrazones; Sintese e avaliacao preliminar de atividade antinociceptiva de novas isoxazolil-aril-hidrazonas

    Energy Technology Data Exchange (ETDEWEB)

    Reis, Silvio Leandro Goncalves Bomfim; Almeida, Valderes Moraes de; Almeida, Gleybson Correia de; Boaviagem, Karinna Moura; Mendes, Charles Christophe du Barriere; Faria, Antonio Rodolfo de, E-mail: rodolfo@ufpe.b [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Ciencias Farmaceuticas; Goes, Alexandre Jose da Silva; Magalhaes, Laudelina Rodrigues; Silva, Teresinha Goncalves da [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Antibioticos

    2011-07-01

    New 2-isoxazoline aldehydes were synthesized, in good yields, from cycloadduct of the 1,3-dipolar cycloaddition reaction between endocyclic enecarbamate and carboethoxyformonitrile oxide (CEFNO). Condensation of these 2-isoxazoline aldehydes with several phenyl-hydrazines produced new isoxazolyl-aryl-hydrazones, which showed low toxicity and excellent antinociceptive activity, when compared to dipyrone. The antinociceptive activity of isoxazolyl-aryl-hydrazones was performed using the acetic acid-induced mice abdominal constrictions test. (author)

  7. An Efficient and Versatile Synthesis of Isoflavones from 2-Methoxybenzoic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jae In [Duksung Women' s University, Seoul (Korea, Republic of)

    2016-07-15

    Isoflavones (3-aryl-4H-1-benzopyran-4-ones) are found naturally in soybeans and many plants of the Leguminosae family. They have attracted much attention due to their biological activities, such as their anti-cancer, anti-inflammatory, and antifungal properties. Isoflavones intake through foods is important to human health, because they potentially regulate fatty acid metabolism and methoxy-substituted isoflavones in particular increase cell permeability. Isoflavones have also been synthesized by the coupling of 3-iodochromones with arylboronic acids. The condensation of 2'-hydroxyacetophenones with DMF dimethyl acetal formed 3-(dimethylamino)-2'-hydroxyphenylpropenones, which were cyclized using iodine to form 3-iodochromones. This process was followed by Suzuki coupling with arylboronic acids or aryl boronates to obtain isoflavones. The synthesis of isoflavones (6) from 5 was based on the formylation of the methylene group of 5 using DMF-POCl{sub 3}. Previously, the reaction of the DMF-POCl{sub 3} complex on benzyl 2-hydroxyphenyl ketones led to isoflavones, for which DMF was used as the reagent and solvent for 18 h at gentle reflux.

  8. Biogeochemical cycle of boron in a forest ecosystem: the case study of Montiers beech-stand

    International Nuclear Information System (INIS)

    Roux, Philippe

    2016-01-01

    This thesis aims at establishing and understanding the biogeochemical cycle of boron and its isotopes within a forest ecosystem. In that context, many questions remain concerning the dynamics of boron within terrestrial ecosystems: - What are the major sources of boron? - What type of transfer occurs between the compartments of the environment? - What mechanisms are controlling those transfers? In order to establish this biogeochemical cycle, we quantified the different stocks (vegetation, humus and soil) and fluxes (atmospheric dust and dissolved deposition, throughfall, stem-flows, litterfall and drainage) of boron in the study site of Montiers. The use of boron isotopes will give us insight concerning the mechanisms controlling the dynamics of boron. This thesis is divided in 4 main parts: 1. The first part aims at establishing a new method of extraction, purification and measurement of boron and its isotopes within vegetation samples. 2. The second part focuses on the sources and mechanisms controlling boron within atmospheric dust and dissolved deposition on the study site of Montiers. 3. The third part aims at establishing the stocks and fluxes of boron on two distinct soils: a rendisoil (basic pH) and an alocrisoil (acid pH). The goal is to determine the influence of different soil properties on boron dynamics within its biogeochemical cycle. 4. The last part aims at establishing a model of boron and boron isotopes dynamics in the soil plant system. This model is mainly based of the measurement made in 2012. (author) [fr

  9. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  10. Boron Removal in Seawater Reverse Osmosis System

    KAUST Repository

    Rahmawati, Karina

    2011-07-01

    Reverse osmosis successfully proves to remove more than 99% of solute in seawater, providing fresh water supply with satisfied quality. Due to some operational constraints, however, some trace contaminants removal, such as boron, cannot be achieved in one pass system. The stringent criterion for boron from World Health Organization (WHO) and Saudi Arabia local standard (0.5 mg/l) is hardly fulfilled by single pass sea water reverse osmosis (SWRO) plants. Some design processes have been proposed to deal with boron removal, but they are not economically efficient due to high energy and chemical consumption. The objective of this study was to study boron removal by different reverse osmosis membranes in two pH conditions, with and without antiscalant addition. Thus, it was expected to observe the possibility of operating single pass system and necessity to operate two pass system using low energy membrane. Five membrane samples were obtained from two different manufacturers. Three types of feed water pH were used, pH 8, pH 10, and pH 10 with antiscalant addition. Experiment was conducted in parallel to compare membrane performance from two manufacturers. Filtration was run with fully recycle mode for three days. Sample of permeate and feed were taken every 12 hours, and analyzed for their boron and TDS concentration. Membrane samples were also tested for their surface charge. The results showed that boron rejection increases as the feed pH increases. This was caused by dissociation of boric acid to negatively charged borate ion and more negatively charged membrane surface at elevated pH which enhance boron rejection. This study found that single pass reverse osmosis system, with and without elevating the pH, may not be possible to be applied because of two reasons. First, permeate quality in term of boron, does not fulfill WHO and local Saudi Arabia regulations. Second, severe scaling occurs due to operation in alkaline condition, since Ca and Mg concentration are

  11. Proposed physiologic functions of boron in plants pertinent to animal and human metabolism.

    Science.gov (United States)

    Blevins, D G; Lukaszewski, K M

    1994-01-01

    Boron has been recognized since 1923 as an essential micronutrient element for higher plants. Over the years, many roles for boron in plants have been proposed, including functions in sugar transport, cell wall synthesis and lignification, cell wall structure, carbohydrate metabolism, RNA metabolism, respiration, indole acetic acid metabolism, phenol metabolism and membrane transport. However, the mechanism of boron involvement in each case remains unclear. Recent work has focused on two major plant-cell components: cell walls and membranes. In both, boron could play a structural role by bridging hydroxyl groups. In membranes, it could also be involved in ion transport and redox reactions by stimulating enzymes like nicotinamide adenine dinucleotide and reduced (NADH) oxidase. There is a very narrow window between the levels of boron required by and toxic to plants. The mechanisms of boron toxicity are also unknown. In nitrogen-fixing leguminous plants, foliarly applied boron causes up to a 1000% increase in the concentration of allantoic acid in leaves. In vitro studies show that boron inhibits the manganese-dependent allantoate amidohydrolase, and foliar application of manganese prior to application of boron eliminates allantoic acid accumulation in leaves. Interaction between borate and divalent cations like manganese may alter metabolic pathways, which could explain why higher concentrations of boron can be toxic to plants. PMID:7889877

  12. Coordination Networks Based on Boronate and Benzoxaborolate Ligands

    Directory of Open Access Journals (Sweden)

    Saad Sene

    2016-05-01

    Full Text Available Despite the extensive range of investigations on boronic acids (R-B(OH2, some aspects of their reactivity still need to be explored. This is the case for the coordination chemistry of boronate anions (R-B(OH3−, which has only recently been started to be studied. The purpose of this review is to summarize some of the key features of boronate ligands (and of their cyclic derivatives, benzoxaborolates in materials: (i coordination properties; (ii spectroscopic signatures; and (iii emerging applications.

  13. Electrodialysis of boron-containing solutions using homogeneuos ionite membranes

    International Nuclear Information System (INIS)

    Pilipenko, A.T.; Grebenyuk, V.D.; Mel'nik, L.A.

    1989-01-01

    Electrodialysis of boron-containing solutions is studied when preparing potable water from the sea one with the limiting admissible concentration (LAC) of boron 0.5 mg/dm 3 . It is ascertained that at pH>7 diffusion permeability of anion- and cation-exchange membranes as regards boron reduces both in the absence of external field and at current density 0.3 A/dm 3 . It is shown that when MK-100 homogeneous cationic membranes and MA-100 homogeneous anionic membranes are used, boron concentration in dialyzate decreases to LAC, if the process is realized in acid and low-acid media and if the depth of freshening increases to 0.2g/l

  14. Corrosion resistance testing of high-boron-content stainless steels

    International Nuclear Information System (INIS)

    Petrman, I.; Safek, V.

    1994-01-01

    Boron steels, i.e. stainless steels with boron contents of 0.2 to 2.25 wt.%, are employed in nuclear engineering for the manufacture of baskets or wells in which radioactive fissile materials are stored, mostly spent nuclear fuel elements. The resistance of such steels to intergranular corrosion and uniform corrosion was examined in the Strauss solution and in boric acid; the dependence of the corrosion rate of the steels on their chemical composition was investigated, and their resistance was compared with that of AISI 304 type steel. Corrosion resistance tests in actual conditions of ''wet'' compact storage (demineralized water or a weak boric acid solution) gave evidence that boron steels undergo nearly no uniform corrosion and, as electrochemical measurements indicated, match standard corrosion-resistant steels. Corrosion resistance was confirmed to decrease slightly with increasing boron content and to increase somewhat with increasing molybdenum content. (Z.S.). 3 tabs., 4 figs., 7 refs

  15. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates

    Science.gov (United States)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.

    2015-08-01

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  16. The sonochemical arylation of malonic esters mediated by manganese triacetate.

    Science.gov (United States)

    Meciarova, M; Toma, S; Luche, J L

    2001-04-01

    The intermolecular arylation of malonate esters in acetic acid solution in the presence of manganese(III) triacetate is known to proceed via an Electron Transfer mechanism. Under sonication, this reaction undergoes only minor changes. In contrast, the intramolecular reaction of dimethyl alpha-(3-phenylpropyl)malonate provides a new case of sonochemical switching, with the formation of compounds 7-9, while conventional thermal conditions generate only the bicyclic compound 6. Reactions using the more powerful oxidant, cerium ammonium nitrate are governed by the formation of the nitrate ester 11. Compounds 7-9 are isolated in yields lower than with MnTA, and in proportions depending on the conditions, thermal or sonochemical.

  17. Asymmetric Transfer Hydrogenation of 1-Aryl-3,4-Dihydroisoquinolines Using a Cp*Ir(TsDPEN) Complex

    Czech Academy of Sciences Publication Activity Database

    Václavíková Vilhanová, B.; Budinská, Alena; Václavík, Jiří; Matoušek, V.; Kuzma, M.; Červený, L.

    2017-01-01

    Roč. 2017, č. 34 (2017), s. 5131-5134 ISSN 1434-193X Institutional support: RVO:61388963 Keywords : 1-aryl-3,4-dihydroisoquinolines * asymmetric synthesis * hydrogenation * iridium * phosphoric acid Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.834, year: 2016

  18. Shock Response of Boron Carbide

    National Research Council Canada - National Science Library

    Dandekar, D. P. (Dattatraya Purushottam)

    2001-01-01

    .... The present work was undertaken to determine tensile/spall strength of boron carbide under plane shock wave loading and to analyze all available shock compression data on boron carbide materials...

  19. Rhodium Catalyzed Intramolecular C-H Insertion of α-Aryl-α-diazo Ketones

    Science.gov (United States)

    Taber, Douglass F.; Tian, Weiwei

    2011-01-01

    Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones. PMID:17385917

  20. Boronated liposome development and evaluation

    International Nuclear Information System (INIS)

    Hawthorne, M.F.

    1995-01-01

    The boronated liposome development and evaluation effort consists of two separate tasks. The first is the development of new boron compounds and the synthesis of known boron species with BNCT potential. These compounds are then encapsulated within liposomes for the second task, biodistribution testing in tumor-bearing mice, which examines the potential for the liposomes and their contents to concentrate boron in cancerous tissues

  1. Intramolecular anionic diels-alder reactions of 1-aryl-4-oxahepta-1,6-diyne systems in DMSO.

    Science.gov (United States)

    Kudoh, Takayuki; Mori, Tomoko; Shirahama, Mitsuhito; Yamada, Masashi; Ishikawa, Teruhiko; Saito, Seiki; Kobayashi, Hisayoshi

    2007-04-25

    Base-promoted cycloaddition reactions of 1-aryl- or 1-aryl-7-substituted-4-oxahepta-1,6-diyne systems in DMSO have proven to involve an anionic intramolecular Diels-Alder process taking place even at room temperature in spite of the reaction suffering from temporary disruption of aromaticity. Although initially formed alpha-arylallenide anion can be protonated by DMSO, it can be back to the allenide anion probably because of a small acidity difference between alpha-arylallene and DMSO. The alpha-arylallenide anion in combination with the alpha-aryl substituent can constitute an anionic diene structure that undergoes the intramolecular Diels-Alder reaction involving the C(6)-yne part, a very fast process probably because of the increased HOMO-1 level of the anionic diene, as shown by DFT calculations. Diversified substituted naphthalenes, benzofurans, phenanthrenes, and quinolines, including biaryl architectures, are available from 4-oxahepta-1,6-diynes in a highly expeditious way.

  2. Synthesis of positron labeled photoactive compounds: 18F labeled aryl azides for positron labeling of biochemical molecules

    International Nuclear Information System (INIS)

    Hashizume, Kazunari; Hashimoto, Naota; Miyake, Yoshihiro

    1995-01-01

    The authors have prepared various [ 18 F] fluorine labeled aryl azides as a novel photoactive compounds suitable for positron labeling of biochemical molecules. The introduction of fluorine substituents to aryl azides can be expected to have dramatic effects on their nature and reactivity toward photolysis. Positron labeled reagents for labeling proteins or peptides have recently attracted considerable attention due to their wide applicability in biochemistry and positron emission tomography (PET). Various labeled azide compounds are often used in biochemistry for radiolabeling biological molecules by photolysis, but there have been no reports on the preparation or use of fluorine-18 labeled azides. The authors now report a novel synthesis of 18 F-labeled aryl azides which will have wide application in the biochemistry and nuclear medicine as a means for 18 F-fluorine labeling for proteins, peptides, and nucleic acids. 2 tabs

  3. Implantation of boron in silicon

    International Nuclear Information System (INIS)

    Hofker, W.K.

    1975-01-01

    The distribution versus depth of boron implanted in silicon and the corresponding electrical activity obtained after annealing are studied. The boron distributions are measured by secondary-ion mass spectrometry. Boron distributions implanted at energies in the range from 30 keV to 800 keV in amorphous and polycrystalline silicon are analysed. Moments of these distributions are determined by a curve-fitting programme and compared with moments calculated by Winterbon. Boron distributions obtained by implantations along a dense crystallographic direction in monocrystalline silicon are found to have penetrating tails. After investigation of some possible mechanisms of tail formation it is concluded that the tails are due to channelling. It was found that the behaviour of boron during annealing is determined by the properties of three boron fractions consisting of precipitated boron, interstitial boron and substitutional boron. The electrical activity of the boron versus depth is found to be consistent with the three boron fractions. A peculiar redistribution of boron is found which is induced by the implantation of a high dose of heavy ions and subsequent annealing. Different mechanisms which may cause the observed effects, such as thermal diffusion which is influenced by lattice strain and damage, are discussed. (Auth.)

  4. Determination of boron in nuclear materials at subppm levels by high pressure liquid chromatography (HPLC)

    International Nuclear Information System (INIS)

    Rao, Radhika M.; Aggarwal, S.K.

    2002-11-01

    Experiments were conducted for the determination of boron in U 3 O 8 powder, aluminium metal and milliQ water using dynamically modified Reversed Phase High Pressure Liquid Chromatography (RP-HPLC) and using two precolumn chromogenic agents viz. chromotropic acid and curcumin for complexing boron. The complex was separated from the excess of reagent and determined by HPLC. When present in subppm levels, chromotropic acid was used successfully only for determination boron in water samples. For determination of boron at subppm levels in uranium and aluminium samples, curcumin was used as the precolumn chromogenic agent. The boron curcumin complex (rosocyanin) was formed after extraction of boron with 2-ethyl-l, 3-hexane diol (EHD). The rosocyanin complex was then separated from excess curcumin by displacement chromatography. Linear calibration curves for boron amounts in the range of 0.02 μg to 0.5 μg were developed with correlation coefficients varying from 0.997 to 0.999 and were used for the determination of boron in aluminium and uranium samples. Precision of about 10% was achieved in samples containing less than 1 ppmw of boron. Detection limit of this method is 0.01 μg boron. (author)

  5. Coupling of dextrans conjugated with boron to γ globulin: a model for NCT

    International Nuclear Information System (INIS)

    Elmore, J.J. Jr.; Borg, D.C.; Micca, P.; Gabel, D.

    1982-01-01

    To achieve the selective localization of boron in or on cancer cells or other target cells, the authors have elected to use water-soluble dextrans as intermediate carriers. This permits each MCA molecule to target many atoms of boron-10 to the specified antigenic receptors while only 5 to 10 of the amino acid residues of the protein are conjugated by dextrans carrying boron-10. As a result, there should be little of the loss of receptor specificity or affinity

  6. Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

    Science.gov (United States)

    Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

    2016-10-26

    To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

  7. Thermoelectric properties of boron and boron phosphide CVD wafers

    Energy Technology Data Exchange (ETDEWEB)

    Kumashiro, Y.; Yokoyama, T.; Sato, A.; Ando, Y. [Yokohama National Univ. (Japan)

    1997-10-01

    Electrical and thermal conductivities and thermoelectric power of p-type boron and n-type boron phosphide wafers with amorphous and polycrystalline structures were measured up to high temperatures. The electrical conductivity of amorphous boron wafers is compatible to that of polycrystals at high temperatures and obeys Mott`s T{sup -{1/4}} rule. The thermoelectric power of polycrystalline boron decreases with increasing temperature, while that of amorphous boron is almost constant in a wide temperature range. The weak temperature dependence of the thermal conductivity of BP polycrystalline wafers reflects phonon scattering by grain boundaries. Thermal conductivity of an amorphous boron wafer is almost constant in a wide temperature range, showing a characteristic of a glass. The figure of merit of polycrystalline BP wafers is 10{sup -7}/K at high temperatures while that of amorphous boron is 10{sup -5}/K.

  8. Rearrangements of Cycloalkenyl Aryl Ethers

    Directory of Open Access Journals (Sweden)

    Mercedesz Törincsi

    2016-04-01

    Full Text Available Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

  9. Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

    International Nuclear Information System (INIS)

    Costa, Carla Regina; Montilla, Francisco; Morallon, Emilia; Olivi, Paulo

    2009-01-01

    The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds.

  10. Determination of boron in sea water by atomic absorption spectrophotometry

    International Nuclear Information System (INIS)

    Horta, A.M.T.C.; Curtius, A.J.

    1978-01-01

    The chelation-extraction of boric acid with are acid solution of 2-ethyl-1,3 hexanediol in methy1-isobutye-ketone is studied. By this way a simple, quick and precise method for boron determination can be obtained [pt

  11. Electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton degradation of the drug ibuprofen in acid aqueous medium using platinum and boron-doped diamond anodes

    International Nuclear Information System (INIS)

    Skoumal, Marcel; Rodriguez, Rosa Maria; Cabot, Pere Lluis; Centellas, Francesc; Garrido, Jose Antonio; Arias, Conchita; Brillas, Enric

    2009-01-01

    The degradation of a 41 mg dm -3 ibuprofen (2-(4-isobutylphenyl)propionic acid) solution of pH 3.0 has been comparatively studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Experiments were performed in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and an O 2 -diffusion cathode. Heterogeneous hydroxyl radical (·OH) is generated at the anode surface from water oxidation, while homogeneous ·OH is formed from Fenton's reaction between Fe 2+ and H 2 O 2 generated at the cathode, being its production strongly enhanced from photo-Fenton reaction induced by sunlight. Higher mineralization is attained in all methods using BDD instead Pt, because the former produces greater quantity of ·OH enhancing the oxidation of pollutants. The mineralization rate increases under UVA and solar irradiation by the rapid photodecomposition of complexes of Fe(III) with acidic intermediates. The most potent method is solar photoelectro-Fenton with BDD giving 92% mineralization due to the formation of a small proportion of highly persistent final by-products. The effect of Fe 2+ content, pH and current density on photoelectro-Fenton degradation has been studied. The ibuprofen decay always follows a pseudo-first-order kinetics and its destruction rate is limited by current density and UV intensity. Aromatics such as 1-(1-hydroxyethyl)-4-isobutylbenzene, 4-isobutylacetophenone, 4-isobutylphenol and 4-ethylbenzaldehyde, and carboxylic acids such as pyruvic, acetic, formic and oxalic have been identified as oxidation by-products. Oxalic acid is the ultimate by-product and the fast photodecarboxylation of its complexes with Fe(III) under UVA or solar irradiation explains the higher oxidation power of photoelectro-Fenton methods in comparison to electro-Fenton procedures

  12. Immunocytochemistry by electron spectroscopic imaging using a homogeneously boronated peptide.

    Science.gov (United States)

    Kessels, M M; Qualmann, B; Klobasa, F; Sierralta, W D

    1996-05-01

    A linear all-L-oligopeptide containing five carboranyl amino acids (corresponding to 50 boron atoms) was synthesized and specifically attached to the free thiol group of monovalent antibody fragments F(ab)'. The boronated immunoreagent was used for the direct post-embedding detection of somatotrophic hormone in ultrathin sections of porcine pituitary embedded in Spurr resin. The specific boron-labelling of secretory vesicles in somatotrophs was detected by electron spectroscopic imaging and confirmed by conventional immunogold labelling run in parallel. In comparison with immunogold, boron-labelled F(ab)'-fragments showed higher tagging frequencies, as was expected; the small uncharged immunoreagents have an elongated shape and carry the antigen-combining structure and the detection tag at opposite ends, thus allowing for high spatial resolution in electron spectroscopic imaging.

  13. Spectrographic determination of traces of boron in steels

    International Nuclear Information System (INIS)

    Alduan, F.A.; Roca, M.

    1976-01-01

    A spectrographic method has been developed to determine quantitatively boron in steels in the 0.5 to 250 ppm concentration range. The samples are dissolved in acids and transformed into oxides, avoiding boron losses by the addition of mannitol. For the fluoride evolution of boron in the dc arc the following compounds have been considered: CuF 2 , LiF, NaF, and SrF 2 . CuF 2 , at a concentration of 10%, provides the highest line-to-background intensity ratio. An arc current of 5 amperes eliminates the interference from iron spectrum on the most sensitive boron line - B 2497.7 A. Variations in chromium and nickel contents have no effect on the analytical results. (author)

  14. Aryl-derivatized, water-soluble functionalized carbon nanotubes for biomedical applications

    International Nuclear Information System (INIS)

    Karousis, N.; Ali-Boucetta, H.; Kostarelos, K.; Tagmatarchis, N.

    2008-01-01

    The functionalization of very-thin multi-walled carbon nanotubes (VT-MWNTs) with an aniline derivative, via the protocol of in situ generated aryl diazonium salts results, upon acidic deprotection of the terminal BOC group, on the formation of the water-soluble positively charged ammonium functionalized VT-MWNTs-NH 3 + material. The new materials have been structurally and morphologically characterized by infra-red (ATR-IR) spectroscopy and transmission electron microscopy (TEM). The quantitative calculation of the grafted aryl units onto the skeleton of VT-MWNTs has been estimated by thermogravimetric analysis (TGA), while the quantitative Kaiser test showed the amine group loaded onto VT-MWNTs-NH 3 + material. The aqueous solubility of this material has allowed the performance of some initial toxicological in vitro investigations

  15. N-Aryl Arenedicarboximides as Tunable Panchromatic Dyes for Molecular Solar Cells

    Directory of Open Access Journals (Sweden)

    Zhi Cao

    2010-01-01

    Full Text Available Three organic dyes designed as molecular dyads were prepared that feature a common naphthalimide acceptor and N-aryl donors. One of these incorporated an additional cyanoacrylic acid linker and conjugated thiophene bridge inserted between donor and acceptor groups. Electrochemical and photochemical characterizations have been carried out on nanocrystalline TiO2 dye-sensitized solar cells which were fabricated with these dyes as the sensitizing component. HOMO and LUMO energies were also calculated using TDDFT methods and validated by the cyclic voltammetry method. A key finding from this study indicates that computational methods can provide energy values in close agreement to experimental for the N-aryl-naphthalimide system. Relative to HOMO/LUMO energy levels of N719, the dyes based on naphthalimide chromophore are promising candidates for metal-free DSSCs.

  16. Synthesis and properties of poly(aryl sulfone benzimidazole) and its copolymers for high temperature membrane electrolytes for fuel cells

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Li, Qingfeng; Cleemann, Lars Nilausen

    2012-01-01

    Poly(aryl sulfone benzimidazole) (SO2PBI) and its copolymers with poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole] (pPBI), termed as Co-SO2PBI, were synthesized with varied feeding ratios of 4,4′-sulfonyldibenzoic acid (SDBA) to terephthalic acid (TPA). Incorporation of the stiff para-phenylene and ......Poly(aryl sulfone benzimidazole) (SO2PBI) and its copolymers with poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole] (pPBI), termed as Co-SO2PBI, were synthesized with varied feeding ratios of 4,4′-sulfonyldibenzoic acid (SDBA) to terephthalic acid (TPA). Incorporation of the stiff para...

  17. Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

    Science.gov (United States)

    Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

    2013-01-01

    The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

  18. A facile synthesis of new 5-aryl-thiophenes bearing sulfonamide moiety via Pd(0-catalyzed Suzuki–Miyaura cross coupling reactions and 5-bromothiophene-2-acetamide: As potent urease inhibitor, antibacterial agent and hemolytically active compounds

    Directory of Open Access Journals (Sweden)

    Mnaza Noreen

    2017-01-01

    Full Text Available The present study reports a convenient approach for the synthesis of thiophene sulfonamide derivatives (3a–3k via Suzuki cross coupling reaction. This method of synthesis involved the reactions of various aryl boronic acids and esters with 5-bromthiophene-2-sulfonamide (2 under mild and suitable temperature conditions. The compounds synthesized in the present study were subjected to urease inhibition and hemolytic activities. The substitution pattern and the electronic effects of different functional groups (i.e., Cl, CH3, OCH3, F etc. available on the aromatic ring are found to have significant effect on the overall results. The compound 5-Phenylthiophene-2-sulfonamide 3a showed the highest urease inhibition activity with IC50 value ∼ 30.8 μg/mL compared with the thiourea (used as standard having IC50 value ∼ 43 μg/mL. Moreover, almost all of the compounds were examined for the hemolytic activity against triton X-100 with positive results obtained in most of the cases. In addition, the antibacterial activities of the derivatives of 5-arylthiophene-2-sulfonamide and 5-bromothiophene-2-acetamide were also investigated during the course of the study.

  19. Adsorption of various types of amino acids on the graphene and boron-nitride nano-sheet, a DFT-D3 study

    International Nuclear Information System (INIS)

    Zhiani, Rahele

    2017-01-01

    Graphical abstract: Dispersion interactions have key role on the adsorption of different amino acids on the graphene and BN-nanosheet surfaces. - Highlights: • The Arginine amino acid makes the most stable complexes with Gra and BN nano sheet. • Dispersion interactions have key role on the amino acid adsorption. • BN nano sheet makes more stable complexes with amino acids compare to the Gra. • Water as a solvent has important effect on these interactions. - Abstract: The binding properties of the adsorption of five different classes of amino acids, namely, alanine (Ala), arginine (Arg), asparagine (Asn), histidine (His) and cysteine (Cys) on the surface of the graphene (Gra) and the born-nitride (BN) nano-sheet structures were studied from molecular viewpoint using quantum mechanics methods. Density functional theory (DFT) and DFT-D3 calculations were carried out to investigate the electronic properties and the dispersion interaction of the amino acid/adsorbent complexes. Several parameters affecting the interactions between the amino acids and the adsorbent surfaces such as solvent effect, adsorption energy and separation distance were investigated. Findings show that Arg forms the most stable complexes with the graphene and the BN nano-sheet compare to the other amino acids used in this study. The observed frequency results which were related to the band gap energies were consistent with the above statement. Results exhibit that adsorption of the amino acids on the surface of the BN nano-sheet and the graphene accompanied with the release of the energy. Calculations show that there are no bonded interactions between the amino acids and adsorbent surfaces. The polarity of the BN nano-sheet provides the more affinity towards the amino acids. These results were proved by the quantum chemistry studies.

  20. Adsorption of various types of amino acids on the graphene and boron-nitride nano-sheet, a DFT-D3 study

    Energy Technology Data Exchange (ETDEWEB)

    Zhiani, Rahele, E-mail: r_zhiani2006@yahoo.com

    2017-07-01

    Graphical abstract: Dispersion interactions have key role on the adsorption of different amino acids on the graphene and BN-nanosheet surfaces. - Highlights: • The Arginine amino acid makes the most stable complexes with Gra and BN nano sheet. • Dispersion interactions have key role on the amino acid adsorption. • BN nano sheet makes more stable complexes with amino acids compare to the Gra. • Water as a solvent has important effect on these interactions. - Abstract: The binding properties of the adsorption of five different classes of amino acids, namely, alanine (Ala), arginine (Arg), asparagine (Asn), histidine (His) and cysteine (Cys) on the surface of the graphene (Gra) and the born-nitride (BN) nano-sheet structures were studied from molecular viewpoint using quantum mechanics methods. Density functional theory (DFT) and DFT-D3 calculations were carried out to investigate the electronic properties and the dispersion interaction of the amino acid/adsorbent complexes. Several parameters affecting the interactions between the amino acids and the adsorbent surfaces such as solvent effect, adsorption energy and separation distance were investigated. Findings show that Arg forms the most stable complexes with the graphene and the BN nano-sheet compare to the other amino acids used in this study. The observed frequency results which were related to the band gap energies were consistent with the above statement. Results exhibit that adsorption of the amino acids on the surface of the BN nano-sheet and the graphene accompanied with the release of the energy. Calculations show that there are no bonded interactions between the amino acids and adsorbent surfaces. The polarity of the BN nano-sheet provides the more affinity towards the amino acids. These results were proved by the quantum chemistry studies.

  1. Mineralization of phthalic acid by solar photoelectro-Fenton with a stirred boron-doped diamond/air-diffusion tank reactor: Influence of Fe3+ and Cu2+ catalysts and identification of oxidation products

    International Nuclear Information System (INIS)

    Garcia-Segura, Sergi; Salazar, Ricardo; Brillas, Enric

    2013-01-01

    Highlights: • Almost total mineralization of phthalic acid by solar photoelectro-Fenton with Fe 3+ , Cu 2+ and Fe 3+ –Cu 2+ mixtures. • Hydroxyl radical generation from photo-Fenton reaction under solar radiation. • Enhancement of the mineralization rate using Fe 3+ and small amounts of Cu 2+ . • Detection of eleven aromatic intermediates and six short-linear carboxylic acids. • Oxidation of Cu(II)-carboxylate complexes with ·OH and photolysis of Fe(III)-carboxylate species. -- Abstract: Here, the substrate decay and mineralization rate for 100 cm 3 of a 2.0 mM phthalic acid solution in 0.10 M Na 2 SO 4 of pH 3.0 have been studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). The electrochemical cell was a stirred tank reactor containing a 3 cm 2 boron-doped diamond (BDD) anode and a 3 cm 2 air-diffusion cathode that generates H 2 O 2 . Cu 2+ and/or Fe 3+ were added as catalysts with total concentration of 0.50 mM and a constant current density of 33.3 mA cm −2 was applied. In EF with Cu 2+ or Fe 3+ alone and SPEF with only Cu 2+ , phthalic acid decayed slowly and poor mineralization was reached because the main oxidant was ·OH produced at the BDD surface from water oxidation. In contrast, the substrate destruction was largely enhanced using SPEF with 0.50 mM Fe 3+ since a high quantity of oxidant ·OH was produced in the bulk induced by photo-Fenton reaction. This treatment led to an almost total mineralization by the photolysis of generated Fe(III)-carboxylate complexes. In all cases, the decay of phthalic acid obeyed a pseudo-first-order reaction. The combination of Cu 2+ and Fe 3+ as catalysts accelerated the mineralization process in SPEF because Cu(II)-carboxylate complexes were also removed with ·OH formed from photo-Fenton reaction. The best SPEF process was found for 0.125 mM Cu 2+ + 0.375 mM Fe 3+ , giving rise to 99% mineralization with 40% current efficiency and 0.294 kWh g −1 TOC energy consumption. Eleven aromatics

  2. On the mechanism of boron transfer through the cation-exchange membrane MK-40

    International Nuclear Information System (INIS)

    Pilipenko, A.T.; Varvaruk, L.A.; Grebenyuk, V.D.; Trachevskij, V.V.

    1985-01-01

    Proceses of boron electromigration in solutions with different pH values are investigated. It is shown, that boron transfer through ion-exchange membranes is determined by pH of solution. Phenomenon of boron transfer (existing in the solution in the form of boric acid) through cation-exchange membrane MK-40 has been detected and described for the first time. The process of boron (3) complexing with sulfate groups of the membrane by means of competing reversible substitution of hydroxoligands is the basis of the phenomenon

  3. Oxytetracycline as a new analytical reagent for the spectrophotometric determination of boron

    Energy Technology Data Exchange (ETDEWEB)

    Narayana, G L

    1984-05-01

    Oxytetracycline hydrochloride, Terramycin, is introduced as a new reagent for the spectrophotometric determination of trace quantities of boron in concentrated sulphuric acid medium. The reagent has an absorption maximum at 430 nm, and that of the boron complex at 520 nm. The colored system conformed to Beer's law between 2 and 10 ..mu..g of boron at 520 nm. The molar absorptivity calculated on the basis of boron is 10,800 1 mol/sup -1/ cm/sup -1/. The composition of the complex has been shown to be 1:1 both by the slope ratio and molar ratio methods. 16 references.

  4. Oxytetracycline as a new analytical reagent for the spectrophotometric determination of boron

    International Nuclear Information System (INIS)

    Narayana, G.L.

    1984-01-01

    Oxytetracycline hydrochloride, Terramycin, is introduced as a new reagent for the spectrophotometric determination of trace quantities of boron in concentrated sulphuric acid medium. The reagent has an absorption maximum at 430 nm, and that of the boron complex at 520 nm. The coloured system conformed to Beer's law between 2 and 10 μg of boron at 520 nm. The molar absorptivity calculated on the basis of boron is 10,800 1 mol -1 cm -1 . The composition of the complex has been shown to be 1:1 both by the slope ratio and molar ratio methods. (author)

  5. Aryl Insertion vs Aryl-Aryl Coupling in C,C-Chelated Organoborates: The "Missing Link" of Tetraarylborate Photochemistry.

    Science.gov (United States)

    Radtke, Julian; Mellerup, Soren K; Bolte, Michael; Lerner, Hans-Wolfram; Wang, Suning; Wagner, Matthias

    2018-06-14

    The photoreactivity of 9-borafluorene-based, C,C-chelated organoborates was investigated. Unlike the related tetraarylborates, the charge-transfer transitions imparted by the biphenyl chelate lead to selective insertion of one aryl substituent into the endocyclic B-C bond of the 9-borafluorene moiety, resulting in the formation of boratanorcaradienes. This photoreaction likely proceeds according to a Zimmerman rearrangement, which is analogous to one of the initially proposed mechanisms for tetraarylborates and provides additional insight into these long-debated photochemical reactions.

  6. Selective copper catalysed aromatic N-arylation in water

    DEFF Research Database (Denmark)

    Engel-Andreasen, Jens; Shimpukade, Bharat; Ulven, Trond.

    2013-01-01

    4,7-Dipyrrolidinyl-1,10-phenanthroline (DPPhen) was identified as an efficient ligand for copper catalyzed selective arom. N-arylation in water. N-Arylation of indoles, imidazoles and purines proceeds with moderate to excellent yields and complete selectivity over aliph. amines. Aq. medium...

  7. Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    CuI/ethylene diamine/K2CO3/dioxane is shown to be a useful system for the cross coupling reactions of various aryl iodides and bromides with aryl and alkyl alkynes. Compared to the conventional Sonogashira reactions, the new procedure is free of palladium and phosphines.

  8. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  9. Mechanism-based inactivation of benzo[a]pyrene hydroxylase by aryl acetylenes and aryl olefins

    International Nuclear Information System (INIS)

    Gan, L.S.; Lu, J.Y.L.; Alworth, W.L.

    1986-01-01

    A series of aryl acetylenes and aryl olefins have been examined as substrates and inhibitors of cytochrome P-450 dependent monooxgenases in liver microsomes from 5,6-benzoflavone or phenobarbital pretreated rats. 1-Ethynylpyrene, 3-ethynylperylene, 2-ethynylfluorene, methyl 1-pyrenyl acetylene, cis- and trans-1-(2-bromovinyl)pyrene, and 1-allylpyrene serve as mechanism-based irreversible inactivators (suicide inhibitors) of benzo[a]pyrene hydroxylase, while 1-vinylpyrene and phenyl 1-pyrenyl acetylene do not cause a detectable suicide inhibition of benzo[a]pyrene hydroxylase. The mechanism-based loss of benzo[a]pyrene hydroxylase caused by the aryl acetylenes is not accompanied by a corresponding loss of the P-450 content of the microsomes (suicide destruction). The suicide inhibition by these aryl acetylenes therefore does not involve covalent binding to the heme moiety of the monooxygenase. Nevertheless, in the presence of NADPH, 3 H-labeled 1-ethynylpyrene becomes covalently attached to the cytochrome P-450 protein; the measured stoichiometry of binding is one 1-ethynylpyrene per P-450 heme unit. The authors conclude that the inhibition of benzo[a]pyrene hydroxylase produced by 1-ethynylpyrene may be related to the mechanism of suicide inhibition of P-450 activity by chloramphenicol rather than the mechanism of suicide destruction of P-450 previously described for acetylene and propyne

  10. Cloning and heterologous expression of two aryl-aldehyde dehydrogenases from the white-rot basidiomycete Phanerochaete chrysosporium

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Tomofumi [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Fukuoka Institute of Health and Environmental Sciences, 39 Mukaizano, Dazaifu-shi, Fukuoka 818-0135 (Japan); Ichinose, Hirofumi [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Wariishi, Hiroyuki, E-mail: hirowari@agr.kyushu-u.ac.jp [Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Bio-Architecture Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Innovation Center for Medical Redox Navigation, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)

    2010-04-09

    We identified two aryl-aldehyde dehydrogenase proteins (PcALDH1 and PcALDH2) from the white-rot basidiomycete Phanerochaete chrysosporium. Both PcALDHs were translationally up-regulated in response to exogenous addition of vanillin, one of the key aromatic compounds in the pathway of lignin degradation by basidiomycetes. To clarify the catalytic functions of PcALDHs, we isolated full-length cDNAs encoding these proteins and heterologously expressed the recombinant enzymes using a pET/Escherichia coli system. The open reading frames of both PcALDH1 and PcALDH2 consisted of 1503 nucleotides. The deduced amino acid sequences of both proteins showed high homologies with aryl-aldehyde dehydrogenases from other organisms and contained ten conserved domains of ALDHs. Moreover, a novel glycine-rich motif 'GxGxxxG' was located at the NAD{sup +}-binding site. The recombinant PcALDHs catalyzed dehydrogenation reactions of several aryl-aldehyde compounds, including vanillin, to their corresponding aromatic acids. These results strongly suggested that PcALDHs metabolize aryl-aldehyde compounds generated during fungal degradation of lignin and various aromatic xenobiotics.

  11. Cloning and heterologous expression of two aryl-aldehyde dehydrogenases from the white-rot basidiomycete Phanerochaete chrysosporium

    International Nuclear Information System (INIS)

    Nakamura, Tomofumi; Ichinose, Hirofumi; Wariishi, Hiroyuki

    2010-01-01

    We identified two aryl-aldehyde dehydrogenase proteins (PcALDH1 and PcALDH2) from the white-rot basidiomycete Phanerochaete chrysosporium. Both PcALDHs were translationally up-regulated in response to exogenous addition of vanillin, one of the key aromatic compounds in the pathway of lignin degradation by basidiomycetes. To clarify the catalytic functions of PcALDHs, we isolated full-length cDNAs encoding these proteins and heterologously expressed the recombinant enzymes using a pET/Escherichia coli system. The open reading frames of both PcALDH1 and PcALDH2 consisted of 1503 nucleotides. The deduced amino acid sequences of both proteins showed high homologies with aryl-aldehyde dehydrogenases from other organisms and contained ten conserved domains of ALDHs. Moreover, a novel glycine-rich motif 'GxGxxxG' was located at the NAD + -binding site. The recombinant PcALDHs catalyzed dehydrogenation reactions of several aryl-aldehyde compounds, including vanillin, to their corresponding aromatic acids. These results strongly suggested that PcALDHs metabolize aryl-aldehyde compounds generated during fungal degradation of lignin and various aromatic xenobiotics.

  12. Functional characterization of Citrus macrophylla BOR1 as a boron transporter.

    Science.gov (United States)

    Cañon, Paola; Aquea, Felipe; Rodríguez-Hoces de la Guardia, Amparo; Arce-Johnson, Patricio

    2013-11-01

    Plants have evolved to develop an efficient system of boron uptake and transport using a range of efflux carriers named BOR proteins. In this work we isolated and characterized a boron transporter of citrus (Citrus macrophylla), which was named CmBOR1 for its high homology to AtBOR1. CmBOR1 has 4403 bp and 12 exons. Its coding region has 2145 bp and encodes for a protein of 714 amino acids. CmBOR1 possesses the molecular features of BORs such as an anion exchanger domain and the presence of 10 transmembrane domains. Functional analysis in yeast indicated that CmBOR1 has an efflux boron transporter activity, and transformants have increased tolerance to excess boron. CmBOR1 is expressed in leaves, stem and flowers and shows the greatest accumulation in roots. The transcript accumulation was significantly increased under boron deficiency conditions in shoots. In contrast, the accumulation of the transcript did not change in boron toxicity conditions. Finally, we observed that constitutive expression of CmBOR1 was able to increase tolerance to boron deficiency conditions in Arabidopsis thaliana, suggesting that CmBOR1 is a xylem loading boron transporter. Based on these results, it was determined that CmBOR1 encodes a boric acid/borate transporter involved in tolerance to boron deficiency in plants. © 2013 Scandinavian Plant Physiology Society.

  13. Boronate esters: Synthesis, characterization and molecular base receptor analysis

    Science.gov (United States)

    Gómez-Jaimes, Gelen; Barba, Victor

    2014-10-01

    The synthesis of three boronate esters obtained by reacting 4-fluorophenylboronic (1), 4-iodophenylboronic (2) and 3,4-chlorophenylboronic (3) acids with 2,4,5-trihidroxybenzaldehyde is reported. The structural characterization was determined by spectroscopic and spectrometric techniques. The boron atom was evaluated to acts as Lewis acid center in the reaction with pyridine (Py), triethylamine (TEA) and fluoride anion (F-). The titration method was followed by UV-Vis and 11B NMR spectroscopy; results indicate the good interaction with the fluoride ion but poor coordination towards pyridine in solution.

  14. The spectrophotometric determination of boron in tourmalines

    Directory of Open Access Journals (Sweden)

    LJILJANA JAKSIC

    2005-02-01

    Full Text Available A procedure for the spectrophotometric determination of macro amounts of boron in tourmaline with azomethine H is described. The used tourmaline concentrate was obtained by magnetic separation and heavy-liquids purification of the schorl zone of pegmatite or granite aplite. The samples of tourmaline were decomposed by fusion with anhydrous sodium carbonate and taken up in dilute hydrochloric acid. The interfering effects of iron and aluminium were eliminated by masking with an EDTA – NTA solution. After pH adjustment, the boron was reacted with azomethine H and the absorbance of the obtained coloured complex was measured at 415 nm. The results are compared with those obtained by other procedures. The relative error of the determination was less than 3 %.

  15. Alkyl and aryl phosphorodiiodidites. Pt. 2

    International Nuclear Information System (INIS)

    Feshchenko, N.G.; Kostina, V.G.

    1976-01-01

    Alkyl phosphorodiiodidites are formed in the reactions of alkyl phosphorodichloridites with lithium iodide. They are stable at -60 to -50 0 . When warmed to 20 0 , they disproportionate with conversion into trialkyl phosphites and phosphorus triiodide. The latter also react together and give alkyl iodides, diphosphorus tetraiodide, and a polymer of unestablished structure. Diaryl and dialkyl phosphoriodidites are stable only in solution at low temperatures. They disproportionate in a similar way to aryl and alkyl phosphorodiiodidites. Alkyl phosphorodiiodidites react with iodine with the formation of alkyl iodides and phosphoryl iodide

  16. C- versus O-Arylation of an Enol-Lactone Using Potassium tert-butoxide

    Directory of Open Access Journals (Sweden)

    El Moktar Essassi

    2003-05-01

    Full Text Available Abstract: The use of potassium tert-butoxide as the base in arylation reactions of an enollactone with a series of benzyl halides was explored. Our work demonstrates that the ratio of C-arylation to O-arylation varies with the substitution pattern of the aryl halide.

  17. Self-assembled coordination nanoparticles from nucleotides and lanthanide ions with doped-boronic acid-fluorescein for detection of cyanide in the presence of Cu2+ in water.

    Science.gov (United States)

    Kulchat, Sirinan; Chaicham, Anusak; Ekgasit, Sanong; Tumcharern, Gamolwan; Tuntulani, Thawatchai; Tomapatanaget, Boosayarat

    2012-01-30

    The sensor molecule, F-oBOH, containing boronic acid-linked hydrazide and fluorescein moieties was synthesized. For anion sensing applications, F-oBOH was studied in aqueous media. Unfortunately, F-oBOH was found to be hydrolyzed in water. Therefore, a new strategy was developed to prevent the hydrolysis of F-oBOH by applying self-assembly coordination nanoparticles network (F-oBOH-AMP/Gd(3+) CNPs). Interestingly, the nanoparticles network displayed the enhancement of fluorescent signal after adding Cu(2+) following by CN(-). The network, therefore, possessed a high selectivity for detection of CN(-) compared to other competitive anions in the presence of Cu(2+). Cyanide ion could promote the Cu(2+) binding to F-oBOH incorporated in AMP/Gd(3+) CNPs to give the opened-ring form of spirolactam resulting in the fourfold of fluorescence enhancement compared to Cu(2+) complexation without CN(-). Additionally, the log K value of F-oBOH-AMP/Gd(3+) CNPs⊂Cu(2+) toward CN(-) was 3.97 and the detection limits obtained from naked-eye and spectrofluorometry detections were 20μM and 4.03μM, respectively. The proposed method was demonstrated to detect CN(-) in drinking water with high accuracy. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. A New Boron Analysis Method

    Energy Technology Data Exchange (ETDEWEB)

    Weitman, J; Daaverhoeg, N; Farvolden, S

    1970-07-01

    In connection with fast neutron (n, {alpha}) cross section measurements a novel boron analysis method has been developed. The boron concentration is inferred from the mass spectrometrically determined number of helium atoms produced in the thermal and epithermal B-10 (n, {alpha}) reaction. The relation between helium amount and boron concentration is given, including corrections for self shielding effects and background levels. Direct and diffusion losses of helium are calculated and losses due to gettering, adsorption and HF-ionization in the release stage are discussed. A series of boron determinations is described and the results are compared with those obtained by other methods, showing excellent agreement. The lower limit of boron concentration which can be measured varies with type of sample. In e.g. steel, concentrations below 10-5 % boron in samples of 0.1-1 gram may be determined.

  19. Boron isotope fractionation in column chromatography with glucamine type fibers

    International Nuclear Information System (INIS)

    Sonoda, Akinari; Makita, Yoji; Hirotsu, Takahiro

    2008-01-01

    Glucamine type polymers have specific affinity toward boric acid and borate ion. Among them, Chelest Fiber GRY-L showed larger fractionation for boron isotopes than other polymers in our previous study. For this study, we used Chelest Fibers with different fiber lengths (1.0 mm, 0.5 mm, and 0.3 mm) as column packing materials to perform chromatographic separation of boron isotopes. The shorter fiber has larger packing density when packed into the column using a dry method. The 0.3-mm-long fiber has a larger backpressure than fibers of other lengths. Boron adsorption capacities were measured using the breakthrough operation. At this time, the 0.5-mm-long fiber showed the highest capacity. When we measured the isotope ratio profile for fibers of different length using column chromatography, 0.5-mm-long fibers displayed the highest boron isotope fractionation. The 0.5-mm-long fiber is promising as a packing material of column chromatography for boron isotope separation. We also changed operation methods. The lower eluent concentration and the slower flow rate are suitable for boron isotope separation. (author)

  20. Structural Modification in Carbon Nanotubes by Boron Incorporation

    Directory of Open Access Journals (Sweden)

    Handuja Sangeeta

    2009-01-01

    Full Text Available Abstract We have synthesized boron-incorporated carbon nanotubes (CNTs by decomposition of ferrocene and xylene in a thermal chemical vapor deposition set up using boric acid as the boron source. Scanning and transmission electron microscopy studies of the synthesized CNT samples showed that there was deterioration in crystallinity and improvement in alignment of the CNTs as the boron content in precursor solution increased from 0% to 15%. Raman analysis of these samples showed a shift of ~7 cm−1in wave number to higher side and broadening of the G band with increasing boron concentration along with an increase in intensity of the G band. Furthermore, there was an increase in the intensity of the D band along with a decrease in its wave number position with increase in boron content. We speculate that these structural modifications in the morphology and microstructure of CNTs might be due to the charge transfer from boron to the graphite matrix, resulting in shortening of the carbon–carbon bonds.

  1. Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

    KAUST Repository

    Li, Huifang

    2018-01-30

    The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.

  2. Identification of 1-Aryl-1H-1,2,3-triazoles as Potential New Antiretroviral Agents.

    Science.gov (United States)

    Gonzaga, Daniel T G; Souza, Thiago M L; Andrade, Viviane M M; Ferreira, Vitor F; de C da Silva, Fernando

    2018-01-01

    Low molecular weight 1-Aryl-1H-1,2,3-triazoles are endowed with various types of biological activities, such as against cancer, HIV and bacteria. Despite the existence of six different classes of antiretroviral drugs in clinical use, HIV/AIDS continue to be an on growing public health problem. In the present study, we synthesized and evaluated thirty 1-Aryl-1H-1,2,3-triazoles against HIV replication. The compounds were prepared by Huisgen 1,3-dipolar cycloaddition protocol catalyzed by Cu(I) between aryl azides and propargylic alcohol followed by further esterification and etherification from a nucleophilic substitution with acid chlorides or alkyl bromides in good yields. The compounds were submitted to the inhibition of HIV replication and evaluation of their cytotoxicity. Initially, the compounds were screened at 10 µM and the most active were further evaluated in order to obtain some pharmacological parameters. Thirty molecules were evaluated, six were selected - because they inhibited more than 80% HIV replication. We further showed that two of these compounds are 8-times more potent, and less cytotoxic, than nevirapine, an antiretroviral drug in clinical use. We identified very simple triazoles with promissing antiretroviral activities that led to the development of new drugs against AIDS. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  3. Aryl sulfonate based anticancer alkylating agents.

    Science.gov (United States)

    Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

    2018-05-01

    This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

  4. Antioxidant Functions of the Aryl Hydrocarbon Receptor

    Directory of Open Access Journals (Sweden)

    Cornelia Dietrich

    2016-01-01

    Full Text Available The aryl hydrocarbon receptor (AhR is a transcription factor belonging to the basic helix-loop-helix/PER-ARNT-SIM family. It is activated by a variety of ligands, such as environmental contaminants like polycyclic aromatic hydrocarbons or dioxins, but also by naturally occurring compounds and endogenous ligands. Binding of the ligand leads to dimerization of the AhR with aryl hydrocarbon receptor nuclear translocator (ARNT and transcriptional activation of several xenobiotic phase I and phase II metabolizing enzymes. It is generally accepted that the toxic responses of polycyclic aromatic hydrocarbons, dioxins, and structurally related compounds are mediated by activation of the AhR. A multitude of studies indicate that the AhR operates beyond xenobiotic metabolism and exerts pleiotropic functions. Increasing evidence points to a protective role of the AhR against carcinogenesis and oxidative stress. Herein, I will highlight data demonstrating a causal role of the AhR in the antioxidant response and present novel findings on potential AhR-mediated antioxidative mechanisms.

  5. Reproductive toxicity in boron exposed workers in Bandirma, Turkey.

    Science.gov (United States)

    Başaran, Nurşen; Duydu, Yalçin; Bolt, Hermann M

    2012-06-01

    Boric acid and sodium borates have been considered as being "toxic to reproduction and development", following results of animal studies with high doses. However unfavorable effects of boron exposure on reproduction and development have not been proved in epidemiological studies so far. The aim of the present study was to investigate the reproductive toxicity indicators in highly exposed workers employed in a boric acid production plant in Bandırma, Turkey. Two hundred and four workers participated in this study. The mean blood boron concentration of the high exposure group of workers was 223.89 ± 69.49 (152.82-454.02)ng/g. Unfavorable effects of boron exposure on the reproductive toxicity indicators were not observed. Copyright © 2012 Elsevier GmbH. All rights reserved.

  6. Analytical methods for the determination of boron in reactor materials programme

    International Nuclear Information System (INIS)

    Chitre, R.S.; Joshi, V.R.; Iyer, C.S.P.

    1983-01-01

    Spectrophotometric methods of determination of boron based on the complexation reaction between boric acid and protonated curcumin are briefly reviewed. Direct determination of boron in heavy water, plant leaves, copper and its alloys, and aluminium and its alloys using a modified method of Hayes and Metcalfe is described. A method for determination of boron, when its content is very low as in case of uranium metal, diuranate, uranium oxide and thorium nitrate, is also described. In this method, boron is first separated as methyl borate by distillation of the sample with methanol in acid media. The distilled ester is absorbed by hydroxide solution and boron is analysed after removal of methanol. The precision obtained is indicated. (M.G.B.)

  7. Electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton degradation of the drug ibuprofen in acid aqueous medium using platinum and boron-doped diamond anodes

    Energy Technology Data Exchange (ETDEWEB)

    Skoumal, Marcel; Rodriguez, Rosa Maria; Cabot, Pere Lluis; Centellas, Francesc; Garrido, Jose Antonio; Arias, Conchita [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)], E-mail: brillas@ub.edu

    2009-02-28

    The degradation of a 41 mg dm{sup -3} ibuprofen (2-(4-isobutylphenyl)propionic acid) solution of pH 3.0 has been comparatively studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Experiments were performed in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and an O{sub 2}-diffusion cathode. Heterogeneous hydroxyl radical ({center_dot}OH) is generated at the anode surface from water oxidation, while homogeneous {center_dot}OH is formed from Fenton's reaction between Fe{sup 2+} and H{sub 2}O{sub 2} generated at the cathode, being its production strongly enhanced from photo-Fenton reaction induced by sunlight. Higher mineralization is attained in all methods using BDD instead Pt, because the former produces greater quantity of {center_dot}OH enhancing the oxidation of pollutants. The mineralization rate increases under UVA and solar irradiation by the rapid photodecomposition of complexes of Fe(III) with acidic intermediates. The most potent method is solar photoelectro-Fenton with BDD giving 92% mineralization due to the formation of a small proportion of highly persistent final by-products. The effect of Fe{sup 2+} content, pH and current density on photoelectro-Fenton degradation has been studied. The ibuprofen decay always follows a pseudo-first-order kinetics and its destruction rate is limited by current density and UV intensity. Aromatics such as 1-(1-hydroxyethyl)-4-isobutylbenzene, 4-isobutylacetophenone, 4-isobutylphenol and 4-ethylbenzaldehyde, and carboxylic acids such as pyruvic, acetic, formic and oxalic have been identified as oxidation by-products. Oxalic acid is the ultimate by-product and the fast photodecarboxylation of its complexes with Fe(III) under UVA or solar irradiation explains the higher oxidation power of photoelectro-Fenton methods in comparison to electro-Fenton procedures.

  8. The effect of the boron source composition ratio on the adsorption performance of hexagonal boron nitride without a template

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ning, E-mail: zhangning5832@163.com; Zhang, Tong; Kan, Hongmin; Wang, Xiaoyang; Long, Haibo; Cui, Xingyu

    2015-08-01

    An inexpensive boric acid (H{sub 3}BO{sub 3}) and borax (Na{sub 2}B{sub 4}O{sub 7}·10H{sub 2}O) mix was used as a source of boron with different composition ratios, and urea was used as a nitrogen source, in flowing ammonia atmosphere, for the preparation of hexagonal boron nitride (h-BN) with different micro-morphologies. Under a certain synthesis process, the effects of the molar ratio of borax and boric acid (or simply the boron source composition ratio for short) on the phase composition of the sample were studied; the work also explored the effect of boron source composition ratio on the micro-morphology, adsorption desorption isotherm and specific surface area of the h-BN powder. The main purpose of this work was to determine the optimum composition ratio of preparing spherical mesoporous h-BN and ensure that the micro-mechanism underpinning the formation of spherical mesoporous h-BN was understood. The results showed that at the optimum boron source composition ratio of 1:1, globular mesoporous spheres with a diameter of approximately 600–800 nm could be obtained with the highest pore volume and specific surface area (230.2 m{sup 2}/g). - Graphical abstract: Display Omitted - Highlights: • Spherical h-BN was synthesized by controlling the boron source composition ratio. • Without extra spherical template, solid Na{sub 2}O was equal to a spherical template. • At boron source composition ratio of 1:1, h-BN had best adsorption performance.

  9. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin; Falivene, Laura; Drinkel, Emma E.; Grant, Sharday; Linden, Anthony; Cavallo, Luigi; Dorta, Reto

    2012-01-01

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Folate Functionalized Boron Nitride Nanotubes and their Selective Uptake by Glioblastoma Multiforme Cells: Implications for their Use as Boron Carriers in Clinical Boron Neutron Capture Therapy.

    Science.gov (United States)

    Ciofani, Gianni; Raffa, Vittoria; Menciassi, Arianna; Cuschieri, Alfred

    2008-11-25

    Boron neutron capture therapy (BNCT) is increasingly being used in the treatment of several aggressive cancers, including cerebral glioblastoma multiforme. The main requirement for this therapy is selective targeting of tumor cells by sufficient quantities of (10)B atoms required for their capture/irradiation with low-energy thermal neutrons. The low content of boron targeting species in glioblastoma multiforme accounts for the difficulty in selective targeting of this very malignant cerebral tumor by this radiation modality. In the present study, we have used for the first time boron nitride nanotubes as carriers of boron atoms to overcome this problem and enhance the selective targeting and ablative efficacy of BNCT for these tumors. Following their dispersion in aqueous solution by noncovalent coating with biocompatible poly-l-lysine solutions, boron nitride nanotubes were functionalized with a fluorescent probe (quantum dots) to enable their tracking and with folic acid as selective tumor targeting ligand. Initial in vitro studies have confirmed substantive and selective uptake of these nanovectors by glioblastoma multiforme cells, an observation which confirms their potential clinical application for BNCT therapy for these malignant cerebral tumors.

  12. Folate Functionalized Boron Nitride Nanotubes and their Selective Uptake by Glioblastoma Multiforme Cells: Implications for their Use as Boron Carriers in Clinical Boron Neutron Capture Therapy

    Directory of Open Access Journals (Sweden)

    Ciofani Gianni

    2008-01-01

    Full Text Available Abstract Boron neutron capture therapy (BNCT is increasingly being used in the treatment of several aggressive cancers, including cerebral glioblastoma multiforme. The main requirement for this therapy is selective targeting of tumor cells by sufficient quantities of10B atoms required for their capture/irradiation with low-energy thermal neutrons. The low content of boron targeting species in glioblastoma multiforme accounts for the difficulty in selective targeting of this very malignant cerebral tumor by this radiation modality. In the present study, we have used for the first time boron nitride nanotubes as carriers of boron atoms to overcome this problem and enhance the selective targeting and ablative efficacy of BNCT for these tumors. Following their dispersion in aqueous solution by noncovalent coating with biocompatible poly-l-lysine solutions, boron nitride nanotubes were functionalized with a fluorescent probe (quantum dots to enable their tracking and with folic acid as selective tumor targeting ligand. Initial in vitro studies have confirmed substantive and selective uptake of these nanovectors by glioblastoma multiforme cells, an observation which confirms their potential clinical application for BNCT therapy for these malignant cerebral tumors.

  13. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion

    Directory of Open Access Journals (Sweden)

    Ana Chira

    2017-02-01

    Full Text Available Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctylaniline, 4-aminoantipyrine, 4-(4-aminophenylbutyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM. The electrodeposited mass varies between 26 ng/cm2 for 4-fluoroaniline formed during 30 s to 442 ng/cm2 for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenylbutyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found.

  14. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion.

    Science.gov (United States)

    Chira, Ana; Bucur, Bogdan; Radu, Gabriel-Lucian

    2017-02-28

    Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctyl)aniline, 4-aminoantipyrine, 4-(4-aminophenyl)butyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM). The electrodeposited mass varies between 26 ng/cm² for 4-fluoroaniline formed during 30 s to 442 ng/cm² for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN) and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenyl)butyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found.

  15. A critical study of the alkalimetric titration of mannitoboric acid complex in relation to the determination of boron in glass and related materials

    International Nuclear Information System (INIS)

    Sinha, B.C.; Dasgupta, S.

    1976-01-01

    The effect of mannitol concentration on the slope of ΔpH/Δv at the equivalence point of neutralisation of mannitoboric acid has been studied. The slope is observed to be dependent on mannitol concentration and it increases with increasing reagent concentration. The minimum pH at which titration of mannitoboric acid complex is possible without any significant error has been found to be 6.4 with a mannitol concentration of at least 15 g/50 ml of solution although the stoichiometric equivalence pH is 9.0. Based on the result of the study, a simple and accurate method has been worked out for the determination of B 2 0 3 up to 141 mg/50 ml in glass and related materials. The titration of mannitoboric acid complex is carried out at the minimum equivalence pH of 6.4 to minimise precipitation of hydroxides and phosphates of certain cations. The interference due to various elements such as Al, Fe, Zr, Pb and Zn when present are eliminated by complexing them with EDTA. Fluorine above 40 mg/50 ml interferes with the determination. (author)

  16. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17-10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  17. The Vibrational Spectra of the Boron Halides and their Molecular ...

    African Journals Online (AJOL)

    The structures, interaction energies and vibrational spectra of the van derWaals complexes formed between boron trifluoride, as Lewis acid, and water and hydrogen sulphide, as Lewis bases, have been determined by means of ab initio calculations at the second-order level of Møller-Plesset perturbation theory, using a ...

  18. Impact of impregnation with boron compounds on combustion ...

    African Journals Online (AJOL)

    This study examined the impacts of varnishing after impregnation with boron compounds on combustion properties of oriental beech. The test samples prepared from oriental beech (Fagus orientalis Lipsky) wood were impregnated according to ASTM D 1413–76–99 with boric acid (Ba) or borax (Bx) using a vacuum ...

  19. Boron atom reactions

    International Nuclear Information System (INIS)

    Estes, R.; Tabacco, M.B.; Digiuseppe, T.G.; Davidovits, P.

    1982-01-01

    The reaction rates of atomic boron with various epoxides have been measured in a flow tube apparatus. The bimolecular rate constants, in units of cm 3 molecule -1 s -1 , are: 1,2-epoxypropane (8.6 x 10 -11 ), 1,2-epoxybutane (8.8 x 10 -11 ), 1,2,3,4-diepoxybutane (5.5 x 10 -11 ), 1-chloro-2,3-epoxypropane (5.7 x 10 -11 ), and 1,2-epoxy-3,3,3-trichloropropane (1.5 x 10 -11 ). (orig.)

  20. Divergent unprotected peptide macrocyclisation by palladium-mediated cysteine arylation.

    Science.gov (United States)

    Rojas, Anthony J; Zhang, Chi; Vinogradova, Ekaterina V; Buchwald, Nathan H; Reilly, John; Pentelute, Bradley L; Buchwald, Stephen L

    2017-06-01

    Macrocyclic peptides are important therapeutic candidates due to their improved physicochemical properties in comparison to their linear counterparts. Here we detail a method for a divergent macrocyclisation of unprotected peptides by crosslinking two cysteine residues with bis-palladium organometallic reagents. These synthetic intermediates are prepared in a single step from commercially available aryl bis-halides. Two bioactive linear peptides with cysteine residues at i , i + 4 and i , i + 7 positions, respectively, were cyclised to introduce a diverse array of aryl and bi-aryl linkers. These two series of macrocyclic peptides displayed similar linker-dependent lipophilicity, phospholipid affinity, and unique volume of distributions. Additionally, one of the bioactive peptides showed target binding affinity that was predominantly affected by the length of the linker. Collectively, this divergent strategy allowed rapid and convenient access to various aryl linkers, enabling the systematic evaluation of the effect of appending unit on the medicinal properties of macrocyclic peptides.

  1. Palladium-catalysed arylation of sulfonamide stabilised enolates

    CSIR Research Space (South Africa)

    Zeevaart, JG

    2005-03-07

    Full Text Available Alpha-Arylation of inethanesulfonamides using palladium catalysis is described. For example, treatment of N-benzyl-Nmethylmethanesulfonamide with catalytic Pd (OAc) (2) in the presence of sodium tert-butoxide, triphenylphosphine and toluene afforded...

  2. Separation of boron isotopes using NMG type anion exchange resin

    International Nuclear Information System (INIS)

    Itagaki, Takaharu; Kosuge, Masao; Fukuda, Junji; Fujii, Yasuhiko.

    1992-01-01

    Ion exchange separation of boron isotopes (B-10 and B-11) has been studied by using a special boron selective ion exchange resin; NMG (n-methyl glucamine)-type anion exchange resin. The resin has shown a large isotope separation coefficient of 1.02 at the experimental conditions of temperature, 80degC, and boric acid concentration, 0.2 M (mole/dm 3 ). Enriched B-10 (92%) was obtained after the migration of 1149 m by a recyclic operation of ion exchange columns in a merry-go-round method. (author)

  3. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    International Nuclear Information System (INIS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Graphical abstract: - Highlights: • Carbon fibers are functionalized with benzoic acid groups via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 66%. • Tensile strength of the carbon fibers is preserved after grafting reaction. • The treatment in molten urea can improve modification efficiency greatly. • Using molten urea as the reaction medium can avoid pollution from organic solvents. - Abstract: Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17–10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  4. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Wu, Guangshun; Ma, Lichun; Zhao, Min [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

    2016-01-30

    Graphical abstract: - Highlights: • Carbon fibers are functionalized with benzoic acid groups via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 66%. • Tensile strength of the carbon fibers is preserved after grafting reaction. • The treatment in molten urea can improve modification efficiency greatly. • Using molten urea as the reaction medium can avoid pollution from organic solvents. - Abstract: Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17–10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  5. Chain-modified radioiodinated fatty acids

    International Nuclear Information System (INIS)

    Otto, C.A.

    1987-01-01

    Several carbon chain manipulations have been studied in terms of their effects on myocardial activity levels and residence time. The manipulations examined included: chain length, chain branching, chain unsaturation, and carbon-iodine bond stabilization. It was found that chain length affects myocardial activity levels for both straight-chain alkyl acids and branched chain alkyl and aryl acids. Similar results have been reported for the straight-chain aryl acids. Generally, the longer chain lengths correlated with higher myocardial activity levels and longer residence times. This behavior is attributed to storage as triglycerides. Branched chain acids are designed to be anti-metabolites but only the aryl β-methyl acids possessed the expected time course of constant or very slowly decreasing activity levels. The alkyl β-methyl acids underwent rapid deiodination - a process apparently independent of β-oxidation. Inhibition of β-oxidation by incorporation of carbon-carbon double and triple bonds was studied. Deiodination of ω-iodo alkyl fatty acids prevented an assessment of suicide inhibition using an unsaturated alkynoic acid. Stabilization of the carbon-iodine bond by attachment of iodine to a vinylic or aryl carbon was studied. The low myocardial values and high blood values observed for an eleven carbon ω-iodo vinylic fatty acid were not encouraging but ω-iodo aryl fatty acids appear to avoid the problems of rapid deiodination. (Auth.)

  6. Depth profiling of hydrogen passivation of boron in Si(100)

    Science.gov (United States)

    Huang, L. J.; Lau, W. M.; Simpson, P. J.; Schultz, P. J.

    1992-08-01

    The properties of SiO2/p-Si were studied using variable-energy positron-annihilation spectroscopy and Raman spectroscopy. The oxide film was formed by ozone oxidation in the presence of ultraviolet radiation at room temperature. Both the positron-annihilation and Raman analyses show that chemical cleaning of boron-doped p-type Si(100) using concentrated hydrofluoric acid prior to the oxide formation leads to hydrogen incorporation in the semiconductor. The incorporated hydrogen passivates the boron dopant by forming a B-H complex, the presence of which increases the broadening of the line shape in the positron-annihilation analysis, and narrows the linewidth of the Raman peak. Annealing of the SiO2/Si sample at a moderate temperature of 220 °C in vacuum was found sufficient to dissociate the complex and reactivate the boron dopant.

  7. Boron compounds in neutron capture therapy of tumors

    International Nuclear Information System (INIS)

    Strouf, O.; Gregor, V.

    1986-01-01

    In the selective incorporation of a sufficient amount of a compound containing boron isotope 10 B in the tumor tissue for neutron capture therapy, high efficiency is achieved in tumor destruction while sparing the surrounding tissues. In the treatment of brain tumors, 4-carboxy phenylboric acid and the disodium salt of mercaptoundecahydrododecaborate were successfully tested. The use of the compounds minimizes radiation damage to the blood stream of the brain. In case of melanomas the L-DOPA-borate complex, boronophenylalanine and chlorpromazine preparations containing 10 B are used. In the treatment of cancer of the reproductive organs, boron derivatives of estradiol and testosterone have been proven. The immunobiological procedure, i.e., the use of antibodies with bound boron compounds, is being intensively studied. (M.D.)

  8. Study and optimization of the carbothermic reduction process for obtaining boron carbide

    International Nuclear Information System (INIS)

    Castro, A.R.M. de.

    1989-01-01

    Boron carbide - B sub(4)C - is a ceramic material of technological importance due to its hardness and high chemical and thermal stabilities. Moreover, its high neutron capture cross section makes it suitable for application as neutron absorber in nuclear technology. The process for obtaining carbothermally derived boron carbide has been studied in two steps: firstly, the parameters of the boric acidboron oxide dehydration reaction have been defined; secondly, the optimization of the carbothermal reduction reaction using boron oxide has been undertaken looking for boron carbide having low level of free carbon. The starting materials as well as the main products have been studied by chemical and spectrographic analyses, X-ray diffractometry, granulometric classification and scanning electron microscopy. The optimization of the carbothermic reduction process allowed for the development and set up of a fabrication procedure yielding high quality B sub(4) C powders, starting from low cost and easily available (in the Brazilian market) raw materials. (author)

  9. Emission spectrochemical determination of boron in steels with pulse height distribution analyzer

    International Nuclear Information System (INIS)

    Ito, Minao; Sato, Shoki; Fushida, Hiroshi; Narita, Masanao

    1983-01-01

    The method for rapid determination of total, acid soluble and insoluble boron was established by using emission spectrochemical apparatus equipped with pulse height distribution analyzer. By using the analyzer, emission intensity can be expressed as different level intensity of pulse height distribution. It was made clear that soluble and insoluble boron had different contribution degree to each intensity and that this contribution degree varied at different pre-spark. Therefore, it is necessary for accurate determination of boron that this contribution degree should be corrected by using two intensities, of which contribution degrees are different. It was found on this two intensities method that total and soluble boron corresponded well to 50 % intensities at zero pre-spark and at 2000 pre-spark and that insoluble boron corresponded well to 70 % intensity at zero pre-spark and 50 % intensity at 2000 pre-spark. (author)

  10. Separation process for boron isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Rockwood, S D

    1975-06-12

    The method according to the invention is characterized by the steps of preparing a gaseous mixture of BCl/sub 3/ containing the isotopes of boron and oxygen as the extractor, irradiating that mixture in the tube of the separator device by means of P- or R-lines of a CO/sub 2/ laser for exciting the molecules containing a given isotope of boron, simultaneously irradiating the mixture with UV for photodissociating the excited BCl/sub 3/ molecules and separating BCl/sub 3/ from the reaction products of photodissociation and from oxygen. Such method is suitable for preparing boron used in nuclear reactors.

  11. Lattice dynamics of α boron and of boron carbide

    International Nuclear Information System (INIS)

    Vast, N.

    1999-01-01

    The atomic structure and the lattice dynamics of α boron and of B 4 C boron carbide have been studied by Density Functional Theory (D.F.T.) and Density Functional Perturbation Theory (D.F.P.T.). The bulk moduli of the unit-cell and of the icosahedron have been investigated, and the equation of state at zero temperature has been determined. In α boron, Raman diffusion and infrared absorption have been studied under pressure, and the theoretical and experimental Grueneisen coefficients have been compared. In boron carbide, inspection of the theoretical and experimental vibrational spectra has led to the determination of the atomic structure of B 4 C. Finally, the effects of isotopic disorder have been modeled by an exact method beyond the mean-field approximation, and the effects onto the Raman lines has been investigated. The method has been applied to isotopic alloys of diamond and germanium. (author)

  12. Non-crystalline composite tissue engineering scaffolds using boron-containing bioactive glass and poly(d,l-lactic acid) coatings

    International Nuclear Information System (INIS)

    Mantsos, T; Chatzistavrou, X; Roether, J A; Boccaccini, A R; Hupa, L; Arstila, H

    2009-01-01

    The aim of this study was the fabrication of three-dimensional, highly porous, bioactive scaffolds using a recently developed bioactive glass powder, denominated '0106', with nominal composition (in wt%): 50 SiO 2 , 22.6 CaO, 5.9 Na 2 O, 4 P 2 O 5 , 12 K 2 O, 5.3 MgO and 0.2 B 2 O 3 . The optimum sintering conditions for the fabrication of scaffolds by the foam-replica method were identified (sintering temperature: 670 deg, C and dwell time: 5 h). Composite samples were also fabricated by applying a biopolymer coating of poly( D,L -lactic acid) (PDLLA) using a dip coating process. The average compressive strength values were 0.4 MPa for uncoated and 0.6 MPa for coated scaffolds. In vitro bioactivity studies in simulated body fluid (SBF) showed that a carbonate hydroxyapatite (HCAp) layer was deposited on uncoated and coated scaffolds after only 4 days of immersion in SBF, demonstrating the high in vitro bioactivity of the scaffolds. It was also confirmed that the scaffold structure remained amorphous (no crystallization) after the specific heat treatment used, with scaffolds exhibiting mechanical properties and bioactivity suitable for use in bone tissue engineering applications.

  13. Non-crystalline composite tissue engineering scaffolds using boron-containing bioactive glass and poly(d,l-lactic acid) coatings

    Energy Technology Data Exchange (ETDEWEB)

    Mantsos, T; Chatzistavrou, X; Roether, J A; Boccaccini, A R [Department of Materials, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Hupa, L; Arstila, H, E-mail: a.boccaccini@imperial.ac.u [Process Chemistry Centre, Abo Akademi University, Piispankatu 8, FI-20500 Turku (Finland)

    2009-10-15

    The aim of this study was the fabrication of three-dimensional, highly porous, bioactive scaffolds using a recently developed bioactive glass powder, denominated '0106', with nominal composition (in wt%): 50 SiO{sub 2}, 22.6 CaO, 5.9 Na{sub 2}O, 4 P{sub 2}O{sub 5}, 12 K{sub 2}O, 5.3 MgO and 0.2 B{sub 2}O{sub 3}. The optimum sintering conditions for the fabrication of scaffolds by the foam-replica method were identified (sintering temperature: 670 deg, C and dwell time: 5 h). Composite samples were also fabricated by applying a biopolymer coating of poly({sub D,L}-lactic acid) (PDLLA) using a dip coating process. The average compressive strength values were 0.4 MPa for uncoated and 0.6 MPa for coated scaffolds. In vitro bioactivity studies in simulated body fluid (SBF) showed that a carbonate hydroxyapatite (HCAp) layer was deposited on uncoated and coated scaffolds after only 4 days of immersion in SBF, demonstrating the high in vitro bioactivity of the scaffolds. It was also confirmed that the scaffold structure remained amorphous (no crystallization) after the specific heat treatment used, with scaffolds exhibiting mechanical properties and bioactivity suitable for use in bone tissue engineering applications.

  14. Nothing Boring About Boron

    Science.gov (United States)

    Pizzorno, Lara

    2015-01-01

    The trace mineral boron is a micronutrient with diverse and vitally important roles in metabolism that render it necessary for plant, animal, and human health, and as recent research suggests, possibly for the evolution of life on Earth. As the current article shows, boron has been proven to be an important trace mineral because it (1) is essential for the growth and maintenance of bone; (2) greatly improves wound healing; (3) beneficially impacts the body’s use of estrogen, testosterone, and vitamin D; (4) boosts magnesium absorption; (5) reduces levels of inflammatory biomarkers, such as high-sensitivity C-reactive protein (hs-CRP) and tumor necrosis factor α (TNF-α); (6) raises levels of antioxidant enzymes, such as superoxide dismutase (SOD), catalase, and glutathione peroxidase; (7) protects against pesticide-induced oxidative stress and heavy-metal toxicity; (8) improves the brains electrical activity, cognitive performance, and short-term memory for elders; (9) influences the formation and activity of key biomolecules, such as S-adenosyl methionine (SAM-e) and nicotinamide adenine dinucleotide (NAD+); (10) has demonstrated preventive and therapeutic effects in a number of cancers, such as prostate, cervical, and lung cancers, and multiple and non-Hodgkin’s lymphoma; and (11) may help ameliorate the adverse effects of traditional chemotherapeutic agents. In none of the numerous studies conducted to date, however, do boron’s beneficial effects appear at intakes > 3 mg/d. No estimated average requirements (EARs) or dietary reference intakes (DRIs) have been set for boron—only an upper intake level (UL) of 20 mg/d for individuals aged ≥ 18 y. The absence of studies showing harm in conjunction with the substantial number of articles showing benefits support the consideration of boron supplementation of 3 mg/d for any individual who is consuming a diet lacking in fruits and vegetables or who is at risk for or has osteopenia; osteoporosis

  15. EFFECTS OF SOME BORON COMPOUNDS ON THE LEACHABILITY OF EUCALYPTUS (Eucalyptus camaldulensis Dehn. WOOD

    Directory of Open Access Journals (Sweden)

    Hüseyin Tan

    2003-04-01

    Full Text Available Wood preservation effectiveness of boron compounds against biological damagers and fire is well known. But these compounds are not widely used in preservation of wood because of their leachability from wood by rain water and making wood more hyroscopic than untreated wood in damp environments. Main aim of this study is; therefore, to improve the undesired leachability properties of some boron compounds by various water repellents (WRs. Aqueous solutions with polyethyleneglycole (PEG-400 of boric acid and sodium perborate were chosen as boron compounds. WRs were used as secondary treatment chemicals which were considered as dimensional stabilizer of wood and phsical bariers of boron retained at innerparts of treated wood. Results indicated that WRs were reduced leachability of boron from wood significantly (P<0.05. Boron salts applied with. PEG were more leachable than were of equeous solutions. WRs were not found effective on reducing the leachability of boron solved in PEG. Longer leaching time caused more leachant and reduction the phsical alleviation of WRs on boron leaching.

  16. Boronization in TEXTOR

    International Nuclear Information System (INIS)

    Winter, J.; Esser, H.G.; Koenen, L.; Reimer, H.; Seggern, J. v.; Schlueter, J.; Waelbroeck, F.; Wienhold, P.; Veprek, S.

    1989-01-01

    The liner and limiters of TEXTOR have been coated in situ with a boron containing carbon film using a RG discharge in a throughflow of 0.8 He + 0.1 B 2 H 6 + 0.1 CH 4 . The average film thickness was 30-50 nm, the ratio of boron and carbon in the layer was about 1:1 according to Auger Electron Spectroscopy. Subsequent tokamak discharges are characterized by a small fraction of radiated power ( eff lower than 1.2 are derived from conductivity measurements. The most prominent change in the impurity concentration compared to good conditions in a carbonized surrounding is measured for oxygen. The value OVI/anti n e of the OVI intensity normalized to the averaged plasma density anti n e decreases by more than a factor of four. The decrease in the oxygen content manifests itself also as a reduction of the CO and CO 2 partial pressures measured during and after the discharge with a sniffer probe. The carbon levels are reduced by a factor of about two as measured by the normalized intensity CII/anti n e of the CII line and via the ratio of the C fluxes and deuterium fluxed measured at the limiter (CI/D α ). The wall shows a pronounced sorption of hydrogen from the plasma, easing the density control and the establishment of low recycling conditions. The beneficial conditions did not show a significant deterioration during more than 200 discharges, including numerous shots at ICRH power levels >2 MW. (orig.)

  17. Determination of boron spectrophotometry in thorium sulfate

    International Nuclear Information System (INIS)

    Federgrun, L.; Abrao, A.

    1976-01-01

    A procedure for the determination of microquantities of boron in nuclear grade thorium sulfate is described. The method is based on the extraction of BF - 4 ion associated to monomethylthionine (MMT) in 1,2 - dichloroethane. The extraction of the colored BF - 4 -MMT complex does not allow the presence of sulfuric and phosphoric acids; other anions interfere seriously. This fact makes the dissolution of the thorium sulfate impracticable, since it is insoluble in both acids. On the other hand, the quantitative separation of thorium is mandatory, to avoid the precipitation of ThF 4 . To overcome this difficulty, the thorium sulfate is dissolved using a strong cationic ion exchanger, Th 4+ being totally retained into the resin. Boron is then analysed in the effluent. The procedure allows the determination of 0.2 to 10.0 microgramas of B, with a maximum error of 10%. Thorium sulfate samples with contents of 0.2 to 2.0μg B/gTh have being analysed [pt

  18. Note on boron toxicity in oats

    Energy Technology Data Exchange (ETDEWEB)

    Langille, W M; Mahoney, J F

    1959-01-01

    Boron was applied at the rate of 35 pounds per acre of borax to a field of oats. With the first noticeable growth there appeared a definite chlorotic condition of the oat seedlings on plots receiving boron treatments. Analysis of chlorotic tissue at 3 weeks after seeding indicated 110 ppm boron, while apparently healthy tissue contained 6.1 ppm boron at the same stage of growth. There was a rapid decline in the boron content of the oat tissue as the crop grew older. At maturity the oat tissue from the boron-treated plots contained an average of 14.15 ppm boron as compared with 4.10 boron from untreated areas. Boron toxicity had no harmful effect so far as yields were concerned, under the conditions of this experiment. 3 references.

  19. Method for producing polycrystalline boron nitride

    International Nuclear Information System (INIS)

    Alexeevskii, V.P.; Bochko, A.V.; Dzhamarov, S.S.; Karpinos, D.M.; Karyuk, G.G.; Kolomiets, I.P.; Kurdyumov, A.V.; Pivovarov, M.S.; Frantsevich, I.N.; Yarosh, V.V.

    1975-01-01

    A mixture containing less than 50 percent of graphite-like boron nitride treated by a shock wave and highly defective wurtzite-like boron nitride obtained by a shock-wave method is compressed and heated at pressure and temperature values corresponding to the region of the phase diagram for boron nitride defined by the graphite-like compact modifications of boron nitride equilibrium line and the cubic wurtzite-like boron nitride equilibrium line. The resulting crystals of boron nitride exhibit a structure of wurtzite-like boron nitride or of both wurtzite-like and cubic boron nitride. The resulting material exhibits higher plasticity as compared with polycrystalline cubic boron nitride. Tools made of this compact polycrystalline material have a longer service life under impact loads in machining hardened steel and chilled iron. (U.S.)

  20. Metal interactions with boron clusters

    International Nuclear Information System (INIS)

    Grimes, R.N.

    1982-01-01

    This book presents information on the following topics: the structural and bonding features of metallaboranes and metallacarboranes; transition-metal derivatives of nido-boranes and some related species; interactions of metal groups with the octahydrotriborate (1-) anion, B 3 H 8 ; metallaboron cage compounds of the main group metals; closo-carborane-metal complexes containing metal-carbon and metal-boron omega-bonds; electrochemistry of metallaboron cage compounds; and boron clusters with transition metal-hydrogen bonds

  1. Synthesis and characterization of boron trifluoride (B F[sub 3]). Sintese e caracterizacao de trifluoreto de boro (BF[sub 3])

    Energy Technology Data Exchange (ETDEWEB)

    Bastos, E T.R.; Umeda, K; Echternacht, M V; Silva, E.F. da.

    1994-08-01

    High purity boron trifluoride (B F[sub 3]) has been prepared from reaction of ammonium fluorborate and boron oxide in concentrated sulfuric acid. Fluorborate was synthesized by reaction of ammonium bi fluoride and boric acid produced from enrichment plant. (author).

  2. Nickel-catalyzed synthesis of aryl trifluoromethyl sulfides at room temperature.

    Science.gov (United States)

    Zhang, Cheng-Pan; Vicic, David A

    2012-01-11

    Inexpensive nickel-bipyridine complexes were found to be active for the trifluoromethylthiolation of aryl iodides and aryl bromides at room temperature using the convenient [NMe(4)][SCF(3)] reagent. © 2011 American Chemical Society

  3. Characterization of substituted aryl meroterpenoids from red seaweed Hypnea musciformis as potential antioxidants.

    Science.gov (United States)

    Chakraborty, Kajal; Joseph, Deepu; Joy, Minju; Raola, Vamshi Krishna

    2016-12-01

    The ethyl acetate fraction of red seaweed Hypnea musciformis was purified to yield three substituted aryl meroterpenoids, namely, 2-(tetrahydro-5-(4-hydroxyphenyl)-4-pentylfuran-3-yl)-ethyl-4-hydroxybenzoate (1), 2-2-[(4-hydroxybenzoyl)-oxy]-ethyl-4-methoxy-4-2-[(4-methylpentyl)oxy]-3,4-dihydro-2H-6-pyranylbutanoic acid (2) and 3-((5-butyl-3-methyl-5,6-dihydro-2H-pyran-2-yl)-methyl)-4-methoxy-4-oxobutyl benzoate (3). The structures of these compounds, as well as their relative stereochemistries, were confirmed by exhaustive NMR spectroscopic data analyses. Compound 1 exhibited similar 2,2'-diphenylpicrylhydrazyl radical inhibiting and Fe(2+) ion chelating activities (IC50 25.05 and 350.7μM, respectively) as that of commercial antioxidant gallic acid (IC50 32.3 and 646.6μM, respectively), followed by 3 (IC50 231.2 and 667.9μM, respectively), and 2 (IC50 322.4 and 5115.3μM, respectively), in descending order of activities. Structure-activity relationship analysis revealed that the antioxidant activities of these compounds were directly proportional to the steric and hydrophobic parameters. The seaweed derived aryl meroterpenoids might serve as potential lead antioxidative molecules for use in pharmaceutical and food industries. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Cascade synthesis of dihydrobenzofuran via Claisen rearrangement of allyl aryl ethers using FeCl3/MCM-41 catalyst

    Directory of Open Access Journals (Sweden)

    Sachin S. Sakate

    2018-05-01

    Full Text Available Dihydrobenzofuran as one of the active ingredients of the naturally occurring motif is synthesized by using in situ generation of ortho allyl phenols. Aryl allyl ethers on reacting with catalytic amounts of non noble metal iron (III chloride supported on MCM-41 under moderate reaction conditions yield dihydrobenzofuran. First step via Claisen rearrangement gives ortho allyl phenol followed by its in situ cyclization to yield dihydrobenzofuran in very good yields. Both Lewis as well as Brønsted acidity of the catalyst as evidenced by Py-FTIR studies was found to catalyze the cascade synthesis of dihydrobenzofuran. The scope of the present strategy was successfully demonstrated for several substrates with varying electronic effects for the synthesis of corresponding dihydrobenzofuran with high yields in a range of 71–86%. Keywords: Claisen rearrangement, Dihydrobenzofuran, Aryl allyl ether, MCM-41, Ferric chloride

  5. Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

    DEFF Research Database (Denmark)

    Sanchez, R.S.; Zhuravlev, Fedor

    2007-01-01

    The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

  6. Aryl hydrocarbon receptor and intestinal immunity.

    Science.gov (United States)

    Lamas, Bruno; Natividad, Jane M; Sokol, Harry

    2018-04-07

    Aryl hydrocarbon receptor (AhR) is a member of the basic helix-loop-helix-(bHLH) superfamily of transcription factors, which are associated with cellular responses to environmental stimuli, such as xenobiotics and oxygen levels. Unlike other members of bHLH, AhR is the only bHLH transcription factor that is known to be ligand activated. Early AhR studies focused on understanding the role of AhR in mediating the toxicity and carcinogenesis properties of the prototypic ligand 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). In recent years, however, it has become apparent that, in addition to its toxicological involvement, AhR is highly receptive to a wide array of endogenous and exogenous ligands, and that its activation leads to a myriad of key host physiological functions. In this study, we review the current understanding of the functions of AhR in the mucosal immune system with a focus on its role in intestinal barrier function and intestinal immune cells, as well as in intestinal homeostasis.

  7. Boron evaporation in thermally-driven seawater desalination: Effect of temperature and operating conditions

    KAUST Repository

    Alpatova, Alla; Alsaadi, Ahmad Salem; Ghaffour, NorEddine

    2018-01-01

    The volatilization of boron in thermal desalination processes, namely multi-stage flash (MSF) and air-gap membrane distillation (AGMD) was investigated for the first time. This phenomenon was observed at feed temperatures above 55 °C in both studied processes. In simulated MSF process with two feeds, model boric acid and Red Sea water, boron concentration in distillate increased with feed temperature increase from 55 °C to 104 °C because of the increase in boric acid vapor pressure. Salinity and pH were the main factors controlling boron evaporation. The achieved boron concentrations in simulated MSF process were consistent with those measured in distillate samples collected from commercial MSF plants. The AGMD process also revealed a strong influence of operating temperature on boron removal. However, unlike MSF process, the boron concentration in AGMD permeate decreased with the feed temperature increase from 55 °C to 80 °C due probably to increase in vapor production and corresponding permeate dilution. When AGMD was operated in concentrating mode at a constant feed temperature of 80 °C, permeate boron concentration increased with process time due to concentration polarization and membrane fouling. A 10% flux decline observed after 21 h was attributed to CaCO scaling on the membrane surface.

  8. Spectrophotometric determination of trace and ultratrace levels of boron in silicon and chlorosilane samples

    International Nuclear Information System (INIS)

    Chen, J.S.; Lin, H.M.; Yang, M.H.

    1991-01-01

    Spectrophotometric methods for the determination of boron in the low μg/g and ng/g range in high-purity silicon and dichloro- and trichlorosilanes were investigated in detail. The procedures established involve dissolution of silicon samples and the hydrolyzed products of chlorosilane samples in hydrofluoric acid-containing reagents followed by evaporation of the silicon matrix as H 2 SiF 6 . The boron retained in the treated sample solution was then determined by a spectrophotometric method using carminic acid as a chromatic reagent. Special effort has been paid to the control of the analytical blank and reproducible determination of boron. The results indicate that addition of mannitol and proper control of the evaporation process are effective in preventing volatilization of boron during the evaporation of silicon matrix and can thus attain high recovery of boron and reproducible analysis. Through meticulous control of the analytical blank and experimental conditions, the limit of detection for boron determination with the established method can be as low as ng/g levels. Application of the methods to the determination of boron in various stages of purification of silicon and trichlorosilane as well as in borophosphosilicate film was conducted. (orig.)

  9. Boron evaporation in thermally-driven seawater desalination: Effect of temperature and operating conditions.

    Science.gov (United States)

    Alpatova, A; Alsaadi, A; Ghaffour, N

    2018-06-05

    The volatilization of boron in thermal desalination processes, namely multi-stage flash (MSF) and air-gap membrane distillation (AGMD) was investigated for the first time. This phenomenon was observed at feed temperatures above 55 °C in both studied processes. In simulated MSF process with two feeds, model boric acid and Red Sea water, boron concentration in distillate increased with feed temperature increase from 55 °C to 104 °C because of the increase in boric acid vapor pressure. Salinity and pH were the main factors controlling boron evaporation. The achieved boron concentrations in simulated MSF process were consistent with those measured in distillate samples collected from commercial MSF plants. The AGMD process also revealed a strong influence of operating temperature on boron removal. However, unlike MSF process, the boron concentration in AGMD permeate decreased with the feed temperature increase from 55 °C to 80 °C due probably to increase in vapor production and corresponding permeate dilution. When AGMD was operated in concentrating mode at a constant feed temperature of 80 °C, permeate boron concentration increased with process time due to concentration polarization and membrane fouling. A 10% flux decline observed after 21 h was attributed to CaCO 3 scaling on the membrane surface. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Boron evaporation in thermally-driven seawater desalination: Effect of temperature and operating conditions

    KAUST Repository

    Alpatova, Alla

    2018-03-26

    The volatilization of boron in thermal desalination processes, namely multi-stage flash (MSF) and air-gap membrane distillation (AGMD) was investigated for the first time. This phenomenon was observed at feed temperatures above 55 °C in both studied processes. In simulated MSF process with two feeds, model boric acid and Red Sea water, boron concentration in distillate increased with feed temperature increase from 55 °C to 104 °C because of the increase in boric acid vapor pressure. Salinity and pH were the main factors controlling boron evaporation. The achieved boron concentrations in simulated MSF process were consistent with those measured in distillate samples collected from commercial MSF plants. The AGMD process also revealed a strong influence of operating temperature on boron removal. However, unlike MSF process, the boron concentration in AGMD permeate decreased with the feed temperature increase from 55 °C to 80 °C due probably to increase in vapor production and corresponding permeate dilution. When AGMD was operated in concentrating mode at a constant feed temperature of 80 °C, permeate boron concentration increased with process time due to concentration polarization and membrane fouling. A 10% flux decline observed after 21 h was attributed to CaCO scaling on the membrane surface.

  11. Proceedings of workshop on 'boron chemistry and boron neutron capture therapy'

    International Nuclear Information System (INIS)

    Kitaoka, Yoshinori

    1993-09-01

    This volume contains the proceedings of the 5th Workshop on 'the Boron Chemistry and Boron Neutron Capture Therapy' held on February 22 in 1993. The solubility of the boron carrier play an important role in the BNCT. New water-soluble p-boronophenylalanine derivatives are synthesized and their biological activities are investigated (Chap. 2 and 3). Some chemical problems on the BNCT were discussed, and the complex formation reaction of hydroxylboryl compounds were studied by the paper electrophoresis (Chap. 4). The results of the medical investigation on the BNCT using BSH compounds are shown in Chap. 5. Syntheses of o- and m-boronophenylalanine were done and their optical resolution was tried (Chap. 6). The complex formation reaction of p-boronophenylalanine (BPA) with L-DOPA and the oxidation reaction of the analogs are found in Chap. 7. The pka of BPA were determined by the isotachophoresis (Chap. 8). The chemical nature of dihydroxyboryl compounds were investigated by an infrared spectroscopy and electrophoresis (Chap. 9). New synthetic methods of BPA and p-boronophenylserine using ester of isocyanoacetic acid are described in Chap. 10. The induction of chromosomal aberations by neutron capture reaction are discussed from a point of the biological view. The a of the presented papers are indexed individually. (J.P.N.)

  12. Boron Fullerenes: A First-Principles Study

    Directory of Open Access Journals (Sweden)

    Gonzalez Szwacki Nevill

    2007-01-01

    Full Text Available AbstractA family of unusually stable boron cages was identified and examined using first-principles local-density functional method. The structure of the fullerenes is similar to that of the B12icosahedron and consists of six crossing double-rings. The energetically most stable fullerene is made up of 180 boron atoms. A connection between the fullerene family and its precursors, boron sheets, is made. We show that the most stable boron sheets are not necessarily precursors of very stable boron cages. Our finding is a step forward in the understanding of the structure of the recently produced boron nanotubes.

  13. Surface modified MXene Ti_3C_2 multilayers by aryl diazonium salts leading to large-scale delamination

    International Nuclear Information System (INIS)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-01-01

    Highlights: • A novel and simple method to delaminate MXene Ti_3C_2 multilayers. • Surface modification using aryl diazonium salts induced swelling that conversely weakened the bonds between MXene layers. • The grafting of phenylsulfonic acid groups on MXene surfaces resulted in excellent water dispersibility. - Abstract: Herein we report a simple and facile method to delaminate MXene Ti_3C_2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti_3AlC_2 and the exfoliation of Ti_3AlC_2 into Ti_3C_2 multilayers, followed by Na"+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti_3C_2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti_3C_2 sheets disperse well in water and the solutions obey Lambert–Beer’s law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti_3C_2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti_3C_2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  14. Boron isotope separation by ion exchange chromatography using weakly basic anion exchange resin

    International Nuclear Information System (INIS)

    Sakuma, Yoichi; Aida, Masao; Okamoto, Makoto; Kakihana, Hidetake

    1980-01-01

    Isotopic plateau displacement chromatography, a useful method for isotope separation is presented. The boric acid band formed in a column of weakly basic anion exchange resin Diaion WA21 can be eluted with pure water. In order to obtain good accumulation of the isotope effect, a series of experiments with different migration length were carried out. The boron-10 enriched part of the boric acid absorbed band was always preceded by the isotopic plateau part, in which the atomic fraction of boron-10 was maintained at its original value. The atomic fraction of boron-10 at the end of the chromatogram increased with migration length, and in the case of 256-m migration, boron-10 was enriched from its original atomic fraction of 19.84 to 91.00%, the separation factor S being constant irrespective of migration length: S = 1.0100 +- 0.0005. (author)

  15. Visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO.

    Science.gov (United States)

    Pramanik, Mukund M D; Rastogi, Namrata

    2016-06-30

    The visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO is illustrated. This is the first example of DMSO being used as the source of the methylsulfinyl group. The procedure tolerates a wide range of functional groups on (het)aryl diazonium salts and provides aryl methyl sulfoxides in excellent yields under mild reaction conditions.

  16. Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

    KAUST Repository

    Fan, Lulu; Jia, Jiaqi; Hou, Hong; Lefebvre, Quentin; Rueping, Magnus

    2016-01-01

    A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

  17. Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

    KAUST Repository

    Fan, Lulu

    2016-09-23

    A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

  18. Increased aryl hydrocarbon receptor expression in patients with allergic rhinitis.

    Science.gov (United States)

    Wei, P; Hu, G-H; Kang, H-Y; Yao, H-B; Kou, W; Liu, H; Hong, S-L

    2014-02-01

    A predominant Th17 population is a marker of allergic rhinitis (AR). As a ligand-activated transcription factor, the aryl hydrocarbon receptor (AhR) plays a vital role in promoting or inhibiting the development of specific Th cells. However, its role in AR remains undefined. To analyze the potential role of AhR in the pathogenesis of AR. In total, 30 AR patients and 13 healthy controls were recruited for this study and AR patients had clinical features, as demonstrated by rhinoconjunctivitis quality of life questionnaires, total symptom scores and visual analog scale scores. The expression of AhR, IL-17 and IL-22 and the presence of Th17 cells in peripheral blood mononuclear cells were measured before and after treatment with the nontoxic AhR ligand 2-(1'H-indole-3'-carbonyl)-thiazole-4-carboxylic acid methyl ester (ITE). Pretreatment ITE studies revealed that all AR patients had a significant increase in AhR expression compared with controls and AhR expression positively correlated with clinical parameters. After ITE intervention, a severe reduction in the differentiation of Th17 cells and the production of IL-17 and IL-22 was noted in both AR patients and normal subjects. Simultaneously, a dramatic enhancement of AhR expression was also observed in all healthy controls, but not in AR patients. The results suggested that the AhR may be one of the mechanisms underlying the Th17 response during the pathogenesis of AR and AhR levels were closely related to clinical severity in all AR patients. Additionally, ITE may represent a new drug candidate in the treatment of AR.

  19. Benefits of Low Boron Core Design Concept for PWR

    Energy Technology Data Exchange (ETDEWEB)

    Daing, Aung Tharn; Kim, Myung Hyun [Kyung Hee University, Yongin (Korea, Republic of)

    2009-10-15

    Nuclear design study was carried out to develop low boron core (LBC) based on one of current PWR concepts, OPR-1000. Most of design parameters were the same with those of Ulchin unit-5 except extensive utilization of burnable poison (BP) pins in order to compensate reactivity increase in LBC. For replacement of reduced soluble boron concentration, four different kinds of integral burnable absorbers (IBAs) such as gadolinia, integral fuel burnable absorber (IFBA), erbia and alumina boron carbide were considered in suppressing more excess reactivity. A parametric study was done to find the optimal core options from many design candidates for fuel assemblies and cores. Among them, the most feasible core design candidate was chosen in accordance with general design requirements. In this paper, the feasibility and design change benefits of the most favorable LBC design were investigated in more detail through the comparison of neutronic and thermal hydraulic design parameters of LBC with the reference plant (REF). As calculation tools, the HELIOS/MASTER code package and the MATRA code were utilized. The main purpose of research herein is to estimate feasibility and capability of LBC which was mainly designed to mitigate boron dilution accident (BDA), and for reduction of corrosion products. The LBC design concept using lower boron concentration with an elevated enrichment in {sup 10}B allows a reduction in the concentration of lithium in the primary coolant required to maintain the optimum coolant pH. All in all, LBC with operation at optimum pH is expected to achieve some benefits from radiation source reduction of reduced corrosion product, the limitation of the Axial Offset Anomaly (AOA) and fuel cladding corrosion. Additionally, several merits of LBC are closely related to fluid systems and system related aspects, reduced boron and lithium costs, equipment size reduction for boric acid systems, elimination of heat tracing, and more aggressive fuel design concepts.

  20. Benefits of Low Boron Core Design Concept for PWR

    International Nuclear Information System (INIS)

    Daing, Aung Tharn; Kim, Myung Hyun

    2009-01-01

    Nuclear design study was carried out to develop low boron core (LBC) based on one of current PWR concepts, OPR-1000. Most of design parameters were the same with those of Ulchin unit-5 except extensive utilization of burnable poison (BP) pins in order to compensate reactivity increase in LBC. For replacement of reduced soluble boron concentration, four different kinds of integral burnable absorbers (IBAs) such as gadolinia, integral fuel burnable absorber (IFBA), erbia and alumina boron carbide were considered in suppressing more excess reactivity. A parametric study was done to find the optimal core options from many design candidates for fuel assemblies and cores. Among them, the most feasible core design candidate was chosen in accordance with general design requirements. In this paper, the feasibility and design change benefits of the most favorable LBC design were investigated in more detail through the comparison of neutronic and thermal hydraulic design parameters of LBC with the reference plant (REF). As calculation tools, the HELIOS/MASTER code package and the MATRA code were utilized. The main purpose of research herein is to estimate feasibility and capability of LBC which was mainly designed to mitigate boron dilution accident (BDA), and for reduction of corrosion products. The LBC design concept using lower boron concentration with an elevated enrichment in 10 B allows a reduction in the concentration of lithium in the primary coolant required to maintain the optimum coolant pH. All in all, LBC with operation at optimum pH is expected to achieve some benefits from radiation source reduction of reduced corrosion product, the limitation of the Axial Offset Anomaly (AOA) and fuel cladding corrosion. Additionally, several merits of LBC are closely related to fluid systems and system related aspects, reduced boron and lithium costs, equipment size reduction for boric acid systems, elimination of heat tracing, and more aggressive fuel design concepts

  1. Facile synthetic approach for 5-aryl-9-hydroxypyrano [3,2-f] indole-2(8H-one

    Directory of Open Access Journals (Sweden)

    Cheng Wang

    2016-11-01

    Full Text Available An appropriate method for the synthesis of 5-aryl-9-hydroxypyrano[3,2-f]indole-2(8H-one was described. The targeted compounds were obtained starting from vanillin via nine steps. Interestingly, in the final cyclization step, the intermediate 4-(2-halogeno phenyl-7-methoxy-1H-indole-6-yl propiolate could convert directly into the final product in one step reaction using PtCl4 or Pd(PPh34/trifluoroacetic acid as catalysts. The possible catalytic mechanism for PtCl4 and Pd(PPh34/trifluoroacetic acid was discussed.

  2. Boron containing poly-(lactide-co-glycolide) (PLGA) scaffolds for bone tissue engineering

    Energy Technology Data Exchange (ETDEWEB)

    Doğan, Ayşegül; Demirci, Selami [Department of Genetics and Bioengineering, Faculty of Engineering and Architecture, Yeditepe University 34755 Istanbul (Turkey); Bayir, Yasin [Department of Biochemistry, Faculty of Pharmacy, Ataturk University, 25240, Erzurum (Turkey); Halici, Zekai [Department of Pharmacology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Karakus, Emre [Department of Pharmacology and Toxicology, Faculty of Veterinary Medicine, Ataturk University, 25240, Erzurum (Turkey); Aydin, Ali [Department of Orthopedics and Traumatology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Cadirci, Elif [Department of Pharmacology, Faculty of Pharmacy, Ataturk University, 25240, Erzurum (Turkey); Albayrak, Abdulmecit [Department of Pharmacology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Demirci, Elif [Department of Pathology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Karaman, Adem [Department of Radiology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Ayan, Arif Kursat [Department of Nuclear Medicine, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Gundogdu, Cemal [Department of Pathology, Faculty of Medicine, Ataturk University, 25240, Erzurum (Turkey); Şahin, Fikrettin, E-mail: fsahin@yeditepe.edu.tr [Department of Genetics and Bioengineering, Faculty of Engineering and Architecture, Yeditepe University 34755 Istanbul (Turkey)

    2014-11-01

    Scaffold-based bone defect reconstructions still face many challenges due to their inadequate osteoinductive and osteoconductive properties. Various biocompatible and biodegradable scaffolds, combined with proper cell type and biochemical signal molecules, have attracted significant interest in hard tissue engineering approaches. In the present study, we have evaluated the effects of boron incorporation into poly-(lactide-co-glycolide-acid) (PLGA) scaffolds, with or without rat adipose-derived stem cells (rADSCs), on bone healing in vitro and in vivo. The results revealed that boron containing scaffolds increased in vitro proliferation, attachment and calcium mineralization of rADSCs. In addition, boron containing scaffold application resulted in increased bone regeneration by enhancing osteocalcin, VEGF and collagen type I protein levels in a femur defect model. Bone mineralization density (BMD) and computed tomography (CT) analysis proved that boron incorporated scaffold administration increased the healing rate of bone defects. Transplanting stem cells into boron containing scaffolds was found to further improve bone-related outcomes compared to control groups. Additional studies are highly warranted for the investigation of the mechanical properties of these scaffolds in order to address their potential use in clinics. The study proposes that boron serves as a promising innovative approach in manufacturing scaffold systems for functional bone tissue engineering. - Highlights: • Boron containing PLGA scaffolds were developed for bone tissue engineering. • Boron incorporation increased cell viability and mineralization of stem cells. • Boron containing scaffolds increased bone-related protein expression in vivo. • Implantation of stem cells on boron containing scaffolds improved bone healing.

  3. Boron containing poly-(lactide-co-glycolide) (PLGA) scaffolds for bone tissue engineering

    International Nuclear Information System (INIS)

    Doğan, Ayşegül; Demirci, Selami; Bayir, Yasin; Halici, Zekai; Karakus, Emre; Aydin, Ali; Cadirci, Elif; Albayrak, Abdulmecit; Demirci, Elif; Karaman, Adem; Ayan, Arif Kursat; Gundogdu, Cemal; Şahin, Fikrettin

    2014-01-01

    Scaffold-based bone defect reconstructions still face many challenges due to their inadequate osteoinductive and osteoconductive properties. Various biocompatible and biodegradable scaffolds, combined with proper cell type and biochemical signal molecules, have attracted significant interest in hard tissue engineering approaches. In the present study, we have evaluated the effects of boron incorporation into poly-(lactide-co-glycolide-acid) (PLGA) scaffolds, with or without rat adipose-derived stem cells (rADSCs), on bone healing in vitro and in vivo. The results revealed that boron containing scaffolds increased in vitro proliferation, attachment and calcium mineralization of rADSCs. In addition, boron containing scaffold application resulted in increased bone regeneration by enhancing osteocalcin, VEGF and collagen type I protein levels in a femur defect model. Bone mineralization density (BMD) and computed tomography (CT) analysis proved that boron incorporated scaffold administration increased the healing rate of bone defects. Transplanting stem cells into boron containing scaffolds was found to further improve bone-related outcomes compared to control groups. Additional studies are highly warranted for the investigation of the mechanical properties of these scaffolds in order to address their potential use in clinics. The study proposes that boron serves as a promising innovative approach in manufacturing scaffold systems for functional bone tissue engineering. - Highlights: • Boron containing PLGA scaffolds were developed for bone tissue engineering. • Boron incorporation increased cell viability and mineralization of stem cells. • Boron containing scaffolds increased bone-related protein expression in vivo. • Implantation of stem cells on boron containing scaffolds improved bone healing

  4. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  5. Adsorption of boron from boron-containing wastewaters by ion exchange in a continuous reactor

    International Nuclear Information System (INIS)

    Yilmaz, A. Erdem; Boncukcuoglu, Recep; Yilmaz, M. Tolga; Kocakerim, M. Muhtar

    2005-01-01

    In this study, boron removal from boron-containing wastewaters prepared synthetically was investigated. The experiments in which Amberlite IRA 743, boron specific resin was used were carried out in a column reactor. The bed volume of resin, boron concentration, flow rate and temperature were selected as experimental parameters. The experimental results showed that percent of boron removal increased with increasing amount of resin and with decreasing boron concentration in the solution. Boron removal decreased with increasing of flow rate and the effect of temperature on the percent of total boron removal increased the boron removal rate. As a result, it was seen that about 99% of boron in the wastewater could be removed at optimum conditions

  6. Sulfonamidation of Aryl and Heteroaryl Halides through Photosensitized Nickel Catalysis.

    Science.gov (United States)

    Kim, Taehoon; McCarver, Stefan J; Lee, Chulbom; MacMillan, David W C

    2018-03-19

    Herein we report a highly efficient method for nickel-catalyzed C-N bond formation between sulfonamides and aryl electrophiles. This technology provides generic access to a broad range of N-aryl and N-heteroaryl sulfonamide motifs, which are widely represented in drug discovery. Initial mechanistic studies suggest an energy-transfer mechanism wherein C-N bond reductive elimination occurs from a triplet excited Ni II complex. Late-stage sulfonamidation in the synthesis of a pharmacologically relevant structure is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Lattice vibrations in α-boron

    International Nuclear Information System (INIS)

    Richter, W.

    1976-01-01

    α-rhombohedral boron is the simplest boron modification, with only 12 atoms per unit cell. The boron atoms are arranged in B 12 icosahedra, which are centered at the lattice points of a primitive rhombohedral lattice. The icosahedra are slightly deformed, as the five-fold symmetry of the ideal icosahedron is incompatible with any crystal structure. The lattice dynamics of α-boron are discussed in terms of the model developed by Weber and Thorpe. (Auth.)

  8. Advanced boron soaking procedure for steam generators

    International Nuclear Information System (INIS)

    Ueno, T.; Tsuge, A.; Kawanishi, K.; Ochi, T.; Kadokami, E.

    1991-01-01

    An experimental study on boric acid penetration into tube to tube-support-plate crevices and Inter-Granular-Attack (hereinafter called 'IGA') cracks in crevices has been performed to obtain the optimum boric acid soaking procedure in operating steam generators with IGA. The penetration rate into the crevice is closely related to various parameters such as heat flux, crevice gap, and porosity of the sludge deposited in crevices. Two experimental crevice models were set up. One was of the packed crevice type; crevice gap is completely packed by sludge, and the other was of the open crevice type; crevice gap is not packed, but reduced by sludge. The porosity of the crevice varied from 100% open porosity to the highly sludge packed porosity of 10∼20%. The relation between heat flux and boric acid penetration rate of the packed crevice type was investigated. For the open crevice type, from the viewpoint that boric acid penetration into the dryout region produces no effects, tube wall superheat in the crevice was measured in order to obtain the dryout heat flux. And it was investigated the boron in IGA cracks using Ion Micro Analysis in order to confirm existence of an anticorrosive film in IGA propagation. The optimum reactor power for effective boric acid penetration onto the tube surface and into the IGA cracks within the tube to tube-support-plate crevice was found to be about a 5% and 30% power level, which are applicable to both the packed and open crevice type. (author)

  9. Surface modified MXene Ti3C2 multilayers by aryl diazonium salts leading to large-scale delamination

    Science.gov (United States)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-10-01

    Herein we report a simple and facile method to delaminate MXene Ti3C2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti3AlC2 and the exfoliation of Ti3AlC2 into Ti3C2 multilayers, followed by Na+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti3C2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti3C2 sheets disperse well in water and the solutions obey Lambert-Beer's law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti3C2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti3C2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  10. Three New Offset {delta}{sup 11}B Isotope Reference Materials for Environmental Boron Isotope Studies

    Energy Technology Data Exchange (ETDEWEB)

    Rosner, M. [BAM Federal Institute for Materials Research and Testing, Berlin (Germany); IsoAnalysis UG, Berlin (Germany); Vogl, J. [BAM Federal Institute for Materials Research and Testing, Berlin (Germany)

    2013-07-15

    The isotopic composition of boron is a well established tool in various areas of science and industry. Boron isotope compositions are typically reported as {delta}{sup 11}B values which indicate the isotopic difference of a sample relative to the isotope reference material NIST SRM 951. A significant drawback of all of the available boron isotope reference materials is that none of them covers a natural boron isotope composition apart from NIST SRM 951. To fill this gap of required {delta}{sup 11}B reference materials three new solution boric acid reference materials were produced, which cover 60 per mille of the natural boron isotope variation (-20 to 40 per mille {delta}{sup 11}B) of about 100 per mille . The new reference materials are certified for their {delta}{sup 11}B values and are commercially available through European Reference Materials (http://www.erm-crm.org). The newly produced and certified boron isotope reference materials will allow straightforward method validation and quality control of boron isotope data. (author)

  11. Use of Crystalline Boron as a Burn Rate Retardant Toward the Development of Green-Colored Handheld Signal Formulations

    Science.gov (United States)

    2011-01-01

    emitter and formed magnesium oxide (MgO) in a highly exothermic process upon reacting with barium nitrate. Although it served as a low-energy fuel...nitric acid under boiling conditions, it fails to react when treated with boiling hydrofluoric and hydrochloric acids [13]. Table 3 Performance of...fuel. It is believed that amorphous boron, when reacted with oxygen, forms metastable boron oxide (BO2) in the excited state, which is responsible for

  12. Development of automatic high-concentration boron measurement technique; Konodo hoso jido sokutei gijutsu no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, T.; Honda, S.; Ito, A. [Kyushu Electric Power Co. Inc., Fukuoka (Japan)

    1997-03-01

    The technology that can automatically measure the boron concentration in boric acid water was developed. A high-concentration boric acid solution must be held at a high temperature to prevent the deposition. Skill and precision ({plus_minus}0.2 to 0.3% for 10 to 2500 ppm as boron concentration, and {plus_minus}2 to 3% for 2500 to 25,000 ppm) are required to analyze the boric acid solution manually. In theory, the boron concentration in a wide range can be measured, and boron has a constant-temperature function. A density hydrometer method that facilitates the treatment and calibration in high precision and at low cost was chosen. The vibration period generated when vibration is given to the solution specimen put in a U-tube is higher as the density is lower. On the basis of this theory, the density of a specimen can be obtained according to the relation with the same data of the known-concentration boric acid water. The high-concentration boric acid water that cannot be measured by the existing boron densitometer can be measured directly. It can also be measured in a low-concentration area. The technique can be used in a laboratory as the simplified method that is replaced by the current manual analysis. The reduction effect of analytical chemical`s waste liquid can also be expected. In the electric power industry, automated equipment is required for high efficiency and labor saving. 13 figs., 3 tabs.

  13. New Icosahedral Boron Carbide Semiconductors

    Science.gov (United States)

    Echeverria Mora, Elena Maria

    Novel semiconductor boron carbide films and boron carbide films doped with aromatic compounds have been investigated and characterized. Most of these semiconductors were formed by plasma enhanced chemical vapor deposition. The aromatic compound additives used, in this thesis, were pyridine (Py), aniline, and diaminobenzene (DAB). As one of the key parameters for semiconducting device functionality is the metal contact and, therefore, the chemical interactions or band bending that may occur at the metal/semiconductor interface, X-ray photoemission spectroscopy has been used to investigate the interaction of gold (Au) with these novel boron carbide-based semiconductors. Both n- and p-type films have been tested and pure boron carbide devices are compared to those containing aromatic compounds. The results show that boron carbide seems to behave differently from other semiconductors, opening a way for new analysis and approaches in device's functionality. By studying the electrical and optical properties of these films, it has been found that samples containing the aromatic compound exhibit an improvement in the electron-hole separation and charge extraction, as well as a decrease in the band gap. The hole carrier lifetimes for each sample were extracted from the capacitance-voltage, C(V), and current-voltage, I(V), curves. Additionally, devices, with boron carbide with the addition of pyridine, exhibited better collection of neutron capture generated pulses at ZERO applied bias, compared to the pure boron carbide samples. This is consistent with the longer carrier lifetimes estimated for these films. The I-V curves, as a function of external magnetic field, of the pure boron carbide films and films containing DAB demonstrate that significant room temperature negative magneto-resistance (> 100% for pure samples, and > 50% for samples containing DAB) is possible in the resulting dielectric thin films. Inclusion of DAB is not essential for significant negative magneto

  14. Boron steel. I Part. Preparation

    International Nuclear Information System (INIS)

    Jaraiz Franco, E.; Esteban Hernandez, J. A.

    1960-01-01

    With the advent of the first nuclear reactors arise the need for control rods and shielding duties for some types of radiations. One of the materials used for this purpose has been the high boron steel. This paper describes the melting and casting procedures employed for the production, at laboratory scale, of steels with Boron content ranging from 1 to 4 per cent, as well as the metallographic and X-Ray techniques used for the identification of the present phases. The electrolytic technique employed for the isolation of the Fe 2 B phase and its subsequent X-Ray identification has proved to be satisfactory. (Author) 11 refs

  15. Chemical separation of boron isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Palko, A.A.

    1978-06-01

    This is the final report of the research performed at ORNL on the chemical fractionation of boron isotopes between BF/sub 3/ gas and the liquid molecular addition compounds of BF/sub 3/. Thirty compounds were studied, ten of them in detail. Graphs and equations are given for variation of isotopic equilibrium constant, vapor pressure, and BF/sub 3/ solubility as a function of temperature. Rate of isotopic exchange and melting points were determined. Several of the compounds are likely candidates for use in a gas-liquid countercurrent exchange system for large-scale separation of boron isotopes. 23 figs, 53 tables, 39 references.

  16. Chemical separation of boron isotopes

    International Nuclear Information System (INIS)

    Palko, A.A.

    1978-06-01

    This is the final report of the research performed at ORNL on the chemical fractionation of boron isotopes between BF 3 gas and the liquid molecular addition compounds of BF 3 . Thirty compounds were studied, ten of them in detail. Graphs and equations are given for variation of isotopic equilibrium constant, vapor pressure, and BF 3 solubility as a function of temperature. Rate of isotopic exchange and melting points were determined. Several of the compounds are likely candidates for use in a gas-liquid countercurrent exchange system for large-scale separation of boron isotopes. 23 figs, 53 tables, 39 references

  17. A comparative study of two digestion methods employed for the determination boron in ferroboron used as an advanced shielding material

    International Nuclear Information System (INIS)

    Kamble, Granthali S.; Manisha, V.; Venkatesh, K.

    2015-01-01

    Shielding of nuclear reactor core is an important requirement of fast reactors. An important objective of future Fast Breeder Reactors (FBRs) is to reduce the volume of shields. A large number of materials have been considered for use to reduce the neutron flux to acceptable levels. A shield material which brings down the energy of neutrons by elastic and inelastic scattering along with absorption will be more effective. Ferro boron is identified as one of the advanced shielding materials considered for use in future FBRs, planned to be constructed in India. Ferroboron is an economical and indigenously available material which qualifies as a promising shield material through literature survey and scoping calculations. Experiments have been conducted in KAMINI reactor to understand the effectiveness of prospective shield material Ferro-boron as an in-core shield material for future FBRs. The Ferro boron used in these experiments contained 11.8% and 15% of boron. Precise determination of boron content in these ferro boron samples is very important to determine its effectiveness as a shield material. In this work a comparative study was carried out to determine the boron content in ferro boron samples. In the first method the sample was treated with incremental amounts of nitric acid under reflux (to prevent rigorous reaction and volatalisation of boron). The solution was gradually heated and the solution was filtered through a Whatman Filter paper no. 41. The undissolved ferro boron residue collected in the filter paper after filtration, is transferred to a platinum crucible; mixed with sodium carbonate and is ashed. The crucible is placed over a burner for 1 h to fuse the contents. The fused mass is leached in dilute hydrochloric acid, added to the nitric acid filtrate and made up to pre-determined volume

  18. Two-channel neutron boron meter

    International Nuclear Information System (INIS)

    Chen Yongqing; Yin Guowei; Chai Songshan; Deng Zhaoping; Zhou Bin

    1993-09-01

    The two-channel neutron boron meter is a continuous on-line measuring device to measure boron concentration of primary cooling liquid of reactors. The neutron-leakage-compensation method is taken in the measuring mechanism. In the primary measuring configuration, the mini-boron-water annulus and two-channel and central calibration loop are adopted. The calibration ring and constant-temperature of boron-water can be remotely controlled by secondary instruments. With the microcomputer data processing system the boron concentration is automatically measured and calibrated in on-line mode. The meter has many advantages such as high accuracy, fast response, multi-applications, high reliability and convenience

  19. Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

    Directory of Open Access Journals (Sweden)

    Michael Gurry

    2014-09-01

    Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

  20. Cyclohexenones Through Addition of Ethyl Acetoacetate to 3-Aryl-1 ...

    African Journals Online (AJOL)

    Chalcone derivatives 3a–i containing a thiophene ring were prepared by the condensation of 1-(thiophen-3-yl)ethanone with aromatic aldehydes in excellent yields. The Michael addition of ethyl acetoacetate 4 to chalcone derivatives 3a–i resulted in the formation of nine novel ethyl 6-aryl ...

  1. Cobalt-promoted regioselective preparation of aryl tetrazole amines

    Indian Academy of Sciences (India)

    KONDRAGANTI LAKSHMI

    2018-04-17

    Apr 17, 2018 ... To the best of .... coupled product with aryl iodide under mild reaction ..... Having the optimal conditions studied, the scope of ... ity, environmental acceptability and cost-effectiveness ... lite as a new and reusable heterogeneous catalyst Chem. ... Aminotetrazoles from Thioureas: A Strategy for Diver-.

  2. Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

    NARCIS (Netherlands)

    Fañanás-Mastral, Martín; Feringa, Ben L

    2014-01-01

    Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

  3. Oxidative electrochemical aryl C-C coupling of spiropyrans

    NARCIS (Netherlands)

    Ivashenko, Oleksii; van Herpt, Jochem T.; Rudolf, Petra; Feringa, Ben L.; Browne, Wesley R.

    2013-01-01

    The isolation and definitive assignment of the species formed upon electrochemical oxidation of nitro-spiropyran (SP) is reported. The oxidative aryl C-C coupling at the indoline moiety of the SP radical cation to form covalent dimers of the ring-closed SP form is demonstrated. The coupling is

  4. Boron-enhanced diffusion of boron from ultralow-energy boron implantation

    International Nuclear Information System (INIS)

    Agarwal, A.; Eaglesham, D.J.; Gossmann, H.J.; Pelaz, L.; Herner, S.B.; Jacobson, D.C.

    1998-01-01

    The authors have investigated the diffusion enhancement mechanism of BED (boron enhanced diffusion), wherein the boron diffusivity is enhanced three to four times over the equilibrium diffusivity at 1,050 C in the proximity of a silicon layer containing a high boron concentration. It is shown that BED is associated with the formation of a fine-grain polycrystalline silicon boride phase within an initially amorphous Si layer having a high B concentration. For 0.5 keV B + , the threshold implantation dose which leads to BED lies between 3 x 10 14 and of 1 x 10 15 /cm -2 . Formation of the shallowest possible junctions by 0.5 keV B + requires that the implant dose be kept lower than this threshold

  5. Killing effect of carboranyl uridine on boron neutron capture reaction

    International Nuclear Information System (INIS)

    Takagaki, M.; Oda, Y.; Zhang, Z.

    1994-01-01

    This paper deals with the killing effect of carboranyl uridine (CU) on thermal neutron capture reaction in cultured glioma cell line (C6). The tumoricidal effect of CU for boron neutron capture therapy in the cultured cell system is presented. To assess the uptake of CU, the number of germ cells was determined by comparing protein concentrations of C6 cells in vitro with that of intracranially transplanted C6 tumor cells in vivo. To assess tumoricidal effects of CU, human glioma cells (T98G), containing 25 ppm natural boron of CU, were irradiated with various doses of thermal neutrons at a constant fluence rate. The uptake and killing effects of mercaptoboron and boric acid were also investigated as controls. Subcellular boron concentrations confirmed the selective affinity to the nucleic acid synthesis. CU was found to have an affinity to nucleic acid synthesis and to be accumulated into nucleus of tumor cells. The irradiation dose which yielded 37% survival rate in the case of CU and control were 3.78+12E nvt and 5.80+12E nvt, respectively. The killing effect of CU was slightly higher than that of B-SH or BA. The effective way of CU injection should be further studied to obtain the uniform CU uptake in tumor cells. (N.K.)

  6. WEED CONTROL AND BORON NUTRITION ON Eucalyptus IN SILVOPASTORAL SYSTEM

    Directory of Open Access Journals (Sweden)

    Alexandre Magno Brighenti

    2015-04-01

    Full Text Available The objective of this study was to evaluate the control of weeds in the rows of eucalyptus (Eucalyptus urograndis with herbicides applied singly or combined with boron (B, as well as, the response of Eucalyptus plants to this micronutrient. The experiments were carried out in a split-plot with randomized complete block design, with three replicates. Six treatments were applied to the plots: (i weeded control, (ii control without weeding, (iii glyphosate (1080 g ae ha-1 + chlorimuron-ethyl (10 g ai ha-1 + 0.05% v / v mineral oil, (iv glyphosate (1080 g ae  ha-1 + isoxaflutole (112.5 g ai ha-1,  (v glyphosate (1080 g ae ha-1 and  (vi oxyfluorfen (480 g ai ha-1. The sub-plots consisted of the absence or presence of 4 kg of boric acid (H3BO3 - 17% B in 100 L of water. The addition of boric acid in the solution containing the herbicides did not affect the weed control. There was an increase in boron content in the soil and consequently an increase in the boron levels in the eucalyptus leaves. The combined application of herbicides plus boric acid is perfectly suitable for preventing dry of the pointer on eucalyptus plants. Keywords: Eucalyptus urograndis; chemical control; herbicides; micronutrients; Urochloa decumbens.

  7. Determination of boron in graphite by a wet oxidation decomposition/curcumin photometric method

    International Nuclear Information System (INIS)

    Watanabe, Kazuo; Toida, Yukio

    1995-01-01

    The wet oxidation decomposition of graphite materials has been studied for the accurate determination of boron using a curcumin photometric method. A graphite sample of 0.5 g was completely decomposed with a mixture of 5 ml of sulfuric acid, 3 ml of perchloric acid, 0.5 ml of nitric acid and 5 ml of phosphoric acid in a silica 100 ml Erlenmeyer flask fitted with an air condenser at 200degC. Any excess of perchloric and nitric acids in the solution was removed by heating on a hot plate at 150degC. Boron was distilled with methanol, and then recovered in 10 ml of 0.2 M sodium hydroxide. The solution was evaporated to dryness. To the residue were added curcumin-acetic acid and sulfuric-acetic acid. The mixture was diluted with ethanol, and the absorbance at 555 nm was measured. The addition of 5 ml of phosphoric acid proved to be effective to prevent any volatilization loss of boron during decomposition of the graphite sample and evaporation of the resulting solution. The relative standard deviation was 4-8% for samples with 2 μg g -1 levels of boron. The results on CRMs JAERI-G5 and G6 were in good agreement with the certified values. (author)

  8. The Arabidopsis-related halophyte Thellungiella halophila: boron tolerance via boron complexation with metabolites?

    Science.gov (United States)

    Lamdan, Netta Li; Attia, Ziv; Moran, Nava; Moshelion, Menachem

    2012-04-01

    Tolerance to boron (B) is still not completely understood. We tested here the hypothesis that Thellungiella halophila, an Arabidopsis thaliana-related 'extremophile' plant, with abundance of B in its natural environment, is tolerant to B, and examined the potential mechanisms of this tolerance. With 1-10 mm B applied ([B](ext)) to Thellungiella and Arabidopsis grown in hydroponics, the steady-state accumulated B concentration ([B](int)) in the root was below [B](ext), and was similar in both, suggesting both extrude B actively. Whether grown in soil or hydroponically, the shoot [B](int) was higher in Arabidopsis than in Thellungiella, suggesting more effective net B exclusion by Thellungiella root. Arabidopsis exhibited toxicity symptoms including reduced shoot fresh weight (FW), but Thellungiella was not affected, even at similar levels of shoot-accumulated [B](int) (about 10 to 40 mm B in 'shoot water'), suggesting additional B tolerance mechanism in Thellungiella shoot. At [B](ext) = 5 mm, the summed shoot concentration of the potentially B-binding polyhydroxyl metabolites (malic acid, fructose, glucose, sucrose and citric acid) in Arabidopsis was below [B](int) , but in Thellungiella it was over twofold higher than [B](int) , and therefore likely to allow appreciable 1:2 boron-metabolite complexation in the shoot. This, we suggest, is an important component of Thellungiella B tolerance mechanism. © 2011 Blackwell Publishing Ltd.

  9. Boron neutron capture therapy of ocular melanoma and intracranial glioma using p-boronophenylalanine

    International Nuclear Information System (INIS)

    Coderre, J.A.; Greenberg, D.; Micca, P.L.; Joel, D.D.; Saraf, S.; Packer, S.

    1990-01-01

    During conventional radiotherapy, the dose that can be delivered to the tumor is limited by the tolerance of the surrounding normal tissue within the treatment volume. Boron Neutron Capture Therapy (BNCT) represents a promising modality for selective tumor irradiation. The key to effective BNCT is selective localization of 10 B in the tumor. We have shown that the synthetic amino acid p-boronophenylalanine (BPA) will selectively deliver boron to melanomas and other tumors such as gliosarcomas and mammary carcinomas. Systemically delivered BPA may have general utility as a boron delivery agent for BNCT. In this paper, BNCT with BPA is used in treatment of experimentally induced gliosarcoma in rats and nonpigmented melanoma in rabbits. The tissue distribution of boron is described, as is response to the BNCT. 6 refs., 4 figs., 1 tab

  10. Structural characterization of electrodeposited boron

    Indian Academy of Sciences (India)

    Structural characterization of electrodeposited boron was carried out by using transmission electron microscopy and Raman spectroscopy. Electron diffraction and phase contrast imaging were carried out by using transmission electron microscopy. Phase identification was done based on the analysis of electron diffraction ...

  11. Boron isotopes in geothermal systems

    International Nuclear Information System (INIS)

    Aggarwal, J.

    1997-01-01

    Boron is a highly mobile element and during water-rock reactions, boron is leached out of rocks with no apparent fractionation. In geothermal systems where the water recharging the systems are meteoric in origin, the B isotope ratio of the geothermal fluid reflects the B isotope ratio of the rocks. Seawater has a distinctive B isotope ratio and where seawater recharges the geothermal system, the B isotope ratio of the geothermal system reflects the mixing of rock derived B and seawater derived B. Any deviations of the actual B isotope ratio of a mixture reflects subtle differences in the water-rock ratios in the cold downwelling limb of the hydrothermal system. This paper will present data from a variety of different geothermal systems, including New Zealand; Iceland; Yellowston, USA; Ibusuki, Japan to show the range in B isotope ratios in active geothermal systems. Some of these systems show well defined mixing trends between seawater and the host rocks, whilst others show the boron isotope ratios of the host rock only. In geothermal systems containing high amounts of CO 2 boron isotope ratios from a volatile B source can also be inferred. (auth)

  12. Structural characterization of electrodeposited boron

    Indian Academy of Sciences (India)

    high temperature reaction between elemental boron and car- bon to form B4C is .... cible was used as the container for the electrolyte and also acted as an anode. ... chosen as cathode due to its availability, low cost, ease of fabrication and ...

  13. Determination of very small contents of boron by pH difference measurement

    International Nuclear Information System (INIS)

    Boehm, H.; Kirmse, E.M.; Schilbach, U.

    1983-01-01

    For the determination of boron as a trace element for food of plants in a very complicated salt matrix an analytical proceeding was developed, which allows to determine the content of boron without separation. The principle of analysis is based on the esterification of boric acid with a multivalent alcohol, which leeds to a monovalent strong complex acid. The change of the pH value of the analysing solution is measured. From the initial pH number, the end pH number, the volume of the analysing solution and the ionic product of water corresponding with the operating temperature the quantity of boric acid of boron that is equivalent the produced quantity of H + -ions is calculated by means of a linear program. The standard deviation of analytical proceeding amounts to 13.9 ng B. For the determination of the contents of boron of an unknown sample, five to ten separate measurements are carried out. For solutions, which are about 1x10 -6 M of boric acid, there are necessary 10 ml of sample for each separate measurement. The confidence interval of analytical results is found to be between +- 0.5 and +- 15.5% (P=0.99). For the determination of the content of boron in plant materials about 50-100 mg of dry weight are necessary. (Author)

  14. Boron-11 MRI and MRS of intact animals infused with a boron neutron capture agent

    International Nuclear Information System (INIS)

    Kabalka, G.W.; Davis, M.; Bendel, P.

    1988-01-01

    Boron neutron capture therapy (BNCT) depends on the delivery of boron-containing drugs to a targeted lesion. Currently, the verification and quantification of in vivo boron content is a difficult problem. Boron-11 spectroscopy was utilized to confirm the presence of a dimeric sulfhydryl dodecaborane BNCT agent contained in an intact animal. Spectroscopy experiments revealed that the decay time of transverse magnetization of the boron-11 spins was less than 1 ms which precluded the use of a 2DFT imaging protocol. A back-projection protocol was developed and utilized to generate the first boron-11 image of a BNCT agent in the liver of an intact Fisher 344 rat

  15. Boron and Coumaphos Residues in Hive Materials Following Treatments for the Control of Aethina tumida Murray

    Science.gov (United States)

    Valdovinos-Flores, Cesar; Gaspar-Ramírez, Octavio; Heras–Ramírez, María Elena; Dorantes-Ugalde, José Antonio; Saldaña-Loza, Luz María

    2016-01-01

    In the search of alternatives for controlling Aethina tumida Murray, we recently proposed the BAA trap which uses boric acid and an attractant which mimics the process of fermentation caused by Kodamaea ohmeri in the hive. This yeast is excreted in the feces of A. tumida causing the fermentation of pollen and honey of infested hives and releasing compounds that function as aggregation pheromones to A. tumida. Since the boron is the toxic element in boric acid, the aim of this article is to assess the amount of boron residues in honey and beeswax from hives treated with the BAA trap. For this aim, the amount of bioaccumulated boron in products of untreated hives was first determined and then compared with the amount of boron of products from hives treated with the BAA trap in two distinct climatic and soil conditions. The study was conducted in the cities of Padilla, Tamaulipas, and Valladolid, Yucatan (Mexico) from August 2014 to March 2015. The quantity of boron in honey was significantly less in Yucatan than in Tamaulipas; this agrees with the boron deficiency among Luvisol and Leptosol soils found in Yucatan compared to the Vertisol soil found in Tamaulipas. In fact, the honey from Yucatan has lower boron levels than those reported in the literature. The BAA treatment was applied for four months, results show that the BAA trap does not have any residual effect in either honey or wax; i.e., there is no significant difference in boron content before and after treatment. On the other hand, the organophosphate pesticide coumaphos was found in 100% of wax samples and in 64% of honey samples collected from Yucatan. The concentration of coumaphos in honey ranges from 0.005 to 0.040 mg/kg, which are below Maximum Residue Limit (MRL) allowed in the European Union (0.1 mg/kg) but 7.14% of samples exceeded the MRL allowed in Canada (0.02 mg/kg). PMID:27092938

  16. Boron and Coumaphos Residues in Hive Materials Following Treatments for the Control of Aethina tumida Murray.

    Directory of Open Access Journals (Sweden)

    Cesar Valdovinos-Flores

    Full Text Available In the search of alternatives for controlling Aethina tumida Murray, we recently proposed the BAA trap which uses boric acid and an attractant which mimics the process of fermentation caused by Kodamaea ohmeri in the hive. This yeast is excreted in the feces of A. tumida causing the fermentation of pollen and honey of infested hives and releasing compounds that function as aggregation pheromones to A. tumida. Since the boron is the toxic element in boric acid, the aim of this article is to assess the amount of boron residues in honey and beeswax from hives treated with the BAA trap. For this aim, the amount of bioaccumulated boron in products of untreated hives was first determined and then compared with the amount of boron of products from hives treated with the BAA trap in two distinct climatic and soil conditions. The study was conducted in the cities of Padilla, Tamaulipas, and Valladolid, Yucatan (Mexico from August 2014 to March 2015. The quantity of boron in honey was significantly less in Yucatan than in Tamaulipas; this agrees with the boron deficiency among Luvisol and Leptosol soils found in Yucatan compared to the Vertisol soil found in Tamaulipas. In fact, the honey from Yucatan has lower boron levels than those reported in the literature. The BAA treatment was applied for four months, results show that the BAA trap does not have any residual effect in either honey or wax; i.e., there is no significant difference in boron content before and after treatment. On the other hand, the organophosphate pesticide coumaphos was found in 100% of wax samples and in 64% of honey samples collected from Yucatan. The concentration of coumaphos in honey ranges from 0.005 to 0.040 mg/kg, which are below Maximum Residue Limit (MRL allowed in the European Union (0.1 mg/kg but 7.14% of samples exceeded the MRL allowed in Canada (0.02 mg/kg.

  17. Methods for separating boron from borated paraffin wax and its determination by ion chromatography

    International Nuclear Information System (INIS)

    Jeyakumar, S.

    2015-01-01

    Boron compounds are found to be useful in shielding against high-energy neutrons. In radiotherapy treatments, in order to protect occupational workers and patients from the undesirable neutron and gamma doses, paraffin wax containing B 4 C/boric acid is used. Low-level borate wastes generated from the nuclear power plants have been immobilized with paraffin wax using a concentrate waste drying system (CWDS). Borated paraffin waxes are prepared by mixing calculated amounts of either boric acid or boron carbide with the molten wax. This necessitates the determination of boron at different locations in order to check the homogeneous distribution of B over the borated wax. The determination of boron in nuclear materials is inevitable due to its high neutron absorption cross section. For the determination of boron in borated waxes, not many methods have been reported. A method based on the pyrohydrolysis extraction of boron and its quantification with ion chromatography was proposed for paraffin waxes borated with H 3 BO 3 and B 4 C. The B 4 C optimum pyrohydrolysis conditions were identified. Wax samples were mixed with U 3 O 8 , which prevents the sample from flare up, and also accelerates the extraction of boron. Pyrohydrolysis was carried out with moist O 2 at 950℃ for 60 and 90 min for wax with H 3 BO 3 and wax with B 4 C, respectively. Two simple methods of separation based on alkali extraction and melting wax in alkali were also developed exclusively for wax with H 3 BO 3 . In all the separations, the recovery of B was above 98%. During IC separation, B was separated as boron-mannitol anion complex. Linear calibration was obtained between 0.1 and 50 ppm of B, and LOD was calculated as 5 ppb (S/N=3). The reproducibility was better than 5% (RSD)

  18. Friction anisotropy in boronated graphite

    International Nuclear Information System (INIS)

    Kumar, N.; Radhika, R.; Kozakov, A.T.; Pandian, R.; Chakravarty, S.; Ravindran, T.R.; Dash, S.; Tyagi, A.K.

    2015-01-01

    Graphical abstract: - Highlights: • Friction anisotropy in boronated graphite is observed in macroscopic sliding condition. • Low friction coefficient is observed in basal plane and becomes high in prismatic direction. • 3D phase of boronated graphite transformed into 2D structure after friction test. • Chemical activity is high in prismatic plane forming strong bonds between the sliding interfaces. - Abstract: Anisotropic friction behavior in macroscopic scale was observed in boronated graphite. Depending upon sliding speed and normal loads, this value was found to be in the range 0.1–0.35 in the direction of basal plane and becomes high 0.2–0.8 in prismatic face. Grazing-incidence X-ray diffraction analysis shows prominent reflection of (0 0 2) plane at basal and prismatic directions of boronated graphite. However, in both the wear tracks (1 1 0) plane become prominent and this transformation is induced by frictional energy. The structural transformation in wear tracks is supported by micro-Raman analysis which revealed that 3D phase of boronated graphite converted into a disordered 2D lattice structure. Thus, the structural aspect of disorder is similar in both the wear tracks and graphite transfer layers. Therefore, the crystallographic aspect is not adequate to explain anisotropic friction behavior. Results of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy shows weak signature of oxygen complexes and functional groups in wear track of basal plane while these species dominate in prismatic direction. Abundance of these functional groups in prismatic plane indicates availability of chemically active sites tends to forming strong bonds between the sliding interfaces which eventually increases friction coefficient

  19. Friction anisotropy in boronated graphite

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, N., E-mail: niranjan@igcar.gov.in [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India); Radhika, R. [Crystal Growth Centre, Anna University, Chennai (India); Kozakov, A.T. [Research Institute of Physics, Southern Federal University, Rostov-on-Don (Russian Federation); Pandian, R. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India); Chakravarty, S. [UGC-DAE CSR, Kalpakkam (India); Ravindran, T.R.; Dash, S.; Tyagi, A.K. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India)

    2015-01-01

    Graphical abstract: - Highlights: • Friction anisotropy in boronated graphite is observed in macroscopic sliding condition. • Low friction coefficient is observed in basal plane and becomes high in prismatic direction. • 3D phase of boronated graphite transformed into 2D structure after friction test. • Chemical activity is high in prismatic plane forming strong bonds between the sliding interfaces. - Abstract: Anisotropic friction behavior in macroscopic scale was observed in boronated graphite. Depending upon sliding speed and normal loads, this value was found to be in the range 0.1–0.35 in the direction of basal plane and becomes high 0.2–0.8 in prismatic face. Grazing-incidence X-ray diffraction analysis shows prominent reflection of (0 0 2) plane at basal and prismatic directions of boronated graphite. However, in both the wear tracks (1 1 0) plane become prominent and this transformation is induced by frictional energy. The structural transformation in wear tracks is supported by micro-Raman analysis which revealed that 3D phase of boronated graphite converted into a disordered 2D lattice structure. Thus, the structural aspect of disorder is similar in both the wear tracks and graphite transfer layers. Therefore, the crystallographic aspect is not adequate to explain anisotropic friction behavior. Results of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy shows weak signature of oxygen complexes and functional groups in wear track of basal plane while these species dominate in prismatic direction. Abundance of these functional groups in prismatic plane indicates availability of chemically active sites tends to forming strong bonds between the sliding interfaces which eventually increases friction coefficient.

  20. Preparation of MIP grafts for quercetin by tandem aryl diazonium surface chemistry and photopolymerization

    International Nuclear Information System (INIS)

    Salmi, Zakaria; Benmehdi, Houcine; Lamouri, Aazdine; Decorse, Philippe; Jouini, Mohamed; Chehimi, Mohamed M.; Yagci, Yusuf

    2013-01-01

    The food antioxidant quercetin was used as a template in an ultrathin molecularly imprinted polymer (MIP) film prepared by photopolymerization. Indium tin oxide (ITO) plates were electrografted with aryl layers via a diazonium salt precursor bearing two terminal hydroxyethyl groups. The latter act as hydrogen donors for the photosensitizer isopropylthioxanthone and enabled the preparation of MIP grafts through radical photopolymerization of methacrylic acid (the functional monomer) and ethylene glycol dimethacrylate (the crosslinker) in the presence of quercetin (the template) on the ITO. The template was extracted, and the remaining ITO electrode used for the amperometric determination of quercetin at a working potential of 0.26 V (vs. SCE). The analytical range is from 5.10 −8 to 10 −4 mol L −1 , and the detection limit is 5.10 −8 mol L −1 . (author)

  1. An endogenous aryl hydrocarbon receptor ligand inhibits proliferation and migration of human ovarian cancer cells.

    Science.gov (United States)

    Wang, Kai; Li, Yan; Jiang, Yi-Zhou; Dai, Cai-Feng; Patankar, Manish S; Song, Jia-Sheng; Zheng, Jing

    2013-10-28

    The aryl hydrocarbon receptor (AhR), a ligand-activated transcription factor mediates many biological processes. Herein, we investigated if 2-(1'H-indole-3'-carbonyl)-thiazole-4-carboxylic acid methyl ester (ITE, an endogenous AhR ligand) regulated proliferation and migration of human ovarian cancer cells via AhR. We found that AhR was widely present in many histotypes of ovarian cancer tissues. ITE suppressed OVCAR-3 cell proliferation and SKOV-3 cell migration in vitro, which were blocked by AhR knockdown. ITE also suppressed OVCAR-3 cell growth in mice. These data suggest that the ITE might potentially be used for therapeutic intervention for at least a subset of human ovarian cancer. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  2. Catalytic activity of some oxime-based Pd(II-complexes in Suzuki coupling of aryl and heteroaryl bromides in water

    Directory of Open Access Journals (Sweden)

    Kamal M. Dawood

    2017-05-01

    Full Text Available The catalytic activity of four Pd(II-complexes of benzoazole-oximes was extensively studied in Suzuki–Miyaura C–C cross coupling reactions in water, as an eco-friendly green solvent, under both thermal heating as well as microwave irradiation conditions. The cross-coupling reactions included different activated and deactivated aryl- or heteroaryl-bromides with several arylboronic acids. The protected oxime-complexes were found to be more efficient than the free ones.

  3. Differentiation in boron distribution in adult male and female rats' normal brain: A BNCT approach

    Energy Technology Data Exchange (ETDEWEB)

    Goodarzi, Samereh, E-mail: samere.g@gmail.com [Department of Nuclear Engineering, Science and Research Branch, Islamic Azad University, PO Box 19395-1943, Tehran (Iran, Islamic Republic of); Pazirandeh, Ali, E-mail: paziran@yahoo.com [Department of Nuclear Engineering, Science and Research Branch, Islamic Azad University, PO Box 19395-1943, Tehran (Iran, Islamic Republic of); Jameie, Seyed Behnamedin, E-mail: behnamjameie@tums.ac.ir [Basic Science Department, Faculty of Allied Medicine, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Department of Anatomy, Faculty of Medicine, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Baghban Khojasteh, Nasrin, E-mail: khojasteh_n@yahoo.com [Department of Nuclear Engineering, Science and Research Branch, Islamic Azad University, PO Box 19395-1943, Tehran (Iran, Islamic Republic of)

    2012-06-15

    Boron distribution in adult male and female rats' normal brain after boron carrier injection (0.005 g Boric Acid+0.005 g Borax+10 ml distilled water, pH: 7.4) was studied in this research. Coronal sections of control and trial animal tissue samples were irradiated with thermal neutrons. Using alpha autoradiography, significant differences in boron concentration were seen in forebrain, midbrain and hindbrain sections of male and female animal groups with the highest value, four hours after boron compound injection. - Highlights: Black-Right-Pointing-Pointer Boron distribution in male and female rats' normal brain was studied in this research. Black-Right-Pointing-Pointer Coronal sections of animal tissue samples were irradiated with thermal neutrons. Black-Right-Pointing-Pointer Alpha and Lithium tracks were counted using alpha autoradiography. Black-Right-Pointing-Pointer Different boron concentration was seen in brain sections of male and female rats. Black-Right-Pointing-Pointer The highest boron concentration was seen in 4 h after boron compound injection.

  4. Effect of boron on fruit quality in pineapple

    Science.gov (United States)

    Wei, Changbin; Ma, Zhiling; Liu, Yuge; Qiao, Jian; Sun, Guangming

    2018-04-01

    Boron (B) is an important element for the plant. The aim of work was to study the effect of B on fruit quality of pineapple. The experiment was carried out with `Comte de paris' variety in pots. The results demonstrated that B had positive effect on fruit weight, TSS, the ratio of TSS/acidity, Vitamin C, the content of aroma volatile compounds. The B had no effect on the content of the three sugars (sucrose, fructose and glucose) and titrable acidity. There was a positive effect on fruit quality by application of B fertilizer in production of pineapple.

  5. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

    Science.gov (United States)

    Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

    2009-01-01

    The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233

  6. Evaluation of selective boron absorption in liver tumors

    International Nuclear Information System (INIS)

    Chiaraviglio, D.; Grazia, F. De; Zonta, A.; Altieri, S.; Pedroni, P.; Braghieri, B.; Fossati, F.; Pinelli, T.; Perotti, A.; Specchiarello, S.; Perlini, G.; Rief, H.

    1988-01-01

    The first step was a pharmacokinetic study to identify substances which are good boron transporters and are therefore able to provide a high concentration of the nuclide with respect to the healthy hepatic tissue in the MHN. For this purpose the tumor M5076/73 (M5), which matastasizes spontaneously in liver, was inoculated subcutaneously in a group of C57B1/6 mice. Thirty days after the inoculation, when 90% of the liver was invaded by metastases, a boric acid 0.3 M solution enriched to 96% 10 B was injected into the caudal vein. The mice were sacrificed and the liver was frozen for measurements. Boron concentration in the various samples was achieved by measuring the energy distribution of α particles produced in the nuclear reaction 10 B(n, α) 7 Li induced by a thermal neutron beam extracted from the Triga Mark II reactor,

  7. Helium diffusion in irradiated boron carbide

    International Nuclear Information System (INIS)

    Hollenberg, G.W.

    1981-03-01

    Boron carbide has been internationally adopted as the neutron absorber material in the control and safety rods of large fast breeder reactors. Its relatively large neutron capture cross section at high neutron energies provides sufficient reactivity worth with a minimum of core space. In addition, the commercial availability of boron carbide makes it attractive from a fabrication standpoint. Instrumented irradiation experiments in EBR-II have provided continuous helium release data on boron carbide at a variety of operating temperatures. Although some microstructural and compositional variations were examined in these experiments most of the boron carbide was prototypic of that used in the Fast Flux Test Facility. The density of the boron carbide pellets was approximately 92% of theoretical. The boron carbide pellets were approximately 1.0 cm in diameter and possessed average grain sizes that varied from 8 to 30 μm. Pellet centerline temperatures were continually measured during the irradiation experiments

  8. Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.; Ramaprabhu, S., E-mail: ramp@iitm.ac.in

    2015-01-15

    Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework with an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.

  9. Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

    International Nuclear Information System (INIS)

    Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.; Ramaprabhu, S.

    2015-01-01

    Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework with an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g −1 at 100 mA g −1 after 30th cycles. At high current density value of 1 A g −1 , B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states

  10. Comparison of the Level of Boron Concentrations in Black Teas with Fruit Teas Available on the Polish Market

    Directory of Open Access Journals (Sweden)

    Anetta Zioła-Frankowska

    2014-01-01

    Full Text Available The determination of boron by inductively coupled plasma-atomic emission spectrometry has been carried in water-soluble and acid soluble (total content fractions of 36 samples of traditional black tea and fruit brew. The estimation of the impact of the type of tea on the concentration of boron in water-soluble and acid extracts and potential human health risk from the daily intake of boron was carried out in this study. The levels of boron differed significantly in black and fruit tea types. The mean total content of boron ranged from 8.31 to 18.40 mg/kg in black teas, from 12.85 to 15.13 mg/kg in black tea with fruit flavor, and from 12.09 to 22.77 mg/kg in fruit brews. The degree of extraction of boron in black tea ranged from 8% to 27% and for fruit tea from 17% to 69%. In addition, the values below 25% were of black teas with fruit flavors. The daily intake of B from tea infusions (three cups/day is still within the average daily intake except for some of the fruit brews which exceed acceptable regulations of the daily intake of total boron by humans. Hence, it may not produce any health risks for human consumption, if other sources of metal contaminated food are not taken at the same time.

  11. Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.

  12. Boron removal efficiency from Red Sea water using different SWRO/BWRO membranes

    KAUST Repository

    Rahmawati, Karina; Ghaffour, NorEddine; Aubry, Cyril; Amy, Gary L.

    2012-01-01

    Seawater reverse osmosis (SWRO) desalination process provides high quality of fresh water. However, due to some operational constraints mainly scaling control some trace contaminant removal, such as acceptable boron concentration, cannot be achieved in a single pass SWRO system. The objective of this study was to investigate the efficiency of five difference reverse osmosis (RO) membranes (seawater SW and brackish water BW) provided by different manufacturers for boron removal. RO experiments using pretreated real Red Sea water were conducted in parallel to compare membrane performance under the same operating conditions. As expected, results showed that boron rejection increased as the feed pH increased. This was caused by dissociation of boric acid to negatively charged borate ions and more negatively charged membrane surface at elevated pH which enhanced boron rejection. Single pass RO system, with and without elevating the pH, may not be sufficient for two reasons. First, boron concentration in permeate does not fulfill local regulations (<0.5ppm). Second, severe scaling occurs due to operation in alkaline condition, since Ca 2+ and Mg 2+ concentrations are still high to cause salts precipitation. Techno-economical study was performed to select the best configuration and membrane giving the highest performance in terms of boron and TDS rejections and energy consumption. © 2012 Elsevier B.V.

  13. Determination of Boron in soils and plants samples using spectrophotometric method

    International Nuclear Information System (INIS)

    Stas, J.; Hariri, Z.

    2011-10-01

    In this work, the concentration of boron in soil and plant samples was determined with UV-vis spectrophotometer by using azomethine-H as a complex reagent. The calibration curve for boron determination in the range of (0μ3 g.mL - 1) was constructed by plotting the measured absorption of the yellow azomethine-H-B complex at λmax = 412.6 nm against boron concentration in the aqueous phase. The detection limit, repeatability limit, intermediate precision, accuracy, and recovery coefficient of this method were calculated and found to be 0.021 μg.mL - 1, 0.335% , 0.81%, 2.93%, (98.4-101.5)% respectively. The influence of some foreign ions on the determination of boron were also investigated in detail, most of the studied ions, like iron, iodide, and calcium can be tolerated within the ranges of (20-35μg.mL-1), (3000-5000μg.mL - 1) , (15000-30000μg.mL - 1) respectively. This is due to the fact, that ascorbic acid and EDTA in the buffer masking reagent reaction system can be very effective in masking these ions. This method was found to be economic and suitable for boron determination in standard and local samples (soil, plant) and requires small amount of sample (1g). This method can also be applied for boron determination in water samples (drinking and industrial waste water).(author)

  14. Study of boron behaviour in two Spanish coal combustion power plants.

    Science.gov (United States)

    Ochoa-González, Raquel; Cuesta, Aida Fuente; Córdoba, Patricia; Díaz-Somoano, Mercedes; Font, Oriol; López-Antón, M Antonia; Querol, Xavier; Martínez-Tarazona, M Rosa; Giménez, Antonio

    2011-10-01

    A full-scale field study was carried out at two Spanish coal-fired power plants equipped with electrostatic precipitator (ESP) and wet flue gas desulfurisation (FGD) systems to investigate the distribution of boron in coals, solid by-products, wastewater streams and flue gases. The results were obtained from the simultaneous sampling of solid, liquid and gaseous streams and their subsequent analysis in two different laboratories for purposes of comparison. Although the final aim of this study was to evaluate the partitioning of boron in a (co-)combustion power plant, special attention was paid to the analytical procedure for boron determination. A sample preparation procedure was optimised for coal and combustion by-products to overcome some specific shortcomings of the currently used acid digestion methods. In addition boron mass balances and removal efficiencies in ESP and FGD devices were calculated. Mass balance closures between 83 and 149% were obtained. During coal combustion, 95% of the incoming boron was collected in the fly ashes. The use of petroleum coke as co-combustible produced a decrease in the removal efficiency of the ESP (87%). Nevertheless, more than 90% of the remaining gaseous boron was eliminated via the FGD in the wastewater discharged from the scrubber, thereby causing environmental problems. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Coupling of dextrans conjugated with boron to gamma globulin: a model for NCT

    International Nuclear Information System (INIS)

    Elmore, J.J. Jr.; Borg, D.C.; Micca, P.; Gabel, D.

    1983-01-01

    Our project is to meet more effectively the well known primary requirement for treatment with boron-10 neutron capture therapy (NCT): namely, the selective localization of a sufficient amount of boron in or on target cells. Monoclonal antibodies (MCA) to tumor-associated antigens are attractive targeting carriers for boron-10 in terms of the needed selective localization. However the densities of surface receptors on tumor cells have seemed deficient to achieve successful NCT. If one seeks the necessary radiotherapeutic ratios by increasing the numbers of boron atoms or carborane cages bound per MCA, then inactivation of the antibody can occur through loss of receptor specificity and/or by precipitation of the protein. To achieve the goal of overcoming the limitations of antibody binding capacity, we have elected to use water-soluble dextrans as intermediate carriers. This permits each MCA molecule to target many atoms of boron-10 to the specified antigenic receptors while only 5 to 10 of the amino acid residues of the protein are conjugated by dextrans carrying boron-10

  16. Removal of boron(III) by N-methylglucamine-type cellulose derivatives with higher adsorption rate

    International Nuclear Information System (INIS)

    Inukai, Yoshinari; Tanaka, Yoshiharu; Matsuda, Toshio; Mihara, Nobutake; Yamada, Kouji; Nambu, Nobuyoshi; Itoh, Osamu; Doi, Takao; Kaida, Yasuhiko; Yasuda, Seiji

    2004-01-01

    To obtain adsorbents for boron(III) derived from a natural polymer, two forms (powder and fiber) of N-methylglucamine-type cellulose derivatives were newly synthesized. After the graft polymerization of two forms of cellulose with vinyl monomer having epoxy groups, the N-methylglucamine-type cellulose derivatives were obtained by the reaction of the grafted cellulose with N-methylglucamine. The adsorption capacities of the cellulose derivatives for boron(III) were the same levels as that of a commercially available N-methylglucamine-type polystyrene resin. However, the cellulose derivatives adsorbed boron(III) more quickly than the polystyrene resin. The adsorption and desorption of boron(III) with a column method using the cellulose fiber were achieved at a higher flow rate than that using the polystyrene resin. In addition, the boron(III), adsorbed on the cellulose fiber column, was quantitatively recovered with dilute hydrochloric acid in 20- and 200-fold increased concentrations. Consequently, it was found that the cellulose derivatives were superior to the polystyrene resin as adsorbents for boron(III) for treatment of a large quantity of wastewater

  17. Determination of trace amounts of boron in steel by high frequency plasma torch spectrometry

    International Nuclear Information System (INIS)

    Akiyoshi, Takanori; Tsukamoto, Takako

    1978-01-01

    Trace amount of boron in steel were determined by means of emission spectrometry using high frequency plasma torch. The sensitivity of this method depended on the kind of solvent used, and methyl alcohol gave the best sensitivity. The determination limit of boron in methanol was 0.002 μg/ml. The established method utilized the high sensibility of the plasma torch and the easy distillation of boron in methanol as trimethyl-borate (B(OCH 3 ) 3 ). The sample was dissolved by acids and dehydrated by hot H 2 SO 4 and H 3 Po 4 . After cooling and addition of methanol (60 ml), the solution was distilled to obtain 40 ml of the distillate. The amount of boron in the distillate was determined by the intensity of the spectral line of B 2497.73 A excited by plasma torch. This method was rapid and accurate, particularly in determining trace amounts of boron and the determination range of boron in steel was 0.2 to 150 ppm. This method was also appliciable to stainless steels and other alloys. (auth.)

  18. Boron removal efficiency from Red Sea water using different SWRO/BWRO membranes

    KAUST Repository

    Rahmawati, Karina

    2012-12-01

    Seawater reverse osmosis (SWRO) desalination process provides high quality of fresh water. However, due to some operational constraints mainly scaling control some trace contaminant removal, such as acceptable boron concentration, cannot be achieved in a single pass SWRO system. The objective of this study was to investigate the efficiency of five difference reverse osmosis (RO) membranes (seawater SW and brackish water BW) provided by different manufacturers for boron removal. RO experiments using pretreated real Red Sea water were conducted in parallel to compare membrane performance under the same operating conditions. As expected, results showed that boron rejection increased as the feed pH increased. This was caused by dissociation of boric acid to negatively charged borate ions and more negatively charged membrane surface at elevated pH which enhanced boron rejection. Single pass RO system, with and without elevating the pH, may not be sufficient for two reasons. First, boron concentration in permeate does not fulfill local regulations (<0.5ppm). Second, severe scaling occurs due to operation in alkaline condition, since Ca 2+ and Mg 2+ concentrations are still high to cause salts precipitation. Techno-economical study was performed to select the best configuration and membrane giving the highest performance in terms of boron and TDS rejections and energy consumption. © 2012 Elsevier B.V.

  19. Linear titration plot for the determination of boron in the primary coolant of a pressurized water reactor

    International Nuclear Information System (INIS)

    Midgley, D.; Gatford, C.

    1992-01-01

    A linear titration plot method has been devised for the determination of boron as boric acid in partly neutralized solution, such as occurs in the primary coolant of pressurized water reactors. The total boron and the alkali in the sample are determined simultaneously. Although it is not essential to add mannitol in this method, it is more accurate when the solution is saturated with mannitol. Comparisons are made with other modes of titration: Gran plots, first and second differential potentiometric titrations and indicator titrations. None of these gives the total boron directly in partly neutralized solutions. (author)

  20. Primary system boron dilution analysis

    International Nuclear Information System (INIS)

    Crump, R.J.; Naretto, C.J.; Borgen, R.A.; Rockhold, H.C.

    1978-01-01

    The results are presented for an analysis conducted to determine the potential paths through which nonborated water or water with insufficient boron concentration might enter the LOFT primary coolant piping system or reactor vessel to cause dilution of the borated primary coolant water. No attempt was made in the course of this analysis to identify possible design modifications nor to suggest changes in administrative procedures or controls

  1. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  2. Boron neutron capture therapy of glioblastoma multiforme using the p- boronophenylalanine-fructose complex and epithermal neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Coderre, J.A.; Chanana, A.D.; Joel, D.D.; Liu, H.B.; Slatkin, D.N.; Wielopolski, L. [Brookhaven National Lab., Upton, NY (United States); Bergland, R.; Elowitz, E. [Beth Israel Medical Center, New York, NY (United States). Dept. of Neurosurgery; Chadha, M. [Beth Israel Medical Center, New York, NY (United States). Dept. of Radiation Oncology

    1994-12-31

    The amino acid analogue p-boronophenylalanine (BPA) is under investigation as a neutron capture agent for BNCT of glioblastoma multiforme. A series of patients undergoing surgical removal of tumor received BPA orally as the free amino acid. Favorable tumor/blood boron concentration ratios were obtained but the absolute amount of boron in the tumor would have been insufficient for BNCT. BPA can be solubilized at neutral pH by complexation with fructose (BPA-F). Studies with rats suggest that intraperitoneal injection of BPA-F complex produces a much higher tumor boron concentration to rat intracerebral 9L gliosarcoma that were possible with oral BPA. Higher boron concentrations have allowed higher tumor radiation doses to be delivered while maintaining the dose to the normal brain vascular endothelium below the threshold of tolerance. The experience to date of the administration of BPA-F to one patient is provided in this report.

  3. Boron neutron capture therapy of glioblastoma multiforme using the p- boronophenylalanine-fructose complex and epithermal neutrons

    International Nuclear Information System (INIS)

    Coderre, J.A.; Chanana, A.D.; Joel, D.D.; Liu, H.B.; Slatkin, D.N.; Wielopolski, L.; Bergland, R.; Elowitz, E.; Chadha, M.

    1994-01-01

    The amino acid analogue p-boronophenylalanine (BPA) is under investigation as a neutron capture agent for BNCT of glioblastoma multiforme. A series of patients undergoing surgical removal of tumor received BPA orally as the free amino acid. Favorable tumor/blood boron concentration ratios were obtained but the absolute amount of boron in the tumor would have been insufficient for BNCT. BPA can be solubilized at neutral pH by complexation with fructose (BPA-F). Studies with rats suggest that intraperitoneal injection of BPA-F complex produces a much higher tumor boron concentration to rat intracerebral 9L gliosarcoma that were possible with oral BPA. Higher boron concentrations have allowed higher tumor radiation doses to be delivered while maintaining the dose to the normal brain vascular endothelium below the threshold of tolerance. The experience to date of the administration of BPA-F to one patient is provided in this report

  4. Boron removal from geothermal waters by electrocoagulation

    Energy Technology Data Exchange (ETDEWEB)

    Yilmaz, A. Erdem [Atatuerk University, Faculty of Engineering, Department of Environmental Engineering., 25240 Erzurum (Turkey)], E-mail: aerdemy@atauni.edu.tr; Boncukcuoglu, Recep [Atatuerk University, Faculty of Engineering, Department of Environmental Engineering., 25240 Erzurum (Turkey); Kocakerim, M. Muhtar [Atatuerk University, Faculty of Engineering, Department of Chemical Engineering, 25240 Erzurum (Turkey); Yilmaz, M. Tolga; Paluluoglu, Cihan [Atatuerk University, Faculty of Engineering, Department of Environmental Engineering., 25240 Erzurum (Turkey)

    2008-05-01

    Most of the geothermal waters in Turkey contain extremely high concentration of boron when they are used for irrigation. The use of geothermal waters for irrigation can results in excess amount deposition of boron in soil. On the other hand, a minimal boron concentration is required for irrigational waters. In this study, electrocoagulation (EC) was selected as a treatment process for the removal of boron from thermal waters obtained from Ilica-Erzurum in Turkey. Current density (CD), pH of solution and temperature of solution were selected as operational parameters. The results showed that boron removal efficiency increased from pH 4.0 to 8.0 and decreased at pH 10.0. Although boron removal efficiency was highest at pH 8.0, energy consumption was very high at this pH value compared to other pH intervals. Boron removal efficiency reached to 95% with increasing current density from 1.5 to 6.0 mA/cm{sup 2}, but energy consumption was also increased in this interval. At higher temperatures of solution, such as 313 and 333 K, boron removal efficiency increased. At optimum conditions, boron removal efficiency in geothermal water reached up to 95%.

  5. Boron removal from geothermal waters by electrocoagulation

    International Nuclear Information System (INIS)

    Yilmaz, A. Erdem; Boncukcuoglu, Recep; Kocakerim, M. Muhtar; Yilmaz, M. Tolga; Paluluoglu, Cihan

    2008-01-01

    Most of the geothermal waters in Turkey contain extremely high concentration of boron when they are used for irrigation. The use of geothermal waters for irrigation can results in excess amount deposition of boron in soil. On the other hand, a minimal boron concentration is required for irrigational waters. In this study, electrocoagulation (EC) was selected as a treatment process for the removal of boron from thermal waters obtained from Ilica-Erzurum in Turkey. Current density (CD), pH of solution and temperature of solution were selected as operational parameters. The results showed that boron removal efficiency increased from pH 4.0 to 8.0 and decreased at pH 10.0. Although boron removal efficiency was highest at pH 8.0, energy consumption was very high at this pH value compared to other pH intervals. Boron removal efficiency reached to 95% with increasing current density from 1.5 to 6.0 mA/cm 2 , but energy consumption was also increased in this interval. At higher temperatures of solution, such as 313 and 333 K, boron removal efficiency increased. At optimum conditions, boron removal efficiency in geothermal water reached up to 95%

  6. Removal of boron (B) from waste liquors.

    Science.gov (United States)

    Jiang, J Q; Xu, Y; Simon, J; Quill, K; Shettle, K

    2006-01-01

    This paper explores the use of electrocoagulation to remove boron from waste effluent in comparison with alum coagulation. In treating model test wastes, greater boron removals were achieved with electrocoagulation at low doses than conventional alum coagulation when reaction was undertaken for the same conditions (pH 8.5, and initial boron concentration was 500 mg/L). Al electrocoagulation can achieve good boron removal performance (68.3%) at a dose of 2.1 (as molar ratio of Al:B, and for current density of 62.1 A/m2), while alum coagulation can only achieve the maximum boron removal of 56% at a dose of 2.4. Also, Al electrocoagulation can remove 15-20% more boron than alum coagulation for the same dose compared in the treatment of both model test wastes and industry effluent. The estimation of running costs shows that to achieve 75% boron removal from industry waste effluent, i.e. removing 150 g of boron from 1 m3 of effluent, electrocoagulation was 6.2 times cheaper than alum coagulation. The economic advantage of electrocoagulation in the treatment of boron-containing waste effluent is thus significant.

  7. Quantitative evaluation of boron neutron capture therapy (BNCT) drugs for boron delivery and retention at subcellular scale resolution in human glioblastoma cells with imaging secondary ion mass spectrometry (SIMS)

    Science.gov (United States)

    Chandra, S.; Ahmad, T.; Barth, R. F.; Kabalka, G. W.

    2014-01-01

    Boron neutron capture therapy (BNCT) of cancer depends on the selective delivery of a sufficient number of boron-10 (10B) atoms to individual tumor cells. Cell killing results from the 10B (n, α)7Li neutron capture and fission reactions that occur if a sufficient number of 10B atoms are localized in the tumor cells. Intranuclear 10B localization enhances the efficiency of cell killing via damage to the DNA. The net cellular content of 10B atoms reflects both bound and free pools of boron in individual tumor cells. The assessment of these pools, delivered by a boron delivery agent, currently cannot be made at subcellular scale resolution by clinically applicable techniques such as PET and MRI. In this study, secondary ion mass spectrometry (SIMS) based imaging instrument, a CAMECA IMS 3f ion microscope, capable of 500 nm spatial resolution was employed. Cryogenically prepared cultured human T98G glioblastoma cells were evaluated for boron uptake and retention of two delivery agents. The first, L-p-boronophenylalanine (BPA), has been used clinically for BNCT of high grade gliomas, recurrent tumors of the head and neck region and melanomas. The second, a boron analogue of an unnatural amino acid, 1-amino-3-borono-cyclopentanecarboxylic acid (cis-ABCPC), has been studied in rodent glioma and melanoma models by quantification of boron in the nucleus and cytoplasm of individual tumor cells. The bound and free pools of boron were assessed by exposure of cells to boron-free nutrient medium. Both BPA and cis-ABCPC delivered almost 70% of the pool of boron in the free or loosely bound form to the nucleus and cytoplasm of human glioblastoma cells. This free pool of boron could be easily mobilized out of the cell and was in some sort of equilibrium with extracellular boron. In the case of BPA, the intracellular free pool of boron also was affected by the presence of phenylalanine in the nutrient medium. This suggests that it might be advantageous if patients were placed on a

  8. The application of FEL-EXPERT system in the interpretation of boron compounds toxicity

    International Nuclear Information System (INIS)

    Strouf, O.; Marik, V.

    1990-01-01

    The effect of substructural features of boron compounds on their toxicity (LD 50 , mice, i.p.) was studied using the FEL-EXPERT system developed by the Czech Technical University of Prague. A set of 108 compounds containing one or two boron atoms in their molecule was arbitrarily divided into three classes: compounds with high toxicity (LD 50 50 50 ≥1000 mg/kg). The compounds were represented by 70 substructural fragments, 27 of them being ''central substructures'' containing boron atom(s). The inference net consisted of 118 nodes (74 of the Bayesian type), 362 production rules and 74 context links. The total classification correctness was 98%. As a case-study, the classification of p-tolylboronic acid (LD 50 =520 mg/kg) and 4-carboxyphenylboronic acid (LD 50 =3838 mg/kg) was discussed. 4 figs., 2 tabs., 11 refs

  9. In silico characterization of boron transporter (BOR1 protein sequences in Poaceae species

    Directory of Open Access Journals (Sweden)

    Ertuğrul Filiz

    2013-01-01

    Full Text Available Boron (B is essential for the plant growth and development, and its primary function is connected with formation of the cell wall. Moreover, boron toxicity is a shared problem in semiarid and arid regions. In this study, boron transporter protein (BOR1 sequences from some Poaceae species (Hordeum vulgare subsp. vulgare, Zea mays, Brachypodium distachyon, Oryza sativa subsp. japonica, Oryza sativa subsp. indica, Sorghum bicolor, Triticum aestivum were evaluated by bioinformatics tools. Physicochemical analyses revealed that most of BOR1 proteins were basic character and had generally aliphatic amino acids. Analysis of the domains showed that transmembrane domains were identified constantly and three motifs were detected with 50 amino acids length. Also, the motif SPNPWEPGSYDHWTVAKDMFNVPPAYIFGAFIPATMVAGLYYFDHSVASQ was found most frequently with 25 repeats. The phylogenetic tree showed divergence into two main clusters. B. distachyon species were clustered separately. Finally, this study contributes to the new BOR1 protein characterization in grasses and create scientific base for in silico analysis in future.

  10. Determination of boron in waters by using methyl borate generation and flame atomic-emission spectrometry

    International Nuclear Information System (INIS)

    Castillo, J.R.; Mir, J.M.; Martinez, C.; Bendicho, C.

    1985-01-01

    An improved method is proposed for the determination of boron in waters. The esterification reaction between boric acid and methanol in a concentrated sulphuric acid medium and the vaporisation of the methyl borate formed (boiling-point, 68 C) are used in the determination by boron by measuring the emission of the BO 2 radical at 548 nm. This reaction is carried out in a simple and inexpensive generator, designed for this purpose, and the heat developed in it causes the rapid volatilisation of the methyl borate. Thus no collection systems or carrier gas are required. The proposed method gives an improved detection limit and it can be applied to the determination of boron in water samples. It is both rapid and highly selective. (author)

  11. CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO_2 at room temperature

    International Nuclear Information System (INIS)

    Yu, B.; Yang, Z.Z.; Zhao, Y.F.; Zhang, H.Y.; Yang, P.; Gao, X.; Liu, Z.M.

    2017-01-01

    A CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO_2 in the presence of trimethylsilylacetylene was developed to give functionalized propiolic acid products at room temperature. A wide range of propiolic acids bearing functional groups was successfully obtained in good to excellent yields. Mechanistic studies demonstrate that in the carboxylation process the alkynyl-silane intermediate was first in situ generated, which was then trapped by CO_2, giving rise to the corresponding functionalized propiolic acids after acidification. The advantages of this approach include avoiding use of transition-metal catalysts, wide substrate scope together with excellent functional group tolerance, ambient conditions and a facile work-up procedure. (authors)

  12. Polyvinylpolypyrrolidone-Supported Boron Trifluoride; Highly Efficient Catalyst for the Synthesis of N-tert-Butyl Amides

    Directory of Open Access Journals (Sweden)

    Masoud Mokhtary

    2012-01-01

    Full Text Available Highly efficient method for the preparation of N-tert-butyl amides by reaction of nitriles with tert-butyl acetate is described using polyvinylpolypyrrolidone-supported boron trifluoride (PVPP-BF3 at 70°C in good to excellent yields. Selective amidation of benzonitrile in the presence of acetonitrile was also achieved. polyvinylpolypyrrolidone-boron trifluoride complex shows non-corrosive and stable solid catalyst elevated Lewis acid property.

  13. Functionalized carbon nanofibers as solid acid catalysts for transesterification

    NARCIS (Netherlands)

    Stellwagen, D.R.; van der Klis, Frits; van Es, D.S.; de Jong, K.P.; Bitter, J.H.

    2013-01-01

    Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient

  14. Functionalized carbon nanofibers as solid-acid catalysts for transesterification

    NARCIS (Netherlands)

    Stellwagen, D.R.; Klis, van der F.; Es, van D.S.; Jong, de K.P.; Bitter, J.H.

    2013-01-01

    Carbon nanofibers (CNFs) were functionalized with aryl sulfonic acid groups using in situ diazonium coupling. The use of diazonium coupling yielded an acidic carbon material, in which the introduced acidic groups are readily accessible to the triglyceride substrate. The material is an efficient

  15. Conversion of Aryl Iodides into Aryliodine(III Dichlorides by an Oxidative Halogenation Strategy Using 30% Aqueous Hydrogen Peroxide in Fluorinated Alcohol

    Directory of Open Access Journals (Sweden)

    Ajda Podgoršek

    2010-04-01

    Full Text Available Oxidative chlorination with HCl/H2O2 in 1,1,1-trifluoroethanol was used to transform aryl iodides into aryliodine(III dihalides. In this instance 1,1,1-trifluoroethanol is not only the reaction medium, but is also an activator of hydrogen peroxide for the oxidation of hydrochloric acid to molecular chlorine. Aryliodine(III dichlorides were formed in 72–91% isolated yields in the reaction of aryl iodides with 30% aqueous hydrogen peroxide and hydrochloric acid at ambient temperature. A study of the effect that substituents on the aromatic ring have on the formation and stability of aryliodine(III dichlorides shows that the transformation is easier to achieve in the presence of the electron-donating groups (i.e. methoxy, but in this case the products rapidly decompose under the reported reaction conditions to form chlorinated arenes. The results suggest that oxidation of hydrogen chloride with hydrogen peroxide is the initial reaction step, while direct oxidation of aryl iodide with hydrogen peroxide is less likely to occur.

  16. Synthesis of nanodispersible 6-aryl-2,4-diamino-1,3,5-triazine and its derivatives

    International Nuclear Information System (INIS)

    Padalkar, Vikas S.; Patil, Vikas S.; Phatangare, Kiran R.; Gupta, Vinod D.; Umape, Prashant G.; Sekar, N.

    2010-01-01

    A series of novel branched derivatives of 6-aryl-2,4-diamino-1,3,5-triazine from corresponding aryl nitriles and dicyanodiamide was synthesized. These compounds show a nanodispersibility and good thermal stability.

  17. Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

    Science.gov (United States)

    Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

    2018-06-29

    The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes.

    Science.gov (United States)

    Akai, Junichiro; Watanabe, Satoshi; Michikawa, Kumiko; Harada, Toshiro

    2017-07-07

    A 3-aryl H 8 -BINOL was grafted on the surface of silica gel using a hydrosilane derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(O i Pr) 4 . The reactions using Et 2 Zn, Et 3 B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable deterioration of the activity.

  19. Analysis of diverse direct arylation polymerization (DArP) conditions toward the efficient synthesis of polymers converging with stille polymers in organic solar cells

    DEFF Research Database (Denmark)

    Livi, Francesco; Gobalasingham, Nemal S.; Thompson, Barry C.

    2016-01-01

    Despite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross-coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation...... for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C-H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5-bis...... was synthesized in superheated THF with Cs2CO3, neodecanoic acid, and P(o-anisyl)3, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO-free and spin-coated ITO devices....

  20. Synthesis and conformational analysis of new arylated-diphenylurea derivatives related to sorafenib drug via Suzuki-Miyaura cross-coupling reaction

    Science.gov (United States)

    Al-Masoudi, Najim A.; Essa, Ali Hashem; Alwaaly, Ahmed A. S.; Saeed, Bahjat A.; Langer, Peter

    2017-10-01

    Sorafenib, is a relatively new cytostatic drug approved for the treatment of renal cell and hepatocellular carcinoma. The development of new sorafenib analogues offers the possibility of generating structures of increased potency. To this end, a series of arylated-diphenylurea analogues 17-31 were synthesized via Suzuki-Miyaura coupling reaction, related to sorafenib by treatment of three diarylureas 2-4 having 3-bromo, 4-chloro and 2-iodo groups with various arylboronic acids. Conformational analysis of the new arylated urea analogues has been investigated using MOPAC 2016 of semi empirical PM7 Hamiltonian computational method. Our results showed that all compounds preferred the trans-trans conformations. Compound 17 has been selected to calculate the torsional energy profiles for rotation around the urea bonds and found to be existed predominantly in the trans-trans conformation with only very minimal fluctuation in conformation.

  1. A technique to prepare boronated B72.3 monoclonal antibody for boron neutron capture therapy

    International Nuclear Information System (INIS)

    Ranadive, G.N.; Rosenzweig, H.S.; Epperly, M.W.

    1993-01-01

    B72.3 monoclonal antibody has been successfully boronated using mercaptoundecahydro-closo-dodecaborate (boron cage compound). The reagent was incorporated by first reacting the lysine residues of the antibody with m-maleimidobenzoyl succinimide ester (MBS), followed by Michael addition to the maleimido group by the mercapto boron cage compound to form a physiologically stable thioether linkage. Boron content of the antibody was determined by atomic absorption spectroscopy. For biodistribution studies, boronated antibody was radioiodinated with iodogen. 125 I-labeled and boronated B72.3 monoclonal antibody demonstrated clear tumor localization when administered via tail vein injections to athymic nude mice bearing LS174-T tumor xenografts. Boronated antibody was calculated to deliver 10 6 boron atoms per tumor cell. Although this falls short of the specific boron content originally proposed as necessary for boron neutron capture therapy (BNCT), recent calculations suggest that far fewer atoms of 10 B per tumor cell would be necessary to effect successful BNCT when the boron is targeted to the tumor cell membrane. (author)

  2. Automatic chemical analysis of traces of boron in steel

    International Nuclear Information System (INIS)

    Ono, Akihiro; Yamaguchi, Naoharu; Matsumoto, Ryutaro

    1976-01-01

    The analyzer is composed of a sample changer, reagent addition devices, a distillation vessel, a color reaction vessel, a spectrophotometer, a controller, etc. The automatic procedure is performed according to the predetermined distillation and color reaction programs after dissolving 0.5 g of steel sample in aqua regia and fuming with sulfuric acid-phosphoric acid. The sample solution on the sample changer is transferred into the distillation vessel, where boron is distilled with methyl alcohol by heating and aeration. The distillate is collected in the distillate vessel, and a 1/2 aliquot is transferred into the color reaction vessel with small amounts of water. After the addition of glacial acetic acid and propionic anhydride, the distillate is circulated through the circulating pipe which is composed of an air blowing tube, a bubble remover, a flow cell and a drain valve. Oxalyl chloride (to eliminate water), sulfuric acid, the curcumin reagent (to form the boron complex) and an acetate buffer are added, and the absorbance of the solution is measured at 545 nm. The analytical results of steel samples were in good agreement with those obtained by the conventional method and with certified values. (auth.)

  3. Contamination of the ground waters and surface waters by boron in Lerma Valley, NW-Argentina - an inventory

    International Nuclear Information System (INIS)

    Bundschuh, J.

    1992-01-01

    Ground- and surface waters in areas unaffected by pollution from borax and boric acid producing plants exhibit low boron concentrations of less than 300 μg B/l. Only at the boric acid plant 'Mineratea' is the groundwater contaminated, with up to 6200 μg B/l occurring within an area of 8 to 10 km 2 with more than 1000 μg boron/l. Even higher boron concentrations (up to 18 μg B/l) are present in polluted surface waters. Not the boron concentration in the irrigation water, but the absolute amount of boron added to the plants by irrigation is what determines plant toxicity. For the contaminated area of the boric acid 'Mineratea', characterized by boron concentrations of between 1000 and 6000 μg B/l, the maximal amounts of irrigation water that can be applied lies between 300 and 8 mm. In order to protect the local groundwater resoures from present and future contamination, environmental impact assessment on industrial projects in the area are required. In this way, the quality of the drinking and irrigation water can be guaranteed through suitable measures, without hindering further necessary industrial development of the region. (orig./UWA) [de

  4. Danburite decomposition by sulfuric acid

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

    2011-01-01

    Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

  5. Spectrophotometric determination of microamounts of boron in water

    International Nuclear Information System (INIS)

    Weber de D'Alessio, Ana; Guido, O.O.; Bandin, N.A.

    1980-01-01

    A fast method of boron in water determination has been studied for the 0.5 .- 2 μg ml -1 concentration range. The procedure is based on the formation of a coloured complex of the tetrafluoroborate of a thionine derivate cation, its extraction by an organic solvent and the further absorptiometric measurement in such media. Methylene blue and azur C were comparatively tested as organic reagents, with 1.2-dichloroethane as the extractant. The absorbance was measured at the maximum (658 nm). The tetrafluoroboric acid formation was reached in 20 min on a water-bath kept at 60 deg C. The sensitivity with methylene blue was higher than with azur C. The molar absorptivities were 65,000 and 38,000 (l mol -1 cm -1 ) respectively. For a boron concentration of 0.1 μg ml -1 the relative standard deviation was 9% for methylene blue and 7% for azur C. The procedure is applicable to the control of boron traces in heavy water of nuclear reactors refrigerating loops. (author) [es

  6. Termite Resistance of MDF Panels Treated with Various Boron Compounds

    Directory of Open Access Journals (Sweden)

    Sedat Ondaral

    2009-06-01

    Full Text Available In this study, the effects of various boron compounds on the termite resistance of MDF panels were evaluated. Either borax (BX, boric acid (BA, zinc borate (ZB, or sodium perborate tetrahydrate (SPT were added to urea-formaldehyde (UF resin at target contents of 1%, 1.5%, 2% and 2.5% based on dry fiber weight. The panels were then manufactured using 12% urea-formaldehyde resin and 1% NH4Cl. MDF samples from the panels were tested against the subterranean termites, Coptotermes formosanus Shiraki. Laboratory termite resistance tests showed that all samples containing boron compounds had greater resistance against termite attack compared to untreated MDF samples. At the second and third weeks of exposure, nearly 100% termite mortalities were recorded in all boron compound treated samples. The highest termite mortalities were determined in the samples with either BA or BX. Also, it was found that SPT showed notable performance on the termite mortality. As chemical loadings increased, termite mortalities increased, and at the same time the weight losses of the samples decreased.

  7. Boron carbide synthesis by carbothermic reduction of boron oxide

    International Nuclear Information System (INIS)

    Castro, A.R.M. de; Paschoal, J.O.A.

    1988-01-01

    Boron carbide (B 4 C) is a ceramic material of technological applications due to its extreme hardness and high chemical as well as thermal stability. Some parameters of the process for obtaining B 4 C by carbothermic reduction of B 2 O 3 have been determined. The starting powders and the final products have been analysed by chemical, spectrographic and X-ray diffraction methods. The results show that the B 4 C obtained by the carbothermic reduction process is suitable for applications with a definite determination of the free carbon content. (author) [pt

  8. Surface modified MXene Ti{sub 3}C{sub 2} multilayers by aryl diazonium salts leading to large-scale delamination

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongbing [College of Mechanics and Materials, Hohai University, Nanjing, Jiangsu Province 210098 (China); Department of Mathematics and Physics, Nanjing Institute of Technology, Nanjing, Jiangsu Province 211167 (China); Zhang, Jianfeng, E-mail: jfzhang_sic@163.com [College of Mechanics and Materials, Hohai University, Nanjing, Jiangsu Province 210098 (China); Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin [College of Mechanics and Materials, Hohai University, Nanjing, Jiangsu Province 210098 (China)

    2016-10-30

    Highlights: • A novel and simple method to delaminate MXene Ti{sub 3}C{sub 2} multilayers. • Surface modification using aryl diazonium salts induced swelling that conversely weakened the bonds between MXene layers. • The grafting of phenylsulfonic acid groups on MXene surfaces resulted in excellent water dispersibility. - Abstract: Herein we report a simple and facile method to delaminate MXene Ti{sub 3}C{sub 2} multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti{sub 3}AlC{sub 2} and the exfoliation of Ti{sub 3}AlC{sub 2} into Ti{sub 3}C{sub 2} multilayers, followed by Na{sup +} intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti{sub 3}C{sub 2} flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti{sub 3}C{sub 2} sheets disperse well in water and the solutions obey Lambert–Beer’s law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti{sub 3}C{sub 2} flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti{sub 3}C{sub 2}via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  9. Fabrication of boron-phosphide neutron detectors

    International Nuclear Information System (INIS)

    Fitzsimmons, M.; Pynn, R.

    1997-01-01

    Boron phosphide is a potentially viable candidate for high neutron flux neutron detectors. The authors have explored chemical vapor deposition methods to produce such detectors and have not been able to produce good boron phosphide coatings on silicon carbide substrates. However, semi-conducting quality films have been produced. Further testing is required

  10. New techniques for producing thin boron films

    International Nuclear Information System (INIS)

    Thomas, G.E.

    1988-01-01

    A review will be presented of methods for producing thin boron films using an electron gun. Previous papers have had the problem of spattering of the boron source during the evaporation. Methods for reducing this problem will also be presented. 12 refs., 4 figs

  11. Boron rates for triticale and wheat crops

    Directory of Open Access Journals (Sweden)

    Corrêa Juliano Corulli

    2005-01-01

    Full Text Available No reports are registered on responses to boron fertilization nutrient deficiency and toxicity in triticale crops. The aim of this study was to evaluate triticale response to different rates of boron in comparison to wheat in an hapludox with initial boron level at 0.08 mg dm-3 4 4 factorial design trial completely randomized blocks design (n = 4. Boron rates were 0; 0.62; 1.24 and 1.86 mg dm-3; triticale cultivars were IAC 3, BR 4 and BR 53 and IAPAR 38 wheat crop was used for comparison. The wheat (IAPAR 38 crop presented the highest boron absorption level of all. Among triticale cultivars, the most responsive was IAC 53, presenting similar characteristics to wheat, followed by BR 4; these two crops are considered tolerant to higher boron rates in soil. Regarding to BR 53, no absorption effect was observed, and the cultivars was sensitive to boron toxicity. Absorption responses differed for each genotype. That makes it possible to choose and use the best-adapted plants to soils with different boron rates.

  12. Hot flow behavior of boron microalloyed steels

    International Nuclear Information System (INIS)

    Lopez-Chipres, E.; Mejia, I.; Maldonado, C.; Bedolla-Jacuinde, A.; El-Wahabi, M.; Cabrera, J.M.

    2008-01-01

    This research work studies the effect of boron contents on the hot flow behavior of boron microalloyed steels. For this purpose, uniaxial hot-compression tests were carried out in a low carbon steel microalloyed with four different amounts of boron over a wide range of temperatures (950, 1000, 1050 and 1100 deg. C) and constant true strain rates (10 -3 , 10 -2 and 10 -1 s -1 ). Experimental results revealed that both peak stress and peak strain tend to decrease as boron content increases, which indicates that boron additions have a solid solution softening effect. Likewise, the flow curves show a delaying effect on the kinetics of dynamic recrystallization (DRX) when increasing boron content. Deformed microstructures show a finer austenitic grain size in the steel with higher boron content (grain refinement effect). Results are discussed in terms of boron segregation towards austenitic grain boundaries during plastic deformation, which increases the movement of dislocations, enhances the grain boundary cohesion and modificates the grain boundary structure

  13. Elastic modulus and fracture of boron carbide

    International Nuclear Information System (INIS)

    Hollenberg, G.W.; Walther, G.

    1978-12-01

    The elastic modulus of hot-pressed boron carbide with 1 to 15% porosity was measured at room temperature. K/sub IC/ values were determined for the same porosity range at 500 0 C by the double torsion technique. The critical stress intensity factor of boron carbide with 8% porosity was evaluated from 25 to 1200 0 C

  14. Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

    Science.gov (United States)

    Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

    2017-01-06

    An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

  15. Visible-light-mediated selective arylation of cysteine in batch and flow

    NARCIS (Netherlands)

    Bottecchia, C.; Rubens, M.; Gunnoo, S.B.; Hessel, V.; Madder, A.

    2017-01-01

    A mild visible-light-mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation

  16. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.

    Science.gov (United States)

    Xia, Zhonghua; Zhu, Qiang

    2013-08-16

    A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.

  17. Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Norrby, Per-Ola

    2007-01-01

    Oxidative addition of aryl chlorides to palladium has been investigated by hybrid density functional theory methods (B3LYP), including a continuum model describing the solvent implicitly. A series of para-substituted aryl chlorides were studied to see the influence of electronic effects...

  18. Metal-Free N-Arylation of Secondary Amides at Room Temperature

    OpenAIRE

    Tinnis, Fredrik; Stridfeldt, Elin; Lundberg, Helena; Adolfsson, Hans; Olofsson, Berit

    2015-01-01

    The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.

  19. Pd-Catalyzed Cross-Coupling Reactions of Amides and Aryl Mesylates

    Science.gov (United States)

    Dooleweerdt, Karin; Fors, Brett P.; Buchwald, Stephen L.

    2010-01-01

    A catalyst, based on a biarylphosphine ligand, for the Pd-catalyzed cross-coupling reactions of amides and aryl mesylates is described. This system allows an array of aryl and heteroaryl mesylates to be transformed into the corresponding N-arylamides in moderate to excellent yields. PMID:20420379

  20. Boron-Doped Diamond Electrodes for the Electrochemical Oxidation and Cleavage of Peptides

    NARCIS (Netherlands)

    Roeser, Julien; Alting, Niels F. A.; Permentier, Hjalmar P.; Bruins, Andries P.; Bischoff, Rainer

    2013-01-01

    Electrochemical oxidation of peptides and proteins is traditionally performed on carbon-based electrodes. Adsorption caused by the affinity of hydrophobic and aromatic amino acids toward these surfaces leads to electrode fouling. We compared the performance of boron-doped diamond (BDD) and glassy

  1. Effect of Boron and Phosphate compounds on Thermal and Fire Properties of wood/HDPE composites

    Science.gov (United States)

    Turgay Akbulut; Nadir Ayrilmis; Turker Dundar; Ali Durmus; Robert H. White; Murat Teker

    2011-01-01

    Melting and non-isothermal crystallization behaviors, oxidative induction time, and fire performance of the injection-molded wood flour-high density polyethylene (HDPE) composites (WPCs) incorporated with different levels (4, 8, or 12 wt %) of boron compounds [borax/boric acid (BX/BA) (0.5:0.5 wt %), zinc borate (ZB)] and phosphorus compounds [mono- and di-ammonium...

  2. Response surface modeling of boron adsorption from aqueous solution by vermiculite using different adsorption agents: Box-Behnken experimental design.

    Science.gov (United States)

    Demirçivi, Pelin; Saygılı, Gülhayat Nasün

    2017-07-01

    In this study, a different method was applied for boron removal by using vermiculite as the adsorbent. Vermiculite, which was used in the experiments, was not modified with adsorption agents before boron adsorption using a separate process. Hexadecyltrimethylammonium bromide (HDTMA) and Gallic acid (GA) were used as adsorption agents for vermiculite by maintaining the solid/liquid ratio at 12.5 g/L. HDTMA/GA concentration, contact time, pH, initial boron concentration, inert electrolyte and temperature effects on boron adsorption were analyzed. A three-factor, three-level Box-Behnken design model combined with response surface method (RSM) was employed to examine and optimize process variables for boron adsorption from aqueous solution by vermiculite using HDTMA and GA. Solution pH (2-12), temperature (25-60 °C) and initial boron concentration (50-8,000 mg/L) were chosen as independent variables and coded x 1 , x 2 and x 3 at three levels (-1, 0 and 1). Analysis of variance was used to test the significance of variables and their interactions with 95% confidence limit (α = 0.05). According to the regression coefficients, a second-order empirical equation was evaluated between the adsorption capacity (q i ) and the coded variables tested (x i ). Optimum values of the variables were also evaluated for maximum boron adsorption by vermiculite-HDTMA (HDTMA-Verm) and vermiculite-GA (GA-Verm).

  3. Recovery of boric acid from nuclear waste

    International Nuclear Information System (INIS)

    Lahoda, E.J.

    1985-01-01

    Disclosed is a process for separating and recovering boric acid from water containing solids which include boric acid and radionuclides. In the first step, the water is separated from the solids by evaporation of the water at a temperature under 130 0 F In the second step, an alcohol selected from the group consisting of methanol, ethanol, propanol, isopropanol, and mixtures thereof is added to the remaining solids in the amount of at least 1.4 times that stoichiometrically required to react with the boric acid to form boron alkoxide and water to about 100 mole % in excess of stoichiometric. In the third step, the boron alkoxide is separated from the remaining solids by evaporation of the boron alkoxide. In the fourth step, water is added to the volatilized boron alkoxide to form boric acid and an alcohol. And finally, the alcohol is separated from the boric acid by evaporating the alcohol

  4. Cathodoluminescence of cubic boron nitride

    International Nuclear Information System (INIS)

    Tkachev, V.D.; Shipilo, V.B.; Zajtsev, A.M.

    1985-01-01

    Three optically active defects are detected in mono- and polycrystal cubic boron nitride (β-BN). Analysis of intensity of temperature dependences, halfwidth and energy shift of 1.76 eV narrow phononless line (center GC-1) makes it possible to interprete the observed cathodoluminescence spectra an optical analog of the Moessbaner effect. Comparison of the obtained results with the known data for diamond monocrystals makes it possible to suggest that the detected center GC-1 is a nitrogen vacancy . The conclusion, concerning the Moessbauer optical spectra application, is made to analyze structural perfection of β-BN crystal lattice

  5. Boron enrichment in martian clay.

    Directory of Open Access Journals (Sweden)

    James D Stephenson

    Full Text Available We have detected a concentration of boron in martian clay far in excess of that in any previously reported extra-terrestrial object. This enrichment indicates that the chemistry necessary for the formation of ribose, a key component of RNA, could have existed on Mars since the formation of early clay deposits, contemporary to the emergence of life on Earth. Given the greater similarity of Earth and Mars early in their geological history, and the extensive disruption of Earth's earliest mineralogy by plate tectonics, we suggest that the conditions for prebiotic ribose synthesis may be better understood by further Mars exploration.

  6. Chemistry and technology of boron and its compounds

    International Nuclear Information System (INIS)

    Zhigach, A.F.; Parfenov, B.P.; Svitsyn, R.A.

    1995-01-01

    The results of research dealing with development of technologies of boron trichloride, boron hydride, aminoderivative boron hydrides, metal borohydrides, carboranes, carborane-containing polymers, carried out at the institute of organoelemental compounds, are presented. Physicochemical properties of the compounds have been studied and analytical methods have been developed. Data on toxicity and fire hazard of boron compounds are provided

  7. Analysis of boron nitride by flame spectrometry methods

    International Nuclear Information System (INIS)

    Telegin, G.F.; Chapysheva, G.Ya.; Shilkina, N.N.

    1989-01-01

    A rapid method has been developed for determination of free and total boron contents as well as trace impurities in boron nitride by using autoclave sample decomposition followed by atomic emission and atomic absorption determination. The relative standard deviation is not greater than 0.03 in the determination of free boron 0.012 in the determination of total boron content

  8. Chemical states of p-boronophenylalanine in aqueous carboxylic acids and polyols

    International Nuclear Information System (INIS)

    Kobayashi, Mitsue; Kitaoka, Yoshinori

    1995-01-01

    Chemical states of p-boronophenylalanine were studied by infrared (IR) spectroscopy in aqueous carboxylic acids and in aqueous fructose. For BPA in water, the absorption band due to the B-O stretching of trigonal boron was observed, while that of tetrahedral boron was observed for BPA in aqueous oxalic acid. This means BPA forms a complex of tetrahedral boron with oxalate. It was proved that BPA also formed complexes of tetrahedral boron with citric acid as well as with fructose. No appreciable interaction was detected between BPA and maleic acid. (author)

  9. Influence of Functionality on Direct Arylation of Model Systems as a Route Toward Fluorinated Copolymers via Direct Arylation Polymerization (DArP)

    DEFF Research Database (Denmark)

    Livi, Francesco; Gobalasingham, Nemal S.; Bundgaard, Eva

    2015-01-01

    A screening of direct arylation conditions on amodel small molecule system is carried out to develop suitableconditions for the direct arylation polymerization (DArP) of fluorinatedcopolymers, which are incompatible with conditionspreviously utilized successfully for nonfluorinated systems. Themo......,4-phenylene)dithiophene. Polymers arefree of β-defects and significant homocoupling. This work furtherunderscores the attractive simplicity, relevance, and easeof DArP while reconfirming its broad compatibility withincreasingly popular fluorinated copolymers....

  10. Electrodeposited tungsten-nickel-boron: A replacement for hexavalent chromium

    International Nuclear Information System (INIS)

    Steffani, C.; Meltzer, M.

    1995-04-01

    Chromium, deposited from acidic solutions of its hexavalent ion, has been the rule for wear resistant, corrosion resistant coatings for many years. Although chromium coatings are durable, the plating process generates air emissions, effluent rinse waters, and process solutions that are toxic, suspected carcinogens, and a risk to human health and the environment. Tungsten-nickel-boron (W-Ni-B) alloy deposition is a potential substitute for hexavalent chrome. It has excellent wear, corrosion, and mechanical properties and also may be less of an environmental risk. This study examines the electroplating process and deposit properties of W-Ni-B and compares them with those of hexavalent chrome

  11. Contamination of urban garden soils with copper, boron, and lead

    Energy Technology Data Exchange (ETDEWEB)

    Purves, D

    1967-04-01

    Spectrochemical analysis of representative samples of topsoil from urban gardens and from individual fields in rural areas indicates that the level of total copper, EDTA-extractable copper, water-soluble boron, and acetic-acid extractable lead are markedly enhanced in urban areas. No significant differences were discovered between levels of these elements in soils from built-up areas in small towns and large conurbations. These results suggest the possibility of general enhancement of the trace element content of plants grown in private gardens in built-up areas.

  12. Contributions te the study of methods and factors affecting the spectrophotometric determination of boron traces with carmin uranium compounds

    International Nuclear Information System (INIS)

    Fernandez Cellini, R.; Gasco Sanchez, L.

    1956-01-01

    The study of some factors affecting the spectrophotometric determination of boron traces with carmin is made; the influence of carmin from different origin, the stability of complex carmin-boric acid in relation with the sulphuric acid concentration, the interference produced by ion nitrate, and the ion uraline and light influence are discussed. (Author) 36 refs

  13. Boronated porphyrins in NCT: Results with a new potent tumor localizer

    International Nuclear Information System (INIS)

    Kahl, S.B.; Koo, M.S.; Laster, B.H.; Fairchild, R.G.

    1988-01-01

    Several chemical methods are available for the solubilization of boronated porphyrins. We have previously reported the tumor localization of nido carboranyl porphyrins in which the icosahedral carborane cages have been opened to give B 9 C 2 anions. One of these species has shown tumor boron levels of nearly 50 μg B/g when delivered by week-long subcutaneous infusions. We report here recent in vivo experiments with a new, highly water-soluble porphyrin based on the hematoporphyrin-type of compound in which aqueous solubility is achieved using the two propionic acid side chains of the ''natural'' porphyrin frame. 7 refs

  14. Role of the Aryl Hydrocarbon Receptor in Colon Neoplasia

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Guofeng, E-mail: gxie@medicine.umaryland.edu; Raufman, Jean-Pierre [Division of Gastroenterology and Hepatology, Veterans Administration Maryland Health Care System, University of Maryland School of Medicine, Baltimore, MD 21201 (United States)

    2015-07-31

    For both men and women, colorectal cancer (CRC) is the second leading cause of cancer death in the United States, primarily as a consequence of limited therapies for metastatic disease. The aryl hydrocarbon receptor (AhR) is a ligand-dependent transcription factor with diverse functions in detoxification of xenobiotics, inflammatory responses, and tissue homeostasis. Emerging evidence indicates that AhR also plays an important role in regulating intestinal cell proliferation and tumorigenesis. Here, we review both the pro- and anti-carcinogenic properties of AhR signaling and its potential role as a therapeutic target in CRC.

  15. Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

    Science.gov (United States)

    Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David W C

    2018-05-04

    The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Prevention of melanin formation during aryl alcohol oxidase production under growth-limited conditions using an Aspergillus nidulans cell factory.

    Science.gov (United States)

    Pardo-Planas, Oscar; Prade, Rolf A; Müller, Michael; Atiyeh, Hasan K; Wilkins, Mark R

    2017-11-01

    An Aspergillus nidulans cell factory was genetically engineered to produce an aryl alcohol oxidase (AAO). The cell factory initiated production of melanin when growth-limited conditions were established using stationary plates and shaken flasks. This phenomenon was more pronounced when the strain was cultured in a trickle bed reactor (TBR). This study investigated different approaches to reduce melanin formation in fungal mycelia and liquid medium in order to increase the enzyme production yield. Removal of copper from the medium recipe reduced melanin formation in agar cultures and increased enzyme activities by 48% in agitated liquid cultures. Copper has been reported as a key element for tyrosinase, an enzyme responsible for melanin production. Ascorbic acid (0.44g/L) stopped melanin accumulation, did not affect growth parameters and resulted in AAO activity that was more than two-fold greater than a control treatment with no ascorbic acid. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Study of ceramic mixed boron element as a neutron shielding

    International Nuclear Information System (INIS)

    Ismail Mustapha; Mohd Reusmaazran Yusof; Md Fakarudin Ab Rahman; Nor Paiza Mohamad Hasan; Samihah Mustaffha; Yusof Abdullah; Mohamad Rabaie Shari; Airwan Affandi Mahmood; Nurliyana Abdullah; Hearie Hassan

    2012-01-01

    Shielding upon radiation should not be underestimated as it can causes hazard to health. Precautions on the released of radioactive materials should be well concerned and considered. Therefore, the combination of ceramic and boron make them very useful for shielding purpose in areas of low and intermediate neutron. A six grades of ceramic tile have been produced namely IMN05 - 5 % boron, IMN06 - 6 % boron, IMN07 - 7 % boron, IMN08 - 8 % boron, IMN09 - 9 % boron, IMN10 - 10 % boron from mixing, press and sintered process. Boron is a material that capable of absorbing and capturing neutron, so that neutron and gamma test were conducted to analyze the effectiveness of boron material in combination with ceramic as shielding. From the finding, percent reduction number of count per minute shows the ceramic tiles are capable to capture neutron. Apart from all the percentage of boron used, 10 % is the most effective shields since the percent reduction indicating greater neutron captured increased. (author)

  18. A study of the distribution and uptake of boron in mango fruits using neutron-capture-radiography

    International Nuclear Information System (INIS)

    Loria, G.; Jimenez, R.; Gallardo, M.; Martini, F.; Thellier, M.

    1992-01-01

    The method of neutron-capture-radiography (NCR) was used to study the distribution of boron in mango fruit. There was a regular decrease of the concentration of natural boron from the skin (83.9 ppm, dry weight) to the interior of the fruit (2.4 ppm, dry weight, 5.6 mm deep in the fruit). When drops of a solution of ( 10 B)BO 3 H 3 were placed on the fruit surface, boron accumulated in restricted zones, within the fruit skin, which apparently corresponded to skin secretory-glands. The apparent coefficient of diffusion of boric acid from these zones of high boron accumulation to the interior of the fruit was of the order of 1.6 x 10 -12 m 2 s -1

  19. Boron-Loaded Silicone Rubber Scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Bell, Z.W.; Maya, L.; Brown, G.M.; Sloop, F.V.Jr

    2003-05-12

    Silicone rubber received attention as an alternative to polyvinyltoluene in applications in which the scintillator is exposed to high doses because of the increased resistance of the rubber to the formation of blue-absorbing color centers. Work by Bowen, et al., and Harmon, et al., demonstrated their properties under gamma/x-ray irradiation, and Bell, et al. have shown their response to thermal neutrons. This last work, however, provided an example of a silicone in which both the boron and the scintillator were contained in the rubber as solutes, a formulation which led to the precipitation of solids and sublimation of the boron component. In the present work we describe a scintillator in which the boron is chemically bonded to the siloxane and so avoids the problem of precipitation and loss of boron to sublimation. Material containing up to 18% boron, by weight, was prepared, mounted on photomultipliers, and exposed to both neutron and gamma fluxes. Pulse height spectra showing the neutron and photon response were obtained, and although the light output was found to be much poorer than from samples in which boron was dissolved, the higher boron concentrations enabled essentially 100% neutron absorption in only a few millimeters' thickness of rubber.

  20. Density separation of boron particles. Final report

    International Nuclear Information System (INIS)

    Smith, R.M.

    1980-04-01

    A density distribution much broader than expected was observed in lots of natural boron powder supplied by two different sources. The material in both lots was found to have a rhombohedral crystal structure, and the only other parameters which seemed to account for such a distribution were impurities within the crystal structure and varying isotopic ratios. A separation technique was established to isolate boron particles in narrow densty ranges. The isolated fractions were subsequently analyzed for B 10 and total boron content in an effort to determine whether selective isotopic enrichment and nonhomogeneous impurity distribution were the causes for the broad density distribution of the boron powders. It was found that although the B 10 content remained nearly constant around 18%, the total boron content varied from 37.5 to 98.7%. One of the lots also was found to contain an apparently high level of alpha rhombohedral boron which broadened the density distribution considerably. During this work, a capability for removing boron particles containing gross amounts of impurities and, thereby, improving the overall purity of the remaining material was developed. In addition, the separation technique used in this study apparently isolated particles with alpha and beta rhombohedral crystal structures, although the only supporting evidence is density data

  1. The influence of boron dopant on the electrochemical properties of graphene as an electrode material and a support for Pt catalysts

    International Nuclear Information System (INIS)

    Bo, Xiangjie; Li, Mian; Han, Ce; Guo, Liping

    2013-01-01

    Highlights: •More defective sites in graphene after the doping of boron atoms. •Fine dispersion of Pt nanoparticles supported on boron-doped graphene. •Low electron transfer resistance at boron-doped graphene. •High performance of boron-doped graphene as an electrode material or a support for Pt catalysts. -- Abstract: Boron-doped graphene (BGR) is prepared by thermal annealing of graphene oxide (GO) in the presence of boric acid. More defective sites are introduced into GR accompanied by the doping of boron. Low electron transfer resistance towards redox probe is observed at BGR. The BGR modified electrode can effectively distinguish the anodic peaks for ascorbic acid (AA), dopamine (DA), and uric acid (UA). The defective sites of BGR can also act as anchoring sites for the deposition of Pt nanoparticles. When used as a support for Pt electrocatalysts, Pt nanoparticles with an average diameter of 3.2 nm are deposited on BGR. The doping of boron into GR facilitates the dispersion of Pt nanoparticles and increases the utilization efficiency of Pt nanoparticles. The Pt/BGR exhibits significant catalytic activity towards the oxidation of methanol. The results demonstrate that BGR is a good support for Pt catalysts or an electrode material compared with the undoped GR

  2. Cell cycle dependence of boron uptake in various boron compounds used for neutron capture therapy

    International Nuclear Information System (INIS)

    Yoshida, F.; Matsumura, A.; Shibata, Y.; Yamamoto, T.; Nose, T.; Okumura, M.

    2000-01-01

    In neutron capture therapy, it is important that the tumor take boron in selectively. Furthermore, it is ideal when the uptake is equal in each tumor cell. Some indirect proof of differences in boron uptake among neoplastic cell cycles has been documented. However, no investigation has yet measured boron uptake directly. Using flow cytometry, in the present study cells were sorted by G0/G1 phase and G2/M phase, and the boron concentration of each fraction was measured with inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The results were that BSH (sodiumborocaptate) and BPA (p-boronophenylalanine) had higher rates of boron uptake in the G2/M group than in the G0/G1 group. However, in BPA the difference was more prominent, which revealed a 2.2-3.3 times higher uptake of boron in the G2/M group than in the G0/G1 group. (author)

  3. Synthesis of sulfadiazinyl acyl/aryl thiourea derivatives as calf intestinal alkaline phosphatase inhibitors, pharmacokinetic properties, lead optimization, Lineweaver-Burk plot evaluation and binding analysis.

    Science.gov (United States)

    Sajid-Ur-Rehman; Saeed, Aamer; Saddique, Gufran; Ali Channar, Pervaiz; Ali Larik, Fayaz; Abbas, Qamar; Hassan, Mubashir; Raza, Hussain; Fattah, Tanzeela Abdul; Seo, Sung-Yum

    2018-06-02

    To seek the new medicinal potential of sulfadiazine drug, the free amino group of sulfadiazine was exploited to obtain acyl/aryl thioureas using simple and straightforward protocol. Acyl/aryl thioureas are well recognized bioactive pharmacophore containing moieties. A new series (4a-4j) of sulfadiazine derived acyl/aryl thioureas was synthesized and characterized through spectroscopic and elemental analysis. The synthesized derivatives 4a-4j were subjected to calf intestinal alkaline phosphatase (CIAP) activity. The derivative 4a-4j showed better inhibition potential compared to standard monopotassium phosphate (MKP). The compound 4c exhibited higher potential in the series with IC 50 0.251 ± 0.012 µM (standard KH 2 PO 4 4.317 ± 0.201 µM). Lineweaver-Burk plots revealed that most potent derivative 4c inhibition CIAP via mixed type pathway. Pharmacological investigations showed that synthesized compounds 4a-4j obey Lipinsk's rule. ADMET parameters evaluation predicted that these molecule show significant lead like properties with minimum possible toxicity and can serve as templates in drug designing. The synthetic compounds show none mutagenic and irritant behavior. Molecular docking analysis showed that compound 4c interacts with Asp273, His317 and Arg166 amino acid residues. Copyright © 2018. Published by Elsevier Ltd.

  4. Synthesis and biological activity of a new class of insecticides: the N-(5-aryl-1,3,4-thiadiazol-2-yl)amides.

    Science.gov (United States)

    Eckelbarger, Joseph D; Parker, Marshall H; Yap, Maurice Ch; Buysse, Ann M; Babcock, Jonathan M; Hunter, Ricky; Adelfinskaya, Yelena; Samaritoni, Jack G; Garizi, Negar; Trullinger, Tony K

    2017-04-01

    Optimization studies on a high-throughput screening (HTS) hit led to the discovery of a series of N-(6-arylpyridazin-3-yl)amides with insecticidal activity. It was hypothesized that the isosteric replacement of the pyridazine ring with a 1,3,4-thiadiazole ring could lead to more potent biological activity and/or a broader sap-feeding pest spectrum. The resulting N-(5-aryl-1,3,4-thiadiazol-2-yl)amides were explored as a new class of insecticides. Several methods for 2-amino-1,3,4-thiadiazole synthesis were used for the preparation of key synthetic intermediates. Subsequent coupling to variously substituted carboxylic acid building blocks furnished the final targets, which were tested for insecticidal activity against susceptible strains of Aphis gossypii (Glover) (cotton aphid), Myzus persicae (Sulzer) (green peach aphid) and Bemisia tabaci (Gennadius) (sweetpotato whitefly). Structure-activity relationship (SAR) studies on both the amide tail and the aryl A-ring of novel N-(5-aryl-1,3,4-thiadiazol-2-yl)amides led to a new class of insecticidal molecules active against sap-feeding insect pests. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  5. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Directory of Open Access Journals (Sweden)

    Rita M. Borik

    2007-08-01

    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  6. Continuous aryl alcohol oxidase production under growth-limited conditions using a trickle bed reactor.

    Science.gov (United States)

    Pardo-Planas, Oscar; Atiyeh, Hasan K; Prade, Rolf A; Müller, Michael; Wilkins, Mark R

    2018-05-01

    An A. nidulans strain with a pyridoxine marker was used for continuous production of aryl alcohol oxidase (AAO) in a trickle bed reactor (TBR). Modified medium with reduced zinc, no copper, and 5 g/L ascorbic acid that reduced melanin production and increased AAO productivity under growth limited conditions was used. Two air flow rates, 0.11 L/min (0.1 vvm) and 1.1 L/min (1.0 vvm) were tested. More melanin formation and reduced protein productivity were observed with air flow rate of 1.1 L/min. Three random packings were used as support for the fungus inside the TBR column, two of which were hydrophobic and one which was hydrophilic, and three different dilution rates were tested. The use of GEA BCN 030 hydrophobic packing resulted in greater AAO yield and productivity than the other packings. Increasing dilution rates favored melanin formation and citric, lactic and succinic acid accumulation, which decreased AAO yield and productivity. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Current data regarding the structure-toxicity relationship of boron-containing compounds.

    Science.gov (United States)

    Farfán-García, E D; Castillo-Mendieta, N T; Ciprés-Flores, F J; Padilla-Martínez, I I; Trujillo-Ferrara, J G; Soriano-Ursúa, M A

    2016-09-06

    Boron is ubiquitous in nature, being an essential element of diverse cells. As a result, humans have had contact with boron containing compounds (BCCs) for a long time. During the 20th century, BCCs were developed as antiseptics, antibiotics, cosmetics and insecticides. Boric acid was freely used in the nosocomial environment as an antiseptic and sedative salt, leading to the death of patients and an important discovery about its critical toxicology for humans. Since then the many toxicological studies done in relation to BCCs have helped to establish the proper limits of their use. During the last 15 years, there has been a boom of research on the design and use of new, potent and efficient boron containing drugs, finding that the addition of boron to some known drugs increases their affinity and selectivity. This mini-review summarizes two aspects of BCCs: toxicological data found with experimental models, and the scarce but increasing data about the structure-activity relationship for toxicity and therapeutic use. As is the case with boron-free compounds, the biological activity of BCCs is related to their chemical structure. We discuss the use of new technology to discover potent and efficient BCCs for medicinal therapy by avoiding toxic effects. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  8. Boron-doped MnO{sub 2}/carbon fiber composite electrode for supercapacitor

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Hong Zhong, E-mail: hzchi@hdu.edu.cn [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Zhu, Hongjie [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Gao, Linhui [Center of Materials Engineering, Zhejiang Sci-Tech University, Hangzhou 310018 (China)

    2015-10-05

    Highlights: • Interstitial ion in MnO{sub 2} lattice. • Porous film composed by interlocking worm-like nanostructure. • Boron-doped birnessite-type MnO{sub 2}/carbon fiber composite electrode. • Enhanced capacitive properties through nonmetal element doping. - Abstract: The boron-doped MnO{sub 2}/carbon fiber composite electrode has been prepared via in situ redox reaction between potassium permanganate and carbon fibers in the presence of boric acid. The addition of boron as dopant results in the increase of growth-rate of MnO{sub 2} crystal and the formation of worm-like nanostructure. Based on the analysis of binding energy, element boron incorporates into the MnO{sub 2} lattice through interstitial mode. The doped electrode with porous framework is beneficial to pseudocapacitive reaction and surface charge storage, leading to higher specific capacitance and superior rate capability. After experienced 1000 cycles, the boron-doped MnO{sub 2} still retain a higher specific capacitance by about 80% of its initial value. The fall in capacitance is blamed to be the combination of the formation of soluble Mn{sup 2+} and the absence of active site on the outer surface.

  9. Developments in boron magnetic resonance imaging (MRI)

    International Nuclear Information System (INIS)

    Schweizer, M.

    1995-01-01

    This report summarizes progress during the past year on maturing Boron-11 magnetic resonance imaging (MRI) methodology for noninvasive determination of BNCT agents (BSH) spatially in time. Three major areas are excerpted: (1) Boron-11 MRI of BSH distributions in a canine intracranial tumor model and the first human glioblastoma patient, (2) whole body Boron-11 MRI of BSH pharmacokinetics in a rat flank tumor model, and (3) penetration of gadolinium salts through the BBB as a function of tumor growth in the canine brain

  10. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    Directory of Open Access Journals (Sweden)

    Wei Zheng

    2016-03-01

    Full Text Available Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  11. Silicon dioxide surfaces with aryl interaction sites for chromatographic applications

    International Nuclear Information System (INIS)

    Gadzal-Kopciuch, R.; Kluska, M.; Welniak, M.; Buszewski, B.

    2005-01-01

    The paper presents the results of a study on aryl phases aimed at the increase of the separation selectivity of substances containing π electrons, and improving the reproducibility of retention data. The above phases contain not only a carbon chain of a different length, linking them to the support, but also one or two aromatic rings. The suitability of the newly obtained packings for the purposes of high-performance liquid chromatography was verified on the basis of a description of surface topography before and after the modification process. Various physicochemical methods were employed to determine the effectiveness of chemical modification, i.e., elemental analysis, infrared spectroscopy, and nuclear magnetic resonance. The aryl packings obtained were used for the separation of polynuclear aromatic hydrocarbons and budesonide epimers, tested under hydroorganic conditions (water/ethanol, water/methanol, water/acetonitrile). The application of a methanol/water mobile phase and a new-generation naphthylpropyl stationary phase for the separation of the 22R and 22S diastereoisomers of budesonide allowed the obtention of reproducible results and make qualitative and quantitative determinations of particular enantiomers

  12. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-14

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  13. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J

    2014-01-01

    This "hands-on" approach to the topic of arylation consolidates the body of key research over the last ten years (and up to around 2014) on various catalytic methods which involve an arylation process. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods. The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies using arylboron reagents. A cross-section of relevant tried-and-tested experimental protocols is included at the end of each chapter for putting into immediate practice, along with patent literature. Due to its emphasis on efficient, "green" methods and industrial applications of the products c...

  14. Characterization of boron tolerant bacteria isolated from a fly ash dumping site for bacterial boron remediation.

    Science.gov (United States)

    Edward Raja, Chellaiah; Omine, Kiyoshi

    2013-08-01

    Boron is an essential micronutrient for plants, but can above certain concentrations be toxic to living organisms. A major environmental concern is the removal of boron from contaminated water and fly ash. For this purpose, the samples were collected from a fly ash dumping site, Nagasaki prefecture, Japan. The chemical characteristics and heavy metal concentration of the samples were performed by X-ray fluorescent analysis and leaching test. For bacterial analysis, samples were collected in sterile plastic sheets and isolation was carried out by serial dilution method. The boron tolerant isolates that showed values of maximum inhibitory concentration toward boron ranging from 100 to 260 mM level were screened. Based on 16S rRNA sequencing and phylogenetic analysis, the isolates were most closely related to the genera Bacillus, Lysinibacillus, Microbacterium and Ralstonia. The boron tolerance of these strains was also associated with resistant to several heavy metals, such as As (III), Cr (VI), Cd, Cu, Pb, Ni, Se (III) and Zn. Indeed, these strains were arsenic oxidizing bacteria confirmed by silver nitrate test. These strains exhibited their salt resistances ranging from 4 to 15 % were determined in Trypticase soy agar medium. The boron tolerant strains were capable of removing 0.1-2.0 and 2.7-3.7 mg l(-1) boron from the medium and fly ash at 168 h. Thus, we have successfully identified the boron tolerant and removal bacteria from a fly ash dumping site for boron remediation.

  15. Investigation of boron extraction process with aid magnesium hydroxide from mother liquor of boron production

    International Nuclear Information System (INIS)

    Balapanova, B.S.; Zhajmina, R.E.; Serazetdinov, D.Z.

    1988-01-01

    Conditions of boron - magnesium concentrate preparation from mother liquor by coprecipitation of borate - ions by magnesium hydroxide are investigated. It is shown that boron - magnesium concentrate and products of its heat treatment at 100 - 500 deg C in water are dissolved partially, and in ammonium citrate - practically completely. Suppositions are made on the composition of the product prepared, on the the structure of its crystal lattice and the processes taking place in it during heat treatment. The conclusion is made on the perspectiveness of processing of mother liquor of boron industry for boron - magnesium concentrate

  16. Radioiodination via isotope exchange in pivalic acid

    International Nuclear Information System (INIS)

    Weichert, J.P.; Van Dort, M.E.; Groziak, M.P.; Counsell, R.E.

    1986-01-01

    A variety of benzoic and aryl aliphatic mono and polyiodinated acids and esters (sterol, triglyceride) were radioiodinated in 55-99% radiochemical yield by isotope exchange with Na 125 i in a melt of pivalic acid. In general, the reaction was complete in 1 h at 155 0 C with little or no substrate decomposition. High specific activity studies afforded 125 I-labeled iopanoic acid with a specific activity of over 700 Ci/mmol. (author)

  17. Electronic states of aryl radical functionalized graphenes: Density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-06-01

    Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

  18. Cathodoluminescence of cubic boron nitride

    International Nuclear Information System (INIS)

    Tkachev, V.D.; Shipilo, V.B.; Zaitsev, A.M.

    1985-01-01

    Three types of optically active defect were observed in single-crystal and polycrystalline cubic boron nitride (β-BN). An analysis of the temperature dependences of the intensity, half-width, and energy shift of a narrow zero-phonon line at 1.76 eV (GC-1 center) made it possible to interpret the observed cathodoluminescence spectra as an optical analog of the Moessbauer effect. A comparison of the results obtained in the present study with the available data on diamond single crystals made it possible to identify the observed GC-1 center as a nitrogen vacancy. It was concluded that optical Moessbauer-type spectra can be used to analyze structure defects in the crystal lattice of β-BN

  19. Lactobacillus bulgaricus OLL1181 activates the aryl hydrocarbon receptor pathway and inhibits colitis

    Science.gov (United States)

    Takamura, Takeyuki; Harama, Daisuke; Fukumoto, Suguru; Nakamura, Yuki; Shimokawa, Naomi; Ishimaru, Kayoko; Ikegami, Shuji; Makino, Seiya; Kitamura, Masanori; Nakao, Atsuhito

    2011-01-01

    Increasing evidence suggests that the aryl hydrocarbon receptor (AhR) pathway has an important role in the regulation of inflammatory responses. Most recently, we have shown that the activation of the AhR pathway by a potent AhR agonist inhibits the development of dextran sodium sulfate (DSS)-induced colitis, a model of human ulcerative colitis, by the induction of prostaglandin E2 (PGE2) in the large intestine. Because several strains of probiotic lactic acid bacteria have been reported to inhibit DSS-induced colitis by unidentified mechanisms, we hypothesized that particular strains of lactic acid bacterium might have the potential to activate the AhR pathway, thereby inhibiting DSS-induced colitis. This study investigated whether there are specific lactic acid bacterial strains that can activate the AhR pathway, and if so, whether this AhR-activating potential is associated with suppression of DSS-induced colitis. By using AhR signaling reporter cells, we found that Lactobacillus bulgaricus OLL1181 had the potential to activate the AhR pathway. OLL1181 also induced the mRNA expression of cytochrome P450 family 1A1 (CYP1A1), a target gene of the AhR pathway, in human colon cells, which was inhibited by the addition of an AhR antagonist, α-naphthoflavon (αNF). In addition, mice treated orally with OLL1181 showed an increase in CYP1A1 mRNA expression in the large intestine and amelioration of DSS-induced colitis. Thus, OLL1181 can induce activation of the intestinal AhR pathway and inhibit DSS-induced colitis in mice. This strain of lactic acid bacterium has therefore the potential to activate the AhR pathway, which may be able to suppress colitis. PMID:21321579

  20. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.