Science.gov

Sample records for boronic acids

  1. Formose reaction controlled by boronic acid compounds

    PubMed Central

    Imai, Toru; Michitaka, Tomohiro

    2016-01-01

    Formose reactions were carried out in the presence of low molecular weight and macromolecular boronic acid compounds, i.e., sodium phenylboronate (SPB) and a copolymer of sodium 4-vinylphenylboronate with sodium 4-styrenesulfonate (pVPB/NaSS), respectively. The boronic acid compounds provided different selectivities; sugars of a small carbon number were formed favorably in the presence of SPB, whereas sugar alcohols of a larger carbon number were formed preferably in the presence of pVPB/NaSS. PMID:28144337

  2. Colorimetric Sugar Sensing Using Boronic Acid-Substituted Azobenzenes.

    PubMed

    Egawa, Yuya; Miki, Ryotaro; Seki, Toshinobu

    2014-02-14

    In association with increasing diabetes prevalence, it is desirable to develop new glucose sensing systems with low cost, ease of use, high stability and good portability. Boronic acid is one of the potential candidates for a future alternative to enzyme-based glucose sensors. Boronic acid derivatives have been widely used for the sugar recognition motif, because boronic acids bind adjacent diols to form cyclic boronate esters. In order to develop colorimetric sugar sensors, boronic acid-conjugated azobenzenes have been synthesized. There are several types of boronic acid azobenzenes, and their characteristics tend to rely on the substitute position of the boronic acid moiety. For example, o-substitution of boronic acid to the azo group gives the advantage of a significant color change upon sugar addition. Nitrogen-15 Nuclear Magnetic Resonance (NMR) studies clearly show a signaling mechanism based on the formation and cleavage of the B-N dative bond between boronic acid and azo moieties in the dye. Some boronic acid-substituted azobenzenes were attached to a polymer or utilized for supramolecular chemistry to produce glucose-selective binding, in which two boronic acid moieties cooperatively bind one glucose molecule. In addition, boronic acid-substituted azobenzenes have been applied not only for glucose monitoring, but also for the sensing of glycated hemoglobin and dopamine.

  3. Boron-containing amino carboxylic acid compounds and uses thereof

    DOEpatents

    Kabalka, George W.; Srivastava, Rajiv R.

    2000-03-14

    Novel compounds which are useful for boron neutron capture therapy (BNCT) are disclosed. The compounds comprise a stable boron-containing group and an aminocycloalkane carboxylic acid group or a boronated acyclic hydrocarbon-linked amino carboxylic acid. Methods for synthesis of the compounds and for use of the compounds in BNCT are disclosed.

  4. Boron containing amino acid compounds and methods for their use

    DOEpatents

    Glass, John D.; Coderre, Jeffrey A.

    2000-01-01

    The present invention provides new boron containing amino acid compounds and methods for making these compounds by contacting melphalan or another nitrogen mustard derivative and sodium borocaptate. The present invention also provides a method of treating a mammal having a tumor by administering to the mammal a therapeutically effective amount of the new boron containing amino acid compounds.

  5. Boron containing amino acid compounds and methods for their use

    SciTech Connect

    Glass, J.D.; Coderre, J.A.

    2000-01-25

    The present invention provides new boron containing amino acid compounds and methods for making these compounds by contacting melphalan or another nitrogen mustard derivative and sodium borocaptate. The present invention also provides a method of treating a mammal having a tumor by administering to the mammal a therapeutically effective amount of the new boron containing amino acid compounds.

  6. Boronic acids for fluorescence imaging of carbohydrates.

    PubMed

    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.

  7. Click reactions and boronic acids: applications, issues, and potential solutions.

    PubMed

    Dai, Chaofeng; Cheng, Yunfeng; Cui, Jianmei; Wang, Binghe

    2010-08-23

    Boronic acids have been widely used in a wide range of organic reactions, in the preparation of sensors for carbohydrates, and as potential pharmaceutical agents. With the growing importance of click reactions, inevitably they are also applied to the synthesis of compounds containing the boronic acid moiety. However, such applications have unique problems. Chief among them is the issue of copper-mediated boronic acid degradation in copper-assisted [2,3]-cycloadditions involving an alkyne and an azido compound as the starting materials. This review summarizes recent developments, analyzes potential issues, and discusses known as well as possible solutions.

  8. Biological Evaluation of Boronated Unnatural Amino Acids as New Boron Carriers

    PubMed Central

    Kabalka, G.W.; Yao, M.-L.; Marepally, S.R.; Chandra, S.

    2010-01-01

    There is a pressing need for new and more efficient boron delivery agents to tumor cells for use in boron neutron capture therapy (BNCT). A class of boronated unnatural cyclic amino acids has demonstrated a remarkable selectivity toward tumors in animal and cell culture models, far superior to currently used agents in clinical BNCT. One of these amino acids, 1-amino-3-boronocyclopentanecarboxylic acid (ABCPC), has shown a tumor to blood ratio of 8 and a tumor to normal brain ratio of nearly 21 in a melanoma bearing mouse model. This work represents further biological characterization of this compound for tumor targeting in an EMT6 murine mammary carcinoma mouse model and a T98G human glioblastoma cell line. Female BALB/c mice bearing EMT6 tumors were injected with the fructose complex form of racemic mixtures of cis- and trans isomers of ABCPC in identical concentrations. Boron concentrations were measured in the tumor, blood, brain, skin, and liver tissues at 1, 3, and 5 hr post injection. These observations revealed a remarkable difference in racemic mixtures of cis and trans isomers in tumor targeting by boron. This implies that further separation of the L and D forms of this compound may enhance tumor targeting to an even higher degree than that provided by the racemic mixtures. Since the uptake measurements were made in homogenized tumor and normal tissues, little is known about the subcellular location of the boron arising from the various isomeric forms of the amino acid. To study subcellular delivery of boron from ABCPC in T98G human glioblastoma cells, we employed secondary ion mass spectrometry (SIMS) based technique of ion microscopy, which is capable of quantitatively imaging isotopic (elemental) gradients in cells and tissues at 500 nm spatial resolution. The T98G cells were exposed to the nutrient medium containing 100 ppm boron equivalent of a mixture of both L and D isomers of ABCPC in the form of a fructose complex for 1 hr. Following this

  9. Hydrolytic Unzipping of Boron Nitride Nanotubes in Nitric Acid

    NASA Astrophysics Data System (ADS)

    Kim, Dukeun; Muramatsu, Hiroyuki; Kim, Yoong Ahm

    2017-02-01

    Boron nitride nanoribbons (BNNRs) have very attractive electrical and optical properties due to their unique edge states and width-related properties. Herein, for the first time, BNNRs were produced by a simple reflux of boron nitride nanotubes (BNNTs) in nitric acid containing water, which had led to unzipped sidewalls through hydrolysis. Their high reactivity that originated from edges was verified via a strong interaction with methylene blue.

  10. Hydrolytic Unzipping of Boron Nitride Nanotubes in Nitric Acid.

    PubMed

    Kim, Dukeun; Muramatsu, Hiroyuki; Kim, Yoong Ahm

    2017-12-01

    Boron nitride nanoribbons (BNNRs) have very attractive electrical and optical properties due to their unique edge states and width-related properties. Herein, for the first time, BNNRs were produced by a simple reflux of boron nitride nanotubes (BNNTs) in nitric acid containing water, which had led to unzipped sidewalls through hydrolysis. Their high reactivity that originated from edges was verified via a strong interaction with methylene blue.

  11. Periodic trends and index of boron LEwis acidity.

    PubMed

    Plumley, Joshua A; Evanseck, Jeffrey D

    2009-05-21

    Lewis acidity is customarily gauged by comparing the relative magnitude of coordinate covalent bonding energies, where the Lewis acid moiety is varied and the Lewis base is kept constant. However, the prediction of Lewis acidity from first principles is sometimes contrary to that suggested by experimental bond energies. Specifically, the order of boron trihalide Lewis acidities predicted from substituent electronegativity arguments is opposite to that inferred by experiment. Contemporary explanations for the divergence between theory, computation, and experiment have led to further consternation. Due to the fundamental importance of understanding the origin of Lewis acidity, we report periodic trends for 21 boron Lewis acids, as well as their coordinate covalent bond strengths with NH(3), utilizing ab initio, density functional theory, and natural bond orbital analysis. Coordinate covalent bond dissociation energy has been determined to be an inadequate index of Lewis acid strength. Instead, acidity is measured in the manner originally intended by Lewis, which is defined by the valence of the acid of interest. Boron Lewis acidity is found to depend upon substituent electronegativity and atomic size, differently than for known Brønsted-Lowry periodic trends. Across the second period, stronger substituent electronegativity correlates (R(2) = 0.94) with increased Lewis acidity. However, across the third period, an equal contribution from substituent electronegativity and atomic radii is correlated (R(2) = 0.98) with Lewis acidity. The data suggest that Lewis acidity depends upon electronegativity solely down group 14, while equal contribution from both substituent electronegativity and atomic size are significant down groups 16 and 17. Originally deduced from Pauling's electronegativities, boron's substituents determine acidity by influencing the population of its valence by withdrawing electron density. However, size effects manifest differently than previously

  12. Synthesis of Sugar-Boronic Acid Derivatives: A Class of Potential Agents for Boron Neutron Capture Therapy.

    PubMed

    Imperio, Daniela; Del Grosso, Erika; Fallarini, Silvia; Lombardi, Grazia; Panza, Luigi

    2017-04-07

    To date, sugar analogues that contain boronic acids as substitutes for hydroxyl groups are a class of compounds nearly unknown in the literature. The challenging synthesis of two sugar-boronic acid analogues is described, and data are retrieved on their solution behavior, stability, and toxicity. As these compounds were expected to mimic the behavior of carbohydrates, they were tested in regards to their future development as potential boron neutron capture therapy agents.

  13. Potential of using boric acid as a boron drug for boron neutron capture therapy for osteosarcoma.

    PubMed

    Hsu, C F; Lin, S Y; Peir, J J; Liao, J W; Lin, Y C; Chou, F I

    2011-12-01

    Osteosarcoma is a malignant tumor commonly found in human and animals. The ability of boric acid (BA) to accumulate in osteosarcoma due to the mechanism of the bone formation of cancer cells would make boron neutron capture therapy (BNCT) an alternative therapy for osteosarcoma. This study evaluated the feasibility of using BA as the boron drug for BNCT of bone cancer. The cytotoxicity of BA to L929 cells exceeded that of UMR-106 cells. With 25 μg (10)B/mL medium of BA treatment, the boron concentration in UMR-106 cells was higher than that in L929 cells. The biodistribution and pharmacokinetics of BA in Sprague-Dawley (SD) rats were studied by administrating 25 mg (10)B/kg body weight to SD rats. Blood boron level decreased rapidly within one hour after BA injection. Boron concentration in the long bone was 4-6 time higher than that of blood. Results of this study suggest that BA may be a potential drug for BNCT for osteosarcoma.

  14. Use of boronic acid nanoparticles in glycoprotein enrichment.

    PubMed

    Xu, Yawei; Zhang, Lijuan; Lu, Haojie

    2013-01-01

    Glyco-specific enrichment methods for mass spectrometry pretreatment are invaluable for the detection of low abundant glycoproteins or glycopeptides. For example, boronic acid can specifically interact with glycans in nonaqueous or basic aqueous solutions. Here, we describe a glyco-specific enrichment method which uses a boronic acid-functionalized "core-satellite" composite nanoparticle to isolate glycoproteins or glycopeptides from complex biological samples. Furthermore, we also demonstrate detection limit improvements and show how to evaluate the percent recovery from the glycoprotein or glycopeptide enrichment process via SDS-PAGE and (16)O/(18)O labeling strategies.

  15. Boron

    USDA-ARS?s Scientific Manuscript database

    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...

  16. Glucose selective bis-boronic acid click-fluor.

    PubMed

    Zhai, Wenlei; Male, Louise; Fossey, John S

    2017-02-14

    Four novel bis-boronic acid compounds were synthesised via copper catalysed azide-alkyne cycloaddition (CuAAC) reactions. Glucose selectivity was observed for a particular structural motif. Moreover, a new glucose selective fluorescent sensor was designed and synthesised as a result.

  17. Synthesis of boron suboxide from boron and boric acid under mild pressure and temperature conditions

    SciTech Connect

    Jiao, Xiaopeng; Jin, Hua; Ding, Zhanhui; Yang, Bin; Lu, Fengguo; Zhao, Xudong; Liu, Xiaoyang; Peng, Liping

    2011-05-15

    Graphical abstract: Well-crystallized and icosahedral B{sub 6}O crystals were prepared by reacting boron and boric acid at milder reaction conditions (1 GPa and 1300 {sup o}C for 2 h) as compared to previous work.. Research highlights: {yields} Well-crystallized icosahedral B{sub 6}O was synthesized by reacting boric acid and boron. {yields} The synthesis conditions (1 GPa and 1300 {sup o}C for 2 h) are milder in comparison with previous work. {yields} The more practical synthesis method may make B{sub 6}O as a potential substitute for diamond in industry. -- Abstract: Boron suboxide (B{sub 6}O) was synthesized by reacting boron and boric acid (H{sub 3}BO{sub 3}) at pressures between 1 and 10 GPa, and at temperatures between 1300 and 1400 {sup o}C. The B{sub 6}O samples prepared were icosahedral with diameters ranging from 20 to 300 nm. Well-crystallized and icosahedral crystals with an average size of {approx}100 nm can be obtained at milder reaction conditions (1 GPa and 1300 {sup o}C for 2 h) as compared to previous work. The bulk B{sub 6}O sample was stable in air at 600 {sup o}C and then slowly oxidized up to 1000 {sup o}C. The relatively mild synthetic conditions developed in this study provide a more practical synthesis of B{sub 6}O, which may potentially be used as a substitute for diamond in industry as a new superhard material.

  18. Protodeboronation of ortho- and para-phenol boronic acids and application to ortho and meta functionalization of phenols using boronic acids as blocking and directing groups.

    PubMed

    Lee, Chun-Young; Ahn, Su-Jin; Cheon, Cheol-Hong

    2013-12-06

    The first metal-free thermal protodeboronation of ortho- and para-phenol boronic acids in DMSO was developed. The protodeboronation was successfully applied to the synthesis of ortho- and meta-functionalized phenols using the boronic acid moiety as a blocking group and a directing group, respectively. Mechanistic studies suggested that this protodeboronation proceeds through the coordination of water to the boron atom followed by σ-bond metathesis.

  19. Reversible click reactions with boronic acids to build supramolecular architectures in water.

    PubMed

    Arzt, Matthias; Seidler, Christiane; Ng, David Y W; Weil, Tanja

    2014-08-01

    The interaction of boronic acids with various bifunctional reagents offers great potential for the preparation of responsive supramolecular architectures. Boronic acids react with 1,2-diols yielding cyclic boronate esters that are stable at pH>7.4 but can be hydrolyzed at pH<5.0. The phenylboronic acid (PBA)-salicylhydroxamic acid (SHA) system offers ultra-fast reaction kinetics and high binding affinities. This Focus Review summarizes the current advances in exploiting the bioorthogonal interaction of boronic acids to build pH-responsive supramolecular architectures in water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Boronated Unnatural Cyclic Amino Acids as Potential Delivery Agents for Neutron Capture Therapy

    PubMed Central

    Kabalka, George W.; Shaikh, Aarif L.; Barth, Rolf F.; Huo, Tianyao; Yang, Weilian; Gordnier, Pamela M.; Chandra, Subhash

    2011-01-01

    Boron delivery characteristics of cis and trans isomers of a boronated unnatural amino acid, 1-amino-3-boronocyclopentanecarboxylic acid (ABCPC) were tested in B16 mouse model for human melanoma. Both ABCPC isomers delivered comparable boron to B16 melanoma tumor cells as L-p-boronophenylalanine (BPA). Secondary ion mass spectrometry (SIMS) analysis revealed the presence of boron throughout the tumor from these compounds, and a near homogeneous distribution between the nucleus and cytoplasm of B16 cells grown in vitro. These encouraging observations support further studies of these new boron carriers in BNCT. PMID:21481596

  1. Boron

    MedlinePlus

    ... body handles other minerals such as magnesium and phosphorus. It also seems to increase estrogen levels in ... happens in men.PhosphorusSupplemental boron might reduce blood phosphorus levels in some people.

  2. Synthesis of Aldehydes by Organocatalytic Formylation Reactions of Boronic Acids with Glyoxylic Acid.

    PubMed

    Huang, He; Yu, Chenguang; Li, Xiangmin; Zhang, Yongqiang; Zhang, Yueteng; Chen, Xiaobei; Mariano, Patrick S; Xie, Hexin; Wang, Wei

    2017-07-03

    Reported herein is a conceptually novel organocatalytic strategy for the formylation of boronic acids. New reactivity is engineered into the α-amino-acid-forming Petasis reaction occurring between aryl boronic acids, amines, and glyoxylic acids to prepare aldehydes. The operational simplicity of the process and its ability to generate structurally diverse and valued aryl, heteroaryl, and α,β-unsaturated aldehydes containing a wide array of functional groups, demonstrates the practical utility of the new synthetic strategy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Boron and nucleic acid chemistries: merging the best of both worlds.

    PubMed

    Martin, Anthony R; Vasseur, Jean-Jacques; Smietana, Michael

    2013-07-07

    At the intersection of nucleic acid and boron chemistries lies a thriving world of possibilities. During the past decades, the merging of these research domains has led to fascinating discoveries in different fields ranging from material to medical sciences. In recent years the interplay of these two worlds has gained a lot of attention, as can be judged by the increasing number of articles in which boron and nucleic acids stand out for their potential medicinal, biotechnological or analytical applications. In this review, we present an outline of this crossroads by focusing on both the interaction of boronated compounds with nucleic acids and the modification of nucleic acids by boron containing moieties.

  4. Development and validation of non-aqueous capillary electrophoresis methods to analyze boronic esters and acids.

    PubMed

    Forst, Mindy B; Warner, Anne M

    2012-05-01

    Boronic esters and acids are potential intermediates in the manufacture of many active pharmaceutical ingredients (API). Accurate quantitation of the intermediate is necessary to assure the stoichiometry of the reaction. The analysis of these compounds is challenging due to their labile nature. For example, the boronic ester can hydrolyze to the acid during storage, when exposed to moisture in the air, during sample preparation and analysis, and thus give erroneous ester results. Traditional analytical techniques like gas chromatography (GC), normal phase chromatography (NPLC), hydrophilic interaction chromatography (HILIC), and reversed phase liquid chromatography (RPLC) have been utilized but with noted limitations such as poor peak shape, variation in retention times, and evidence of hydrolysis. All of these limitations impact accurate quantitation needed for selected situations. For the proprietary boronic ester evaluated here, these traditional techniques were insufficient for the accurate determination of assay and residual boronic acid. Non-aqueous capillary electrophoresis (NACE) is an accurate quantitative technique that can be used to analyze boronic esters and their corresponding acids without the limitations noted for traditional analytical techniques. The present study describes the development of methodology for the determination of the potency of a proprietary boronic ester as well as methodology for the determination of residual boronic acid in the ester. In addition, nine model boronic ester and acid pairs with a range in polarity, based on the electronic properties of the attached side group, were tested to evaluate and demonstrate the general applicability of these conditions. Under the conditions used for potency, all ten pairs had a resolution between the boronic ester and acid of greater than 1.5, acceptable peak shape for the boronic ester (tailing factor of less than 2.0), and a run time of less than 3 min. In addition, this work describes

  5. Fluorescent Boronic Acid Polymer Grafted on Silica Particles for Affinity Separation of Saccharides

    PubMed Central

    2014-01-01

    Boronic acid affinity gels are important for effective separation of biological active cis-diols, and are finding applications both in biotech industry and in biomedical research areas. To increase the efficacy of boronate affinity separation, it is interesting to introduce repeating boronic acid units in flexible polymer chains attached on solid materials. In this work, we synthesize polymer brushes containing boronic acid repeating units on silica gels using surface-initiated atom transfer radical polymerization (ATRP). A fluorescent boronic acid monomer is first prepared from an azide-tagged fluorogenic boronic acid and an alkyne-containing acrylate by Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction (the CuAAC click chemistry). The boronic acid monomer is then grafted to the surface of silica gel modified with an ATRP initiator. The obtained composite material contains boronic acid polymer brushes on surface and shows favorable saccharide binding capability under physiological pH conditions, and displays interesting fluorescence intensity change upon binding fructose and glucose. In addition to saccharide binding, the flexible polymer brushes on silica also enable fast separation of a model glycoprotein based on selective boronate affinity interaction. The synthetic approach and the composite functional material developed in this work should open new opportunities for high efficiency detection, separation, and analysis of not only simple saccharides, but also glycopeptides and large glycoproteins. PMID:24444898

  6. Interaction of Boron with Components of Nucleic Acid Metabolism in Cotton Ovules Cultured in Vitro

    PubMed Central

    Birnbaum, Elliott H.; Dugger, W. Mack; Beasley, Bud C. A.

    1977-01-01

    Cotton (Gossypium hirsutum L.) ovules grown in a defined nutrient medium undergo normal morphogenesis, including fiber production. In identical medium lacking boron, ovules callus and accumulate brown substances. Boron deficiency-like symptoms were induced by 6-azauracil and 6-azauridine in ovules growing in boron-sufficient media. Other nucleoside base analogs either reduced or had no effect on over-all growth, but did not cause typical boron-deficient callus growth of cotton ovules. Orotic acid and uracil countered the effects of 6-azauracil. Actinomycin D, fluorodeoxyuridine, and ethidium bromide reduced not only fiber production on ovules growing in boron-sufficient media but also callusing of ovules in boron-deficient media. Similarities between symptoms of boron deficiency and 6-azauracil injury, and the ability of uracil to suppress both, suggest that boron deficiency symptoms are related to reduced activity in the pyrimidine biosynthetic pathway. Growth inhibition by most nucleoside base analogs tested, actinomycin D, fluorodeoxyuridine, and ethidium bromide, as compared to callusing brought on by boron deficiency and 6-azauracil, indicates that boron deficiency symptoms are not related to a reduction in nucleic acid biosynthesis. Based on this information, a discussion of the possibility that boron deficiency causes reduced synthesis of UDP-glucose is presented. Images PMID:16659987

  7. Boric acid and boronic acids inhibition of pigeonpea urease.

    PubMed

    Reddy, K Ravi Charan; Kayastha, Arvind M

    2006-08-01

    Urease from the seeds of pigeonpea was competitively inhibited by boric acid, butylboronic acid, phenylboronic acid, and 4-bromophenylboronic acid; 4-bromophenylboronic acid being the strongest inhibitor, followed by boric acid > butylboronic acid > phenylboronic acid, respectively. Urease inhibition by boric acid is maximal at acidic pH (5.0) and minimal at alkaline pH (10.0), i.e., the trigonal planar B(OH)3 form is a more effective inhibitor than the tetrahedral B(OH)4 -anionic form. Similarly, the anionic form of phenylboronic acid was least inhibiting in nature.

  8. Preparation of tert-butyl esters via Pd-catalyzed tert-butoxycarbonylation of (hetero)aryl boronic acid derivatives.

    PubMed

    Li, Xinjian; Zou, Dapeng; Zhu, Helong; Wang, Yaping; Li, Jingya; Wu, Yangjie; Wu, Yusheng

    2014-04-04

    A novel protocol to synthesize tert-butyl esters from boronic acids or boronic acid pinacol esters and di-t-butyl dicarbonate has been successfully achieved. The cross-coupling reactions can produce up to 94% yields by using palladium acetate and triphenylphosphine as catalyst system, dioxane as a solvent. Moreover, a wide range of substrates including benzenes, pyridines, and quinolines boronic acids or boronic acid pinacol esters can fit with this system as well.

  9. Proteus mirabilis urease. Partial purification and inhibition by boric acid and boronic acids.

    PubMed Central

    Breitenbach, J M; Hausinger, R P

    1988-01-01

    Urease was purified 800-fold and partially characterized from Proteus mirabilis, the predominant microorganism associated with urinary stones. Boric acid is a rapid reversible competitive inhibitor of urease. The pH-dependence of inhibition exhibited pKa values of 6.25 and 9.3, where the latter value is probably due to the inherent pKa of boric acid. Three boronic acids also were shown to inhibit urease competitively. PMID:3291857

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

    PubMed Central

    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

  11. 10-Boronic acid substituted camptothecin as prodrug of SN-38.

    PubMed

    Wang, Lei; Xie, Shao; Ma, Longjun; Chen, Yi; Lu, Wei

    2016-06-30

    Malignant tumor cells have been found to have high levels of reactive oxygen species such as hydrogen peroxide (H2O2), supporting the hypothesis that a prodrug could be activated by intracellular H2O2 and lead to a potential antitumor therapy. In this study, the 7-ethyl-10-boronic acid camptothecin (B1) was synthesized for the first time as prodrug of SN-38, by linking a cleavable aryl carbon-boron bond to the SN-38. Prodrug B1 selectively activated by H2O2, converted rapidly to the active form SN-38 under favorable oxidative conditions in cancer cells with elevated levels of H2O2. The cell survival assay showed that prodrug B1 was equally or more effective in inhibiting the growth of six different cancer cells, as compared to SN-38. Unexpectedly, prodrug B1 displayed even more potent Topo I inhibitory activity than SN-38, suggesting that it was not only a prodrug of SN-38 but also a typical Topo I inhibitor. Prodrug B1 also demonstrated a significant antitumor activity at 2.0 mg/kg in a xenograft model using human brain star glioblastoma cell lines U87MG.

  12. Highly fructose selective transport promoted by boronic acids based on a pentaerythritol core.

    PubMed

    Draffin, S P; Duggan, P J; Duggan, S A

    2001-03-22

    We have designed and synthesized a highly lipophilic boronic acid (11) with a molecular shape that makes it much more effective at carrying sugars through organic membranes than a previously used steroidal boronic acid. The corresponding diboronic acid (12) was also found to transport fructose ahead of glucose with a very high selectivity (7.6:1.0). Modeling suggests that 12 is able to carry two fructose molecules at once in a complex stabilized through hydrogen bonding and ion pairing.

  13. Exposure assessment of boron in Bandırma boric acid production plant.

    PubMed

    Duydu, Yalçin; Başaran, Nurşen; 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. Experimentally, a NOAEL of 17.5mg B/kg-bw/day (corresponds to ∼2020 ng boron/g blood) has been identified for the (male) reproductive effects of boron in a multigenerational study of rats, and a NOAEL for the developmental effects in rats was identified at 9.6 mg B/kg-bw/day (corresponds to 1270 ng boron/g blood). These values are being taken as the basis of current EU safety assessments. The present study was conducted to assess the boron exposure under extreme exposure conditions in a boric acid production plant located in Bandırma, Turkey. The mean blood boron concentrations of low and high exposure groups were 72.94 ± 15.43 (48.46-99.91) and 223.89 ± 60.49 (152.82-454.02)ng/g respectively. The mean blood boron concentration of the high exposure group is still ≈ 6 times lower than the highest no effect level of boron in blood with regard to the developmental effects in rats and ≈ 9 times lower than the highest no effect level of boron in blood with regard to the reprotoxic effects in male rats. In this context, boric acid and sodium borates should not be considered as toxic to reproduction for humans in daily life.

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

    PubMed Central

    Vancoillie, Gertjan; Hoogenboom, Richard

    2016-01-01

    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. PMID:27775572

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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 (Ka = 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.

  16. Probing the interactions between boronic acids and cis-diol-containing biomolecules by affinity capillary electrophoresis.

    PubMed

    Lü, Chenchen; Li, Hengye; Wang, Heye; Liu, Zhen

    2013-02-19

    The affinity of boronic acids to cis-diol-containing biomolecules has found wide applications in many fields, such as sensing, separation, drug delivery, and functional materials. A sound understanding of the binding interactions will greatly facilitate exquisite applications of this chemistry. Although a few analytical tools have been available for the characterization of the interactions, these techniques are associated with some apparent drawbacks, so they are only applicable to a limited range of boronic acids and cis-diol-containing biomolecules. Therefore, a widely applicable method is still greatly needed. In this work, an affinity capillary electrophoresis (ACE) method was established and validated to probe the interactions between boronic acids and cis-diol-containing biomolecules. The method was proven to be applicable to almost all types of cis-diol-containing biomolecules and boronic acids. Based on this method, a quantitative, comparative study on the interactions between 14 boronic acids that have important potentials for application with 5 typical monosaccharides of biological importance was carried out. The findings provided new insights into boronate affinity interactions, particularly the relationship between the binding strength with the molecular structures of the binding species. Besides, effects of pH and temperature on the binding strength were also investigated. This method exhibited several significant advantages, including (1) possibility of simultaneous study of multiple interactions, (2) low requirement on the purity of the binding species, (3) wide applicability, and (4) high accuracy and precision.

  17. Two forms of (naphthalen-1-yl)boronic acid.

    PubMed

    Bemisderfer, Kayleigh; Nazarenko, Alexander Y

    2016-09-01

    Two polymorphs of the title compound, C10H9BO2, were prepared by recystallization from different solvents at room temperature. Both forms demonstrate nearly identical mol-ecular structures with all naphthalene group atoms located in one plane and all boronic acid atoms in another: the dihedral angles between these planes are 39.88 (5) and 40.15 (5)° for the two asymmetric mol-ecules of the ortho-rhom-bic form and 40.60 (3)° for the single asymmetric mol-ecule in the monoclinic form. In each extended structure, mol-ecules form dimers, connected via two O-H⋯O hydrogen bonds. The dimers are connected by further O-H⋯O hydrogen bonds, forming layered networks in the (001) plane and the (100) plane in the ortho-rhom-bic and monoclinic forms, respectively. The resulting layers are practically identical in both forms. However, these layers are shifted along the [010] axis in the two forms, resulting in a slightly more effective packing for monoclinic structure (packing index = 0.692) compared to the ortho-rhom-bic form (0.688).

  18. Evaluation of unnatural cyclic amino acids as boron delivery agents for treatment of melanomas and gliomas.

    PubMed

    Barth, Rolf F; Kabalka, George W; Yang, Weilian; Huo, Tianyao; Nakkula, Robin J; Shaikh, Aarif L; Haider, Syed A; Chandra, Subhash

    2014-06-01

    Unnatural cyclic amino acids (UNAAs) are a new class of boron delivery agents that are in a pre-clinical stage of evaluation. In the present study, the biodistribution of racemic forms of the cis- and trans-isomers of the boronated UNAA 1-amino-3-boronocyclopentanecarboxylic acid (ABCPC) and 1-amino-3-boronocycloheptanecarboxylic acid (ABCHC) were evaluted in B16 melanoma bearing mice and this was compared to l-p-boronophenylalanine (BPA). Boron concentrations were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) at 2.5h following intraperitoneal (i.p.) injection of the test agents at a concentration equivalent to 24mg/B/kg. While all compounds attained comparable tumor boron concentrations, the tumor/blood (T/Bl) boron concentration ratios were far superior for both cis-ABCPC and cis-ABCHC compared to BPA (T/Bl=16.4, and 15.1 vs. 5.4). Secondary ion mass spectrometry (SIMS) imaging revealed that the cis-ABCPC delivered boron to the nuclei, as well as the cytoplasm of B16 cells. Next, a biodistribution study of cis-ABCPC and BPA was carried out in F98 glioma bearing rats following i.p. administration. Both compounds attained comparable tumor boron concentrations but the tumor/brain (T/Br) boron ratio was superior for cis-ABCPC compared to BPA (6 vs. 3.3). Since UNAAs are water soluble and cannot be metabolized by tumor cells, they could be potentially more effective boron delivery agents than BPA. Our data suggest that further studies are warranted to evaluate these compounds prior to the initiation of clinical studies.

  19. Oxygenation of Organoboronic Acids by a Nonheme Iron(II) Complex: Mimicking Boronic Acid Monooxygenase Activity.

    PubMed

    Chatterjee, Sayanti; Paine, Tapan Kanti

    2015-10-19

    Phenolic compounds are important intermediates in the bacterial biodegradation of aromatic compounds in the soil. An Arthrobacter sp. strain has been shown to exhibit boronic acid monooxygenase activity through the conversion of different substituted phenylboronic acids to the corresponding phenols using dioxygen. While a number of methods have been reported to cleave the C-B bonds of organoboronic acids, there is no report on biomimetic iron complex exhibiting this activity using dioxygen as the oxidant. In that direction, we have investigated the reactivity of a nucleophilic iron-oxygen oxidant, generated upon oxidative decarboxylation of an iron(II)-benzilate complex [(Tp(Ph2))Fe(II)(benzilate)] (Tp(Ph2) = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), toward organoboronic acids. The oxidant converts different aryl/alkylboronic acids to the corresponding oxygenated products with the incorporation of one oxygen atom from dioxygen. This method represents an efficient protocol for the oxygenation of boronic acids with dioxygen as the terminal oxidant.

  20. Real-time measurements of amino acid and protein hydroperoxides using coumarin boronic acid.

    PubMed

    Michalski, Radoslaw; Zielonka, Jacek; Gapys, Ewa; Marcinek, Andrzej; Joseph, Joy; Kalyanaraman, Balaraman

    2014-08-08

    Hydroperoxides of amino acid and amino acid residues (tyrosine, cysteine, tryptophan, and histidine) in proteins are formed during oxidative modification induced by reactive oxygen species. Amino acid hydroperoxides are unstable intermediates that can further propagate oxidative damage in proteins. The existing assays (oxidation of ferrous cation and iodometric assays) cannot be used in real-time measurements. In this study, we show that the profluorescent coumarin boronic acid (CBA) probe reacts with amino acid and protein hydroperoxides to form the corresponding fluorescent product, 7-hydroxycoumarin. 7-Hydroxycoumarin formation was catalase-independent. Based on this observation, we have developed a fluorometric, real-time assay that is adapted to a multiwell plate format. This is the first report showing real-time monitoring of amino acid and protein hydroperoxides using the CBA-based assay. This approach was used to detect protein hydroperoxides in cell lysates obtained from macrophages exposed to visible light and photosensitizer (rose bengal). We also measured the rate constants for the reaction between amino acid hydroperoxides (tyrosyl, tryptophan, and histidine hydroperoxides) and CBA, and these values (7-23 M(-1) s(-1)) were significantly higher than that measured for H2O2 (1.5 M(-1) s(-1)). Using the CBA-based competition kinetics approach, the rate constants for amino acid hydroperoxides with ebselen, a glutathione peroxidase mimic, were also determined, and the values were within the range of 1.1-1.5 × 10(3) M(-1) s(-1). Both ebselen and boronates may be used as small molecule scavengers of amino acid and protein hydroperoxides. Here we also show formation of tryptophan hydroperoxide from tryptophan exposed to co-generated fluxes of nitric oxide and superoxide. This observation reveals a new mechanism for amino acid and protein hydroperoxide formation in biological systems.

  1. Real-time Measurements of Amino Acid and Protein Hydroperoxides Using Coumarin Boronic Acid*

    PubMed Central

    Michalski, Radoslaw; Zielonka, Jacek; Gapys, Ewa; Marcinek, Andrzej; Joseph, Joy; Kalyanaraman, Balaraman

    2014-01-01

    Hydroperoxides of amino acid and amino acid residues (tyrosine, cysteine, tryptophan, and histidine) in proteins are formed during oxidative modification induced by reactive oxygen species. Amino acid hydroperoxides are unstable intermediates that can further propagate oxidative damage in proteins. The existing assays (oxidation of ferrous cation and iodometric assays) cannot be used in real-time measurements. In this study, we show that the profluorescent coumarin boronic acid (CBA) probe reacts with amino acid and protein hydroperoxides to form the corresponding fluorescent product, 7-hydroxycoumarin. 7-Hydroxycoumarin formation was catalase-independent. Based on this observation, we have developed a fluorometric, real-time assay that is adapted to a multiwell plate format. This is the first report showing real-time monitoring of amino acid and protein hydroperoxides using the CBA-based assay. This approach was used to detect protein hydroperoxides in cell lysates obtained from macrophages exposed to visible light and photosensitizer (rose bengal). We also measured the rate constants for the reaction between amino acid hydroperoxides (tyrosyl, tryptophan, and histidine hydroperoxides) and CBA, and these values (7–23 m−1 s−1) were significantly higher than that measured for H2O2 (1.5 m−1 s−1). Using the CBA-based competition kinetics approach, the rate constants for amino acid hydroperoxides with ebselen, a glutathione peroxidase mimic, were also determined, and the values were within the range of 1.1–1.5 × 103 m−1 s−1. Both ebselen and boronates may be used as small molecule scavengers of amino acid and protein hydroperoxides. Here we also show formation of tryptophan hydroperoxide from tryptophan exposed to co-generated fluxes of nitric oxide and superoxide. This observation reveals a new mechanism for amino acid and protein hydroperoxide formation in biological systems. PMID:24928516

  2. OsNIP3;1, a rice boric acid channel, regulates boron distribution and is essential for growth under boron-deficient conditions.

    PubMed

    Hanaoka, Hideki; Uraguchi, Shimpei; Takano, Junpei; Tanaka, Mayuki; Fujiwara, Toru

    2014-06-01

    Boron is an essential micronutrient for higher plants. Boron deficiency is an important agricultural issue because it results in loss of yield quality and/or quantity in cereals and other crops. To understand boron transport mechanisms in cereals, we characterized OsNIP3;1, a member of the major intrinsic protein family in rice (Oryza sativa L.), because OsNIP3;1 is the most similar rice gene to the Arabidopsis thaliana boric acid channel genes AtNIP5;1 and AtNIP6;1. Yeast cells expressing OsNIP3;1 imported more boric acid than control cells. GFP-tagged OsNIP3;1 expressed in tobacco BY2 cells was localized to the plasma membrane. The accumulation of OsNIP3;1 transcript increased fivefold in roots within 6 h of the onset of boron starvation, but not in shoots. Promoter-GUS analysis suggested that OsNIP3;1 is expressed mainly in exodermal cells and steles in roots, as well as in cells around the vascular bundles in leaf sheaths and pericycle cells around the xylem in leaf blades. The growth of OsNIP3;1 RNAi plants was impaired under boron limitation. These results indicate that OsNIP3;1 functions as a boric acid channel, and is required for acclimation to boron limitation. Boron distribution among shoot tissues was altered in OsNIP3;1 knockdown plants, especially under boron-deficient conditions. This result demonstrates that OsNIP3;1 regulates boron distribution among shoot tissues, and that the correct boron distribution is crucial for plant growth. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.

  3. Boron

    SciTech Connect

    Cozen, L.F. )

    1991-05-01

    This paper reports that borate minerals and refined borates are used extensively for the manufacture of vitreous materials such as insulation and textile fiberglasses, borosilicate glass, and porcelain enamels and frits. In North America, these applications are estimated to account for over 54% of the borate consumption. Other substantial uses are in soaps and detergents, metallurgy, fire retardants, industrial biocides, agriculture, and various miscellaneous applications. Reported domestic borate consumption in 1990 was estimated by the U.S. Bureau of Mines to be 320 000 metric tons B{sub 2}O{sub 3} versus 354 000 metric tons B{sub 2}O{sub 3} in 1989. Consumption is projected to remain essentially static in 1991. Imports were estimated by the Bureau to be 50 000 metric tons B{sub 2}O{sub 3} in 1990. Exports of boric acid and refined borates were approximately 650 000 metric tons of product, a 15 000 metric ton increase from the 1989 level. This increase partially offsets the drop in the 1990 consumption level.

  4. Photodegradation of lipopolysaccharides and the inhibition of macrophage activation by anthraquinone-boronic acid hybrids.

    PubMed

    Takahashi, Daisuke; Miura, Takuya; Toshima, Kazunobu

    2012-08-07

    Target-selective photodegradation of 3-deoxy-D-manno-2-octulopyranosonic acid (KDO) was achieved without additives and under neutral conditions using a designed anthraquinone-boronic acid hybrid and long wavelength UV light irradiation. The hybrid can photodegrade lipopolysaccharides (LPS) and inhibit macrophage activation induced by LPS.

  5. Boronic acid-tethered amphiphilic hyaluronic acid derivative-based nanoassemblies for tumor targeting and penetration.

    PubMed

    Jeong, Jae Young; Hong, Eun-Hye; Lee, Song Yi; Lee, Jae-Young; Song, Jae-Hyoung; Ko, Seung-Hak; Shim, Jae-Seong; Choe, Sunghwa; Kim, Dae-Duk; Ko, Hyun-Jeong; Cho, Hyun-Jong

    2017-02-16

    (3-Aminomethylphenyl)boronic acid (AMPB)-installed hyaluronic acid-ceramide (HACE)-based nanoparticles (NPs), including manassantin B (MB), were fabricated for tumor-targeted delivery. The amine group of AMPB was conjugated to the carboxylic acid group of hyaluronic acid (HA) via amide bond formation, and synthesis was confirmed by spectroscopic methods. HACE-AMPB/MB NPs with a 239-nm mean diameter, narrow size distribution, negative zeta potential, and >90% drug encapsulation efficiency were fabricated. Exposed AMPB in the outer surface of HACE-AMPB NPs (in the aqueous environment) may react with sialic acid of cancer cells. The improved cellular accumulation efficiency, in vitro antitumor efficacy, and tumor penetration efficiency of HACE-AMPB/MB NPs, compared with HACE/MB NPs, in MDA-MB-231 cells (CD44 receptor-positive human breast adenocarcinoma cells) may be based on the CD44 receptor-mediated endocytosis and phenylboronic acid-sialic acid interaction. Enhanced in vivo tumor targetability, infiltration efficiency, and antitumor efficacies of HACE-AMPB NPs, compared with HACE NPs, were observed in a MDA-MB-231 tumor-xenografted mouse model. In addition to passive tumor targeting (based on an enhanced permeability and retention effect) and active tumor targeting (interaction between HA and CD44 receptor), the phenylboronic acid-sialic acid interaction can play important roles in augmented tumor targeting and penetration of HACE-AMPB NPs. STATEMENT OF SIGNIFICANCE: (3-Aminomethylphenyl)boronic acid (AMPB)-tethered hyaluronic acid-ceramide (HACE)-based nanoparticles (NPs), including manassantin B (MB), were fabricated and their tumor targeting and penetration efficiencies were assessed in MDA-MB-231 (CD44 receptor-positive human adenocarcinoma) tumor models. MB, which exhibited antitumor efficacies via the inhibition of angiogenesis and hypoxia inducible factor (HIF)-1, was entrapped in HACE-AMPB NPs in this study. Phenylboronic acid located in the outer surface

  6. Molecular complexes of alprazolam with carboxylic acids, boric acid, boronic acids, and phenols. Evaluation of supramolecular heterosynthons mediated by a triazole ring.

    PubMed

    Varughese, Sunil; Azim, Yasser; Desiraju, Gautam R

    2010-09-01

    A series of molecular complexes, both co-crystals and salts, of a triazole drug-alprazolam-with carboxylic acids, boric acid, boronic acids, and phenols have been analyzed with respect to heterosynthons present in the crystal structures. In all cases, the triazole ring behaves as an efficient hydrogen bond acceptor with the acidic coformers. The hydrogen bond patterns exhibited with aromatic carboxylic acids were found to depend on the nature and position of the substituents. Being a strong acid, 2,6-dihydroxybenzoic acid forms a salt with alprazolam. With aliphatic dicarboxylic acids alprazolam forms hydrates and the water molecules play a central role in synthon formation and crystal packing. The triazole ring makes two distinct heterosynthons in the molecular complex with boric acid. Boronic acids and phenols form consistent hydrogen bond patterns, and these are seemingly independent of the substitutional effects. Boronic acids form noncentrosymmetric cyclic synthons, while phenols form O--H...N hydrogen bonds with the triazole ring.

  7. Boronic acids as probes for investigation of allosteric modulation of the chemokine receptor CXCR3.

    PubMed

    Bernat, Viachaslau; Admas, Tizita Haimanot; Brox, Regine; Heinemann, Frank W; Tschammer, Nuska

    2014-11-21

    The chemokine receptor CXCR3 is a G protein-coupled receptor, which conveys extracellular signals into cells by changing its conformation upon agonist binding. To facilitate the mechanistic understanding of allosteric modulation of CXCR3, we combined computational modeling with the synthesis of novel chemical tools containing boronic acid moiety, site-directed mutagenesis, and detailed functional characterization. The design of boronic acid derivatives was based on the predictions from homology modeling and docking. The choice of the boronic acid moiety was dictated by its unique ability to interact with proteins in a reversible covalent way, thereby influencing conformational dynamics of target biomolecules. During the synthesis of the library we have developed a novel approach for the purification of drug-like boronic acids. To validate the predicted binding mode and to identify amino acid residues responsible for the transduction of signal through CXCR3, we conducted a site-directed mutagenesis study. With the use of allosteric radioligand RAMX3 we were able to establish the existence of a second allosteric binding pocket in CXCR3, which enables different binding modes of structurally closely related allosteric modulators of CXCR3. We have also identified residues Trp109(2.60) and Lys300(7.35) inside the transmembrane bundle of the receptor as crucial for the regulation of the G protein activation. Furthermore, we report the boronic acid 14 as the first biased negative allosteric modulator of the receptor. Overall, our data demonstrate that boronic acid derivatives represent an outstanding tool for determination of key receptor-ligand interactions and induction of ligand-biased signaling.

  8. Iterative reactions of transient boronic acids enable sequential C-C bond formation.

    PubMed

    Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N; Allwood, Daniel M; Blakemore, David C; Ley, Steven V

    2016-04-01

    The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

  9. Boronic Acid Group: A Cumbersome False Negative Case in the Process of Drug Design.

    PubMed

    Katsamakas, Sotirios; Papadopoulos, Anastasios G; Hadjipavlou-Litina, Dimitra

    2016-09-07

    Herein we present, an exhaustive docking analysis considering the case of autotaxin (ATX). HA155, a small molecule inhibitor of ATX, is co-crystallized. In order to further extract conclusions on the nature of the bond formed between the ligands and the amino acid residues of the active site, density functional theory (DFT) calculations were undertaken. However, docking does not provide reproducible results when screening boronic acid derivatives and their binding orientations to protein drug targets. Based on natural bond orbital (NBO) calculations, the formed bond between Ser/Thr residues is characterized more accurately as a polar covalent bond instead of a simple nonpolar covalent one. The presented results are acceptable and could be used in screening as an active negative filter for boron compounds. The hydroxyl groups of amino acids are bonded with the inhibitor's boron atom, converting its hybridization to sp³.

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

    PubMed Central

    Wang, Xiaojin; Xia, Ning; Liu, Lin

    2013-01-01

    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. PMID:24141187

  11. Superacidity of boron acids H2(B12X12) (X = Cl, Br).

    PubMed

    Avelar, Amy; Tham, Fook S; Reed, Christopher A

    2009-01-01

    Acid remarks: The anhydrous diprotic boron acids H(2)(B(12)X(12)) (X = Cl, Br; see picture, B orange, X green) are the first examples of diprotic superacids and may be the strongest acids yet isolated. Both protons protonate benzene to give benzenium ion salts that are stable at room temperature. These acids owe their existence to the stability of the icosahedral B(12) cluster with its dinegative charge buried beneath a layer of halide substituents.

  12. Click with a boronic acid handle: a neighboring group-assisted click reaction that allows ready secondary functionalization.

    PubMed

    Draganov, Alexander B; Wang, Ke; Holmes, Jalisa; Damera, Krishna; Wang, Danzhu; Dai, Chaofeng; Wang, Binghe

    2015-10-21

    The feasibility of a neighboring boronic acid-facilitated facile condensation of an aldehyde is described. This reaction is bio-orthogonal, complete at room temperature within minutes, and suitable for bioconjugation chemistry. The boronic acid group serves the dual purpose of catalyzing the condensation reaction and being a handle for secondary functionalization.

  13. Ammonolysis of esters of hydroxybenzoic acids on a boron phosphate catalyst

    SciTech Connect

    Suvorov, B.V.; Bukeikhanov, N.R.; Li, L.V.; Zulkasheva, A.Z.

    1987-09-10

    In this investigation boron phosphate catalyst was used for ammonolysis of methyl and ethyl esters of salicylic and 4-hydroxybenzoic acids. It was shown that ammonolysis of methyl and ethyl esters of salicylic and 4-hydroxybenzoic acids in presence of boron phosphate catalyst at a ratio of 3-7 moles of ammonia per mole of ester in a contact time of 1-5 sec at 380-400/sub 0/ can be used for obtaining o- and p- hydroxybenzonitriles in yields of over 90% of the theoretical.

  14. Boronic acid shell-crosslinked dextran-b-PLA micelles for acid-responsive drug delivery.

    PubMed

    Zhao, Ziwei; Yao, Xuemei; Zhang, Zhe; Chen, Li; He, Chaoliang; Chen, Xuesi

    2014-11-01

    Herein, 3-carboxy-5-nitrophenylboronic acid (CNPBA) shell-crosslinked micelles based on amphiphilic dextran-block-polylactide (Dex-b-PLA) are prepared and used for efficient intracellular drug deliveries. Due to the reversible pH-dependent binding with diols to form boronate esters, CNPBA modified Dex-b-PLA shows excellent pH-sensitivity. In neutral aqueous conditions, CNPBA-Dex-b-PLA forms shell-crosslinked micelles to enable DOX loading, while in acid conditions, the boronate esters hydrolyze and the micelles de-crosslink to release loaded DOX. In vitro release studies indicate that the release of the DOX cargo is minimized at physiological conditions, while there is a burst release in response to low pHs. The cell viability of CNPBA-Dex-b-PLA investigated by MTT assay was more than 90%, indicating that, as a drug delivery system, CNPBA-Dex-b-PLA has good cytocompatibility. These features suggest that the pH-responsive biodegradable CNPBA-Dex-b-PLA can efficiently load and deliver DOX into tumor cells and enhance the inhibition of cellular proliferation in vitro, providing a favorable platform as a drug delivery system for cancer therapy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Boronic acid flux synthesis and crystal growth of uranium and neptunium boronates and borates: a low-temperature route to the first neptunium(V) borate.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Miller, Hannah M; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2010-11-01

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO(2)[B(3)O(4)(OH)(2)] (NpBO-1), and the first actinide boronate, UO(2)(CH(3)BO(2))(H(2)O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure.

  16. A human health risk assessment of boron (boric acid and borax) in drinking water.

    PubMed

    Murray, F J

    1995-12-01

    A human health risk assessment was conducted to derive an appropriate safe exposure level in drinking water of inorganic boron-containing compounds (boric acid and borax). Several regulatory agencies have set or plan to set drinking water guidelines or standards for boron (B). Recent publication of reproductive and developmental toxicity studies by the National Toxicology Program prompted this risk assessment, along with the understanding that boron may be nutritionally essential. A rat developmental toxicity study with a NOAEL of 9.6 mg B/kg/day was selected as the pivotal study on which to base this risk assessment, since it represents the most sensitive endpoint of toxicity. A detailed evaluation of these and other studies allowed modifications of the default values for uncertainty factors to account for the pharmacokinetic similarities among species, the lack of metabolism of inorganic boron-containing compounds, the similarity of the toxicity profile across species, the quality of the toxicological database, and other factors according to the approach described by Renwick previously. Benchmark dose calculations were performed, and the results were in close agreement with the NOAEL selected for this risk assessment. The Reference Dose was calculated to be 0.3 mg B/kg/day, resulting in an acceptable daily intake of 18 mg B/day. Considering that the U.S. average dietary intake of boron is 1.5 mg B/day, 16.5 mg B/day could be available for drinking water or other exposures, if any. A preliminary review of boron data in the National Inorganic Radionuclide Survey by the EPA indicates the median boron level in U.S. drinking water supplies to be 0.031 mg B/liter, and most exposures are less than 2.44 mg B/liter (99th percentile). It is concluded that boron in U.S. drinking water would not be expected to pose any health risk to the public.

  17. Qualitative identification of carboxylic acids, boronic acids, and amines using cruciform fluorophores.

    PubMed

    Schwaebel, Thimon; Lirag, Rio Carlo; Davey, Evan A; Lim, Jaebum; Bunz, Uwe H F; Miljanić, Ognjen Š

    2013-08-19

    Molecular cruciforms are X-shaped systems in which two conjugation axes intersect at a central core. If one axis of these molecules is substituted with electron-donors, and the other with electron-acceptors, cruciforms' HOMO will localize along the electron-rich and LUMO along the electron-poor axis. This spatial isolation of cruciforms' frontier molecular orbitals (FMOs) is essential to their use as sensors, since analyte binding to the cruciform invariably changes its HOMO-LUMO gap and the associated optical properties. Using this principle, Bunz and Miljanić groups developed 1,4-distyryl-2,5-bis(arylethynyl)benzene and benzobisoxazole cruciforms, respectively, which act as fluorescent sensors for metal ions, carboxylic acids, boronic acids, phenols, amines, and anions. The emission colors observed when these cruciform are mixed with analytes are highly sensitive to the details of analyte's structure and - because of cruciforms' charge-separated excited states - to the solvent in which emission is observed. Structurally closely related species can be qualitatively distinguished within several analyte classes: (a) carboxylic acids; (b) boronic acids, and (c) metals. Using a hybrid sensing system composed from benzobisoxazole cruciforms and boronic acid additives, we were also able to discern among structurally similar: (d) small organic and inorganic anions, (e) amines, and (f) phenols. The method used for this qualitative distinction is exceedingly simple. Dilute solutions (typically 10(-6) M) of cruciforms in several off-the-shelf solvents are placed in UV/Vis vials. Then, analytes of interest are added, either directly as solids or in concentrated solution. Fluorescence changes occur virtually instantaneously and can be recorded through standard digital photography using a semi-professional digital camera in a dark room. With minimal graphic manipulation, representative cut-outs of emission color photographs can be arranged into panels which permit quick naked

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

    PubMed

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

    2015-12-01

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Sensitive SERS glucose sensing in biological media using alkyne functionalized boronic acid on planar substrates.

    PubMed

    Kong, Kien Voon; Ho, Chris Jun Hui; Gong, Tianxun; Lau, Weber Kam On; Olivo, Malini

    2014-06-15

    In this work, we propose a novel glucose binding mechanism on a highly sensitive SERS substrate, in order to overcome challenges in specific glucose detection in bio-fluids. We make use of phenylboronic acid as a receptor for saccharide capture onto the substrate and the ability of the captured glucose molecule to undergo secondary binding with an alkyne-functionalized boronic acid to form a glucose-alkyne-boronic acid complex. The formation of this complex shows high selectivity for glucose, over other saccharides. In addition, the alkyne group of the alkyne-functionalized boronic acid exhibits a distinct Raman peak at 1996 cm(-1) in a biological silent region (1800-2800 cm(-1)) where most endogenous molecules, including glucose, show no Raman scattering, thus offering a high sensitivity over other SERS glucose sensing. The substrate offers long-term stability, as well as high SERS enhancement to the glucose-alkyne boronic acid complex on substrate. In addition, the reversibility of SERS signals at various incubation stages also shows reusability capabilities, whereas positive results in clinical urine samples demonstrate clinical feasibility. All these strongly suggest that this newly developed SERS-based assay offers great potential in glucose sensing.

  20. Boron reclamation

    SciTech Connect

    Smith, R.M.

    1980-07-01

    A process to recover high purity /sup 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.

  1. Environmental boron exposure and activity of delta-aminolevulinic acid dehydratase (ALA-D) in a newborn population.

    PubMed

    Huel, Guy; Yazbeck, Chadi; Burnel, Daniel; Missy, Pascale; Kloppmann, Wolfram

    2004-08-01

    Following boron intake, multiple effects have been observed in animal experiments. However, human data is lacking, and no data is available on the ability of boron to accumulate in fetal tissues. Positive responses in animal species suggest that developmental toxicity may be an area of concern in humans, following exposure to boron. Two hypotheses have seemed to account for the multiple effects described in scientific findings. One hypothesis is that boron is a negative regulator that influences a number of metabolic pathways by competitively inhibiting some key enzyme reactions. The other hypothesis is that boron has a role in ionic membrane transport regulations. To better understand boron potential toxicity, the present study examined the relationship between boron exposure and some key enzymes, well-known for their affinity for mineral elements, such as delta-aminolevulinic acid dehydratase (ALA-D), and two fundamental enzymes having a role in ionic membrane transport regulations (Ca-pump and Na(+)K(+)-ATPase). We investigated the potential effects of an environmental boron exposure on the activity of these enzymes in an urban population of 197 "normal" newborns. Environmental boron exposure was assessed in placental tissue. Because of the well-known inhibiting effect of lead on these enzymes, cord blood and placental lead were also analyzed. After adjustment for potential confounders, including lead, placental boron levels were negatively significantly correlated to ALA-D activity while Ca-pump and Na(+)K(+)-ATPase activities did not seem to be affected by the level of boron exposure. Given boron's ability, as a Lewis acid, to complex with hydroxyl groups, we suggest that such a mechanism would explain the inhibiting effect of boron on ALA-D.

  2. Copper-catalyzed Chan-Lam coupling between sulfonyl azides and boronic acids at room temperature.

    PubMed

    Moon, Soo-Yeon; Nam, Jungsoo; Rathwell, Kris; Kim, Won-Suk

    2014-01-17

    A mild and efficient method for the synthesis of N-arylsulfonamides in the presence of 10 mol % of CuCl is demonstrated. The reaction proceeds readily at room temperature in an open flask using a variety of sulfonyl azides and boronic acids without any base, ligand, or additive.

  3. A colorimetric pH indicators and boronic acids ensemble array for quantitative sugar analysis.

    PubMed

    Ghosh, Krishna Kanta; Yap, Eunice; Kim, Hanjo; Lee, Jun-Seok; Chang, Young-Tae

    2011-04-07

    The colorimetric response patterns of pH indicators and boronic acids ensemble array were used to analyze serial concentrations of mono-, disaccharides quantitatively. Furthermore, this ensemble array was successfully applied to quantify the sugar content in clinically used saline solutions.

  4. Nuclease stability of boron-modified nucleic acids: application to label-free mismatch detection.

    PubMed

    Reverte, Maëva; Vasseur, Jean-Jacques; Smietana, Michael

    2015-11-21

    5'-End boronic acid-modified oligonucleotides were evaluated against various nucleases at single and double stranded levels. The results show that these modifications induce a high resistance to degradation by calf-spleen and snake venom phosphodiesterases. More importantly, this eventually led to the development of a new label-free enzyme-assisted fluorescence-based method for single mismatch detection.

  5. A Three-Component Assembly Promoted by Boronic Acids Delivers a Modular Fluorophore Platform (BASHY Dyes).

    PubMed

    Santos, Fábio M F; Rosa, João N; Candeias, Nuno R; Carvalho, Cátia Parente; Matos, Ana I; Ventura, Ana E; Florindo, Helena F; Silva, Liana C; Pischel, Uwe; Gois, Pedro M P

    2015-12-22

    Invited for the cover of this issue are Uwe Pischel, Pedro Gois and co-workers at the Universities of Huelva and Lisbon. The image depicts a puzzle, which symbolizes the multicomponent reaction used to prepare a series of boronic acid salicylidenehydrazone (BASHY) dyes that are applied in cell staining. Read the full text of the article at 10.1002/chem.201503943.

  6. Cu(I)-catalyzed (11)C carboxylation of boronic acid esters: a rapid and convenient entry to (11)C-labeled carboxylic acids, esters, and amides.

    PubMed

    Riss, Patrick J; Lu, Shuiyu; Telu, Sanjay; Aigbirhio, Franklin I; Pike, Victor W

    2012-03-12

    Rapid and direct: the carboxylation of boronic acid esters with (11)CO(2) provides [(11)C]carboxylic acids as a convenient entry into [(11)C]esters and [(11)C]amides. This conversion of boronates is tolerant to diverse functional groups (e.g., halo, nitro, or carbonyl).

  7. A Boronic Acid Conjugate of Angiogenin that Shows ROS-Responsive Neuroprotective Activity.

    PubMed

    Hoang, Trish T; Smith, Thomas P; Raines, Ronald T

    2017-03-01

    Angiogenin (ANG) is a human ribonuclease that is compromised in patients with amyotrophic lateral sclerosis (ALS). ANG also promotes neovascularization, and can induce hemorrhage and encourage tumor growth. The causal neurodegeneration of ALS is associated with reactive oxygen species, which are also known to elicit the oxidative cleavage of carbon-boron bonds. We have developed a synthetic boronic acid mask that restrains the ribonucleolytic activity of ANG. The masked ANG does not stimulate endothelial cell proliferation but protects astrocytes from oxidative stress. By differentiating between the two dichotomous biological activities of ANG, this strategy could provide a viable pharmacological approach for the treatment of ALS.

  8. Separate vaporisation of boric acid and inorganic boron from tungsten sample cuvette-tungsten boat furnace followed by the detection of boron species by inductively coupled plasma mass spectrometry and atomic emission spectrometry (ICP-MS and ICP-AES).

    PubMed

    Kataoka, Hiroko; Okamoto, Yasuaki; Tsukahara, Satoshi; Fujiwara, Terufumi; Ito, Kazuaki

    2008-03-10

    Utilising extremely different vaporisation properties of boron compounds, the determination procedures of volatile boric acid and total boron using tungsten boat furnace (TBF) ICP-MS and TBF-ICP-AES have been investigated. For the determination of volatile boric acid by TBF-ICP-MS, tetramethylammonium hydroxide (TMAH, Me(4)NOH) was used as a chemical modifier to retain it during drying and ashing stages. As for the total boron, not only non-volatile inorganic boron such as boron nitride (BN), boron carbide (B(4)C), etc. but also boric acid (B(OH)(3)) was decomposed by a furnace-fusion digestion with NaOH to produce sodium salt of boron, a suitable species for the electrothermal vaporisation (ETV) procedure. The proposed method was applied to the analysis of various standard reference materials. The analytical results for various biological and steel samples are described.

  9. Growth of boric acid crystallites on the surface of boron-doped silicon carbide samples

    SciTech Connect

    Vassen, R.; Stoever, D.

    1996-06-01

    White crystallites were visually observed on fractured or polished surfaces of SiC samples (grain sizes below {approx}500 nm) during exposure to air at room temperature for several days. Characterization of the crystallites by scanning electron microscopy, secondary ion mass spectroscopy, and X-ray diffraction identified B(OH){sub 3} crystals with a strong (002) texture. The rate of boric acid formation was determined by a gravimetric experiment. The rate of weight gain increased significantly after an incubation period of 1 week. Nucleation is initially the rate-limiting process. Subsequently small B(OH){sub 3} crystals form on the surface, whose growth rate is determined by grain boundary diffusion of boron to the SiC surface. An estimated grain boundary boron to the SiC surface. An estimated grain boundary diffusion coefficient of boron in SiC was many orders of magnitude higher than extrapolated literature values.

  10. Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels.

    PubMed

    Pettignano, Asja; Grijalvo, Santiago; Häring, Marleen; Eritja, Ramon; Tanchoux, Nathalie; Quignard, Françoise; Díaz Díaz, David

    2017-03-16

    One-step functionalization of alginate with boronic acid groups allowed spontaneous formation of biocompatible hydrogels under basic conditions without additional complementary molecules or crosslinking agents. The dynamic nature of boronate ester bonds formed with vicinal diols present on alginate pyranose rings provided remarkable self-healing, injectable and multi-stimuli responsive properties to the material.

  11. Early Effects of Boron Deficiency on Indoleacetic Acid Oxidase Levels of Squash Root Tips

    PubMed Central

    Bohnsack, Charles W.; Albert, Luke S.

    1977-01-01

    The indoleacetic acid (IAA) oxidase activity of root tips of boron-sufficient, -deficient, recovering, and IAA-treated boron-sufficient squash plants (Cucurbita pepo L.) was determined. Apical and subapical root sections displayed an increase in IAA oxidase activity between 6 and 9 hours after boron was withheld, and after 24 hours the activity of the apical sections showed a 20-fold increase over +B controls. Root elongation of -B plants was inhibited before an increase in oxidase activity could be detected. Roots of plants subjected to 12 hours of -B treatment and then transferred to +B treatment for recovery regained normal elongation rates and oxidase activity within 18 to 20 hours. IAA treatment of +B plants increased IAA oxidase activity of apical and subapical root sections and also inhibited root elongation and caused symptoms similar to -B treatments. These results have demonstrated the earliest enzymic change for intact boron-deficient plants. The results are in agreement with the theory that boron deficiency symptoms may be the result of supraoptimal endogenous levels of IAA. These high levels of IAA may inhibit cell division and lead to an induction of the IAA oxidase enzyme. PMID:16659990

  12. The boron oxide{endash}boric acid system: Nanoscale mechanical and wear properties

    SciTech Connect

    Ma, X.; Unertl, W.N.; Erdemir, A.

    1999-08-01

    The film that forms spontaneously when boron oxide (B{sub 2}O{sub 3}) is exposed to humid air is a solid lubricant. This film is usually assumed to be boric acid (H{sub 3}BO{sub 3}), the stable bulk phase. We describe the nanometer-scale surface morphology, mechanical properties, and tribological properties of these films and compare them with crystals precipitated from saturated solutions of boric acid. Scanning force microscopy (SFM) and low-load indentation were the primary experimental tools. Mechanical properties and their variation with depth are reported. In all cases, the surfaces were covered with a layer that has different mechanical properties than the underlying bulk. The films formed on boron oxide showed no evidence of crystalline structure. A thin surface layer was rapidly removed, followed by slower wear of the underlying film. The thickness of this initial layer was sensitive to sample preparation conditions, including humidity. Friction on the worn surface was lower than on the as-formed surface in all cases. In contrast, the SFM tip was unable to cause any wear to the surface film on the precipitated crystals. Indentation pop-in features were common for precipitated crystals but did not occur on the films formed on boron oxide. The surface structures were more complex than assumed in models put forth previously to explain the mechanism of lubricity in the boron oxide{endash}boric acid{endash}water system. {copyright} {ital 1999 Materials Research Society.}

  13. Some Lewis acid-base adducts involving boron trifluoride as electrolyte additives for lithium ion cells

    NASA Astrophysics Data System (ADS)

    Nie, Mengyun; Madec, L.; Xia, J.; Hall, D. S.; Dahn, J. R.

    2016-10-01

    Three complexes with boron trifluoride (BF3) as the Lewis acid and different Lewis bases were synthesized and used as electrolyte additives in Li[Ni1/3Mn1/3Co1/3]O2/graphite and Li[Ni0.42Mn0.42Co0.16]O2/graphite pouch cells. Lewis acid-base adducts with a boron-oxygen (Bsbnd O) bond were trimethyl phosphate boron trifluoride (TMP-BF) and triphenyl phosphine oxide boron trifluoride (TPPO-BF). These were compared to pyridine boron trifluoride (PBF) which has a boron-nitrogen (Bsbnd N) bond. The experimental results showed that cells with PBF had the least voltage drop during storage at 4.2 V, 4.4 V and 4.7 V at 40 °C and the best capacity retention during long-term cycling at 55 °C compared to cells with the other additives. Charge-hold-discharge cycling combined with simultaneous electrochemical impedance spectroscopy measurements showed that impedance growth in TMP-BF and TPPO-BF containing cells was faster than cells containing 2%PBF, suggesting that PBF is useful for impedance control at high voltages (>4.4 V). XPS analysis of the SEI films highlighted a specific reactivity of the PBF-derived SEI species that apparently hinders the degradation of both LiPF6 and solvent during formation and charge-hold-discharge cycling. The modified SEI films may explain the improved impedance, the smaller voltage drop during storage and the improved capacity retention during cycling of cells containing the PBF additive.

  14. A Rapid Approach for Fabricating Boronic Acid-Functionalized Plates for On-Probe Detection of Glycoprotein and Glycopeptide

    PubMed Central

    Liu, Yu-Ching; Chen, Chao-Jung

    2017-01-01

    We developed a rapid and simple approach without using complex mechanical or chemical protocols to fabricate boronic acid-functionalized plates for glycoprotein or glycopeptide enrichment and mass spectrometry (MS) analysis. By coating the boronic acid-functionalized silica particles on a polydimethylsiloxane (PDMS)-coated matrix-assisted laser desorption/ionization (MALDI) plate, these particles can form a firmly monolayer of particles on PDMS membrane for sample handling without peeling off. The boronic acid particles-coated PDMS plate (BP plate) was successfully applied to the enrichment of horseradish peroxidase (HRP) protein and their digested glycopeptides. PMID:28337401

  15. One-step synthesis of boronic acid functionalized gold nanoclusters for photoluminescence sensing of dopamine

    NASA Astrophysics Data System (ADS)

    Chen, Huide; Liu, Chunxiu; Xia, Yunsheng

    2017-03-01

    This study is the first to report one-step synthesis of boronic acid functionalized gold nanoclusters (AuNCs) using mixed ligands of 4-mercaptophenylboronic acid (MPBA) and glutathione. Furthermore, the emission color of the products can be fancily tuned from green to near-infrared by simply changing the proportion of the two stabilizers. In basic media, dopamine (DA) molecules themselves polymerize each other and form polydopamine with large amounts of cis-diol groups, which then react with boronic acid groups on the AuNC’s surface based on the formation of boronate esters. As a result, the photoluminescence of the AuNCs is well quenched by the electron transfer effect. Accordingly, DA molecules are assayed from 0.5 to 9 μM, and the detection limit is as low as 0.1 μM. The as-prepared AuNCs exhibit high selectivity; the existing biomolecules including various amino acids, ascorbic acid, uric acid, glucose, etc, do not interfere with the assay. The proposed method is successfully applied to the assay of DA in human serum, indicating its practical potential.

  16. Synthesis and in vitro evaluation of thiododecaborated α, α- cycloalkylamino acids for the treatment of malignant brain tumors by boron neutron capture therapy.

    PubMed

    Hattori, Yoshihide; Kusaka, Shintaro; Mukumoto, Mari; Ishimura, Miki; Ohta, Yoichiro; Takenaka, Hiroshi; Uehara, Kouki; Asano, Tomoyuki; Suzuki, Minoru; Masunaga, Shin-Ichiro; Ono, Koji; Tanimori, Shinji; Kirihata, Mitsunori

    2014-12-01

    Boron-neutron capture therapy (BNCT) is an attractive technique for cancer treatment. As such, α, α-cycloalkyl amino acids containing thiododecaborate ([B12H11](2-)-S-) units were designed and synthesized as novel boron delivery agents for BNCT. In the present study, new thiododecaborate α, α-cycloalkyl amino acids were synthesized, and biological evaluation of the boron compounds as boron carrier for BNCT was carried out.

  17. Facile synthesis of boronic acid-functionalized magnetic carbon nanotubes for highly specific enrichment of glycopeptides

    NASA Astrophysics Data System (ADS)

    Ma, Rongna; Hu, Junjie; Cai, Zongwei; Ju, Huangxian

    2014-02-01

    A stepwise strategy was developed to synthesize boronic acid functionalized magnetic carbon nanotubes (MCNTs) for highly specific enrichment of glycopeptides. The MCNTs were synthesized by a solvothermal reaction of Fe3+ loaded on the acid-treated CNTs and modified with 1-pyrenebutanoic acid N-hydroxysuccinimidyl ester (PASE) to bind aminophenylboronic acid (APBA) via an amide reaction. The introduction of PASE could bridge the MCNT and APBA, suppress the nonspecific adsorption and reduce the steric hindrance among the bound molecules. Due to the excellent structure of the MCNTs, the functionalization of PASE and then APBA on MCNTs was quite simple, specific and effective. The glycopeptides enrichment and separation with a magnetic field could be achieved by their reversible covalent binding with the boronic group of APBA-MCNTs. The exceptionally large specific surface area and the high density of boronic acid groups of APBA-MCNTs resulted in rapid and highly efficient enrichment of glycopeptides, even in the presence of large amounts of interfering nonglycopeptides. The functional MCNTs possessed high selectivity for enrichment of 21 glycopeptides from the digest of horseradish peroxidase demonstrated by MALDI-TOF mass spectrometric analysis showing more glycopeptides detected than the usual 9 glycopeptides with commercially available APBA-agarose. The proposed system showed better specificity for glycopeptides even in the presence of non-glycopeptides with 50 times higher concentration. The boronic acid functionalized MCNTs provide a promising selective enrichment platform for precise glycoproteomic analysis.A stepwise strategy was developed to synthesize boronic acid functionalized magnetic carbon nanotubes (MCNTs) for highly specific enrichment of glycopeptides. The MCNTs were synthesized by a solvothermal reaction of Fe3+ loaded on the acid-treated CNTs and modified with 1-pyrenebutanoic acid N-hydroxysuccinimidyl ester (PASE) to bind aminophenylboronic acid

  18. Characterization of the binding strengths between boronic acids and cis-diol-containing biomolecules by affinity capillary electrophoresis.

    PubMed

    Lü, Chenchen; Liu, Zhen

    2015-01-01

    The affinity of boronic acids toward cis-diol-containing biomolecules has found wide applications in many fields, such as sensing, separation, drug delivery, and functional materials. A sound understanding of the binding interactions will greatly facilitate exquisite applications of this chemistry. Traditional techniques are associated with some apparent drawbacks, so they are only applicable to a limited range of boronic acids and cis-diol-containing biomolecules. This chapter describes an affinity capillary electrophoresis (ACE) method for the characterization of the binding strengths between boronic acids and cis-diol-containing biomolecules. As compared with existing approaches, such as (11)B NMR, the ACE method exhibits several significant advantages: (1) possibility of simultaneous study of multiple interactions, (2) low requirement on the purity of the binding species, (3) widely applicable to almost all types of cis-diol-containing compounds and boronic acids, and (4) high accuracy and precision.

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

    PubMed

    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.

  20. Stereoselective formation of trisubstituted vinyl boronate esters by the acid-mediated elimination of α-hydroxyboronate esters.

    PubMed

    Guan, Weiye; Michael, Alicia K; McIntosh, Melissa L; Koren-Selfridge, Liza; Scott, John P; Clark, Timothy B

    2014-08-01

    The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki-Miyaura coupling reaction to obtain alkenes of known geometry.

  1. Stereoselective Formation of Trisubstituted Vinyl Boronate Esters by the Acid-Mediated Elimination of α-Hydroxyboronate Esters

    PubMed Central

    2015-01-01

    The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki–Miyaura coupling reaction to obtain alkenes of known geometry. PMID:24915498

  2. Exploring the potential of boronic acids as inhibitors of OXA-24/40 β-lactamase.

    PubMed

    Werner, Josephine P; Mitchell, Joshua M; Taracila, Magdalena A; Bonomo, Robert A; Powers, Rachel A

    2017-03-01

    β-lactam antibiotics are crucial to the management of bacterial infections in the medical community. Due to overuse and misuse, clinically significant bacteria are now resistant to many commercially available antibiotics. The most widespread resistance mechanism to β-lactams is the expression of β-lactamase enzymes. To overcome β-lactamase mediated resistance, inhibitors were designed to inactivate these enzymes. However, current inhibitors (clavulanic acid, tazobactam, and sulbactam) for β-lactamases also contain the characteristic β-lactam ring, making them susceptible to resistance mechanisms employed by bacteria. This presents a critical need for novel, non-β-lactam inhibitors that can circumvent these resistance mechanisms. The carbapenem-hydrolyzing class D β-lactamases (CHDLs) are of particular concern, given that they efficiently hydrolyze potent carbapenem antibiotics. Unfortunately, these enzymes are not inhibited by clinically available β-lactamase inhibitors, nor are they effectively inhibited by the newest, non-β-lactam inhibitor, avibactam. Boronic acids are known transition state analog inhibitors of class A and C β-lactamases, and are not extensively characterized as inhibitors of class D β-lactamases. Importantly, boronic acids provide a novel way to potentially inhibit class D β-lactamases. Sixteen boronic acids were selected and tested for inhibition of the CHDL OXA-24/40. Several compounds were identified as effective inhibitors of OXA-24/40, with Ki values as low as 5 μM. The X-ray crystal structures of OXA-24/40 in complex with BA3, BA4, BA8, and BA16 were determined and revealed the importance of interactions with hydrophobic residues Tyr112 and Trp115. These boronic acids serve as progenitors in optimization efforts of a novel series of inhibitors for class D β-lactamases.

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

    PubMed

    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.

  4. Boronic Acid Flux Synthesis and Crystal Growth of Uranium and Neptunium Boronates and Borates: A Low Temperature Route to the First Neptunium(V) Borate

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Miller, Hannah M.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2010-10-04

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO2[B3O4(OH)2] (NpBO-1), and the first actinide boronate, UO2(CH3BO2)(H2O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure.

  5. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions.

    PubMed

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu

    2015-06-10

    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst.

  6. A Three-Component Assembly Promoted by Boronic Acids Delivers a Modular Fluorophore Platform (BASHY Dyes).

    PubMed

    Santos, Fábio M F; Rosa, João N; Candeias, Nuno R; Carvalho, Cátia Parente; Matos, Ana I; Ventura, Ana E; Florindo, Helena F; Silva, Liana C; Pischel, Uwe; Gois, Pedro M P

    2016-01-26

    The modular assembly of boronic acids with Schiff-base ligands enabled the construction of innovative fluorescent dyes [boronic acid salicylidenehydrazone (BASHY)] with suitable structural and photophysical properties for live cell bioimaging applications. This reaction enabled the straightforward synthesis (yields up to 99%) of structurally diverse and photostable dyes that exhibit a polarity-sensitive green-to-yellow emission with high quantum yields of up to 0.6 in nonpolar environments. These dyes displayed a high brightness (up to 54,000 M(-1) cm(-1)). The promising structural and fluorescence properties of BASHY dyes fostered the preparation of non-cytotoxic, stable, and highly fluorescent poly(lactide-co-glycolide) nanoparticles that were effectively internalized by dendritic cells. The dyes were also shown to selectively stain lipid droplets in HeLa cells, without inducing any appreciable cytotoxicity or competing plasma membrane labeling; this confirmed their potential as fluorescent stains.

  7. 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.

    PubMed

    Chiriac, Constantin I; Tanasa, Fulga; Onciu, Marioara

    2005-02-28

    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 degrees C) for 8-12 hours.

  8. A multi-stimuli responive, self-assembling, boronic acid dipeptide

    DOE PAGES

    Jones, Brad Howard; Martinez, Alina Marissa; Wheeler, Jill S.; ...

    2015-08-11

    Modification of the dipeptide of phenylalanine, FF, with a boronic acid (BA) functionality imparts unique aqueous self-assembly behavior that responds to multiple stimuli. Changes in pH and ionic strength are used to trigger hydrogelation via the formation of nanoribbon networks. Thus, we show for the first time that the binding of polyols to the BA functionality can modulate a peptide between its assembled and disassembled states.

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

    PubMed

    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.

  10. Design and reactions of a carbon Lewis base/boron Lewis acid frustrated Lewis pair.

    PubMed

    Möricke, Jennifer; Wibbeling, Birgit; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

    2017-08-28

    The conjugated dienamine 4 selectively adds Piers' borane [HB(C6F5)2] to give the enamine/borane system 5, which features a boratirane structure by internal enamine carbon Lewis base to boron Lewis acid interaction. Compound 5 behaves as a C/B frustrated Lewis pair and undergoes typical addition reactions to benzaldehyde, several nitriles and to sulfur dioxide.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  11. Removal of boron from aqueous solution using magnetic carbon nanotube improved with tartaric acid

    PubMed Central

    2014-01-01

    Boron removal capacity of multi-walled carbon nanotubes (MWCNTs) modified with tartaric acid was investigated in this study. Modification of MWCNTs with tartaric acid was confirmed by Boehm surface chemistry method and fourier transform infra-red (FT-IR) spectroscopy. Experiments were performed to determine the adsorption isotherm and adsorption thermodynamic parameters of boron adsorption on tartaric acid modified MWCNTs (TA-MWCNTs). The effect of variables including initial pH, dosage of adsorbent, contact time and temperature was investigated. Analysis of data showed that adsorption equilibrium could be better described by Freundlich isotherm and the maximum adsorption capacities obtained at the pH of 6.0 was 1.97 mg/g. The estimated thermodynamic values of free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated a spontaneous and an endothermic process. Furthermore, the TA-MWCNTs was magnetized for separation of boron-contaminated adsorbent from aqueous solution by applying magnetic field. The results showed that magnetic TA-MWCNTs particles were separated effectively after adsorption from contaminated water. PMID:24393401

  12. Novel impedimetric dopamine biosensor based on boronic acid functional polythiophene modified electrodes.

    PubMed

    Dervisevic, Muamer; Senel, Mehmet; Cevik, Emre

    2017-03-01

    In this study we report a new, simple and first impedimetric biosensor based on 3-Thienyl boronic acid for dopamine detection. Biosensor electrode preparation is 1min long by simple electro-polymerization of 3-Thienyl boronic acid and copolymer Thiophene P(TBA0.50Th0.50). Strong interaction between dopamine and thin layer of boronic acid has provided bio-sensing electrode high selectivity and stability, linear range of 7.8 to 125μM, and detection limit of 0.3μM. Characterization and optimization studies were conducted using electrochemical impedance spectroscopy (EIS) and cyclic voltammogram (CV). In order to test reliability of proposed biosensor real sample application study has been conducted using non-diluted human urine and it has been found that biosensor selectivity and recovery is excellent. As well P(TBA0.50Th0.50) based electrode and dopamine interaction has been proven by single frequency impedance measurements. Biosensors acquired good reproducibility, stability, selectivity and very low interference.

  13. Determination of boron in produced water using the carminic acid assay.

    PubMed

    Floquet, Cedric F A; Sieben, Vincent J; MacKay, Bruce A; Mostowfi, Farshid

    2016-04-01

    Using the carminic acid assay, we determined the concentration of boron in oilfield waters. We investigated the effect of high concentrations of salts and dissolved metals on the assay performance. The influence of temperature, development time, reagent concentration, and water volume was studied. Ten produced and flowback water samples of different origins were measured, and the method was successfully validated against ICP-MS measurements. In water-stressed regions, produced water is a potential source of fresh water for irrigation, industrial applications, or consumption. Therefore, boron concentration must be determined and controlled to match the envisaged waste water reuse. Fast, precise, and onsite measurements are needed to minimize errors introduced by sample transportation to laboratories. We found that the optimum conditions for our application were a 5:1 mixing volume ratio (reagent to sample), a 1 g L(-1) carminic acid concentration in 99.99% sulfuric acid, and a 30 min reaction time at ambient temperature (20 °C to 23 °C). Absorption values were best measured at 610 nm and 630 nm and baseline corrected at 865 nm. Under these conditions, the sensitivity of the assay to boron was maximized while its cross-sensitivity to dissolved titanium, iron, barium and zirconium was minimized, alleviating the need for masking agents and extraction methods. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Benchtop monitoring of reaction progress via visual recognition with a handheld UV lamp: in situ monitoring of boronic acids in the Suzuki-Miyaura reaction.

    PubMed

    Barder, Timothy E; Buchwald, Stephen L

    2007-01-04

    [reaction: see text] Although boronic acids are widely used in metal-catalyzed reactions, it is difficult to assay their consumption. As such, we developed a reversible fluorescent sensor that is activated upon binding a boronic acid. The sensor can be used to monitor consumption of a boronic acid in Suzuki-Miyaura reactions. Importantly, only a standard handheld long-wave UV lamp (365 nm) is required and fluorescence is easily detectable with the naked eye without disturbing the reaction mixture.

  15. A new boron compound (guanidine biboric acid adduct) as an antitumour agent against Ehrlich ascites carcinoma in mice.

    PubMed

    Ghosh, P; Sur, B; Bag, S P; Sur, P

    1999-01-01

    The inhibitory effects of a new boron compound of guanidine biboric acid adduct (GB) and guanidium chloride (L1) on the growth of ascites tumour in female Swiss mice were studied by monitoring the survival, tumour weight, tumour cell count, transplantability of Ehrlich ascites cells, precursor incorporation and the haematological parameters of the treated mice. 5-Fluorouracil, a known anticancer drug, was used as a positive control. The most important parameter was the survival time, which increased significantly when tumour-bearing mice were treated with the boron compound. Haematological parameters of the treated animals showed minimum toxic effects when boron was coupled with guanidine.

  16. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    DOE PAGES

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; ...

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  17. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    SciTech Connect

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; Miller, Lance Lee; Alam, Todd M.; Spoerke, Erik David

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  18. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water.

    PubMed

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun

    2009-01-01

    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated.

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

    PubMed Central

    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

  20. Hyaluronan/Tannic Acid Nanoparticles Via Catechol/Boronate Complexation as a Smart Antibacterial System.

    PubMed

    Montanari, Elita; Gennari, Arianna; Pelliccia, Maria; Gourmel, Charlotte; Lallana, Enrique; Matricardi, Pietro; McBain, Andrew J; Tirelli, Nicola

    2016-12-01

    Nanoparticles based on hyaluronic acid (HA) are designed to deliver tannic acid (TA) as an antimicrobial agent. The presence of HA makes these particles potentially useful to target bacteria that colonize cells presenting HA membrane receptors (e.g. CD44), such as macrophages. HA bearing 3-aminophenyl boronic acid groups (HA-APBA) is reacted with TA, yielding nanoparticles with a size that decreases with decreasing HA molecular weight (e.g. 200 nm for 44 kDa, 400 nm for 737 kDa). The boronate esters make the nanoparticles stable at physiological pH, but their hydrolysis in an acidic environment (pH = 5) leads to swelling/solubilization, therefore potentially allowing TA release in endosomal compartments. We have assessed the nanoparticle toxicity profile (on RAW 264.7 macrophages) and their antimicrobial activity (on E. coli and on both methicillin-sensitive and -resistant S. aureus). The antibacterial effect of HA-APBA/TA nanoparticles was significantly higher than that of TA alone, and has very similar activity to TA coformulated with a reducing agent (ascorbic acid), which indicates both the nanoparticles to protect TA catechols from oxidation, and the effective release of TA after nanoparticle internalization. Therefore, there is potential for these nanoparticles to be used in stable, effective, and potentially targetable nanoparticle-based antimicrobial formulations.

  1. A new boronic acid based fluorescent reporter for catechol.

    PubMed

    Wu, Zhongyu; Li, Minyong; Fang, Hao; Wang, Binghe

    2012-12-01

    Catechol skeleton widely exists in natural products and bioactive substances. Fluorescent reporters which could recognize catechol are very promising for the construction of chemosensors to detect catechol and its derivatives in biological environment. Herein, we reported a novel catechol reporter, 2-(4-boronophenyl)quinoline-4-carboxylic acid, which exhibits significant fluorescent property changes upon binding catechol containing molecules in an aqueous solution.

  2. Boronic acid-containing aminopyridine- and aminopyrimidinecarboxamide CXCR1/2 antagonists: Optimization of aqueous solubility and oral bioavailability.

    PubMed

    Schuler, Aaron D; Engles, Courtney A; Maeda, Dean Y; Quinn, Mark T; Kirpotina, Liliya N; Wicomb, Winston N; Mason, S Nicholas; Auten, Richard L; Zebala, John A

    2015-09-15

    The chemokine receptors CXCR1 and CXCR2 are important pharmaceutical targets due to their key roles in inflammatory diseases and cancer progression. We have previously identified 2-[5-(4-fluoro-phenylcarbamoyl)-pyridin-2-ylsulfanylmethyl]-phenylboronic acid (SX-517) and 6-(2-boronic acid-5-trifluoromethoxy-benzylsulfanyl)-N-(4-fluoro-phenyl)-nicotinamide (SX-576) as potent non-competitive boronic acid-containing CXCR1/2 antagonists. Herein we report the synthesis and evaluation of aminopyridine and aminopyrimidine analogs of SX-517 and SX-576, identifying (2-{(benzyl)[(5-boronic acid-2-pyridyl)methyl]amino}-5-pyrimidinyl)(4-fluorophenylamino)formaldehyde as a potent chemokine antagonist with improved aqueous solubility and oral bioavailability.

  3. Reversible lysine modification on proteins by using functionalized boronic acids.

    PubMed

    Cal, Pedro M S D; Frade, Raquel F M; Cordeiro, Carlos; Gois, Pedro M P

    2015-05-26

    Iminoboronates have been utilized to successfully install azide and alkyne bioorthogonal functions on proteins, which may then be further reacted with their bioorthogonal counterparts. These constructs were also used to add polyethylene glycol (PEG) to insulin, a modification which has been shown to be reversible in the presence of fructose. Finally, iminoboronates were used to assemble a folic acid/paclitaxel small-molecule/drug conjugate in situ with an IC50  value of 20.7 nM against NCI-H460 cancer cells and negligible cytotoxicity against the CRL-1502 noncancer cells.

  4. Cross-coupling reactions of aryl pivalates with boronic acids.

    PubMed

    Quasdorf, Kyle W; Tian, Xia; Garg, Neil K

    2008-11-05

    The first cross-coupling of acylated phenol derivatives has been achieved. In the presence of an air-stable Ni(II) complex, readily accessible aryl pivalates participate in the Suzuki-Miyaura coupling with arylboronic acids. The process is tolerant of considerable variation in each of the cross-coupling components. In addition, a one-pot acylation/cross-coupling sequence has been developed. The potential to utilize an aryl pivalate as a directing group has also been demonstrated, along with the ability to sequentially cross-couple an aryl bromide followed by an aryl pivalate, using palladium and nickel catalysis, respectively.

  5. Enantioselective Additions of Boronates to Chromene Acetals Catalyzed by a Chiral Brønsted acid-Lewis acid System

    PubMed Central

    Moquist, Philip N.; Kodama, Tomohiro; Schaus, Scott E.

    2011-01-01

    Chiral α,β-dihydroxy carboxylic acids catalyze the enantioselective addition of alkenyl- and aryl boronates to chromene acetals. The optimal carboxylic acid is a tartaric acid amide, easily synthesized via a 3-step procedure. The reaction is enhanced by the addition of Lanthanide triflate salts such as cerium(IV)-and ytterbium(III) triflate. The chiral Brønsted acid and metal Lewis acid may be used in as low as 5 mol % relative to acetal substrate. Optimization of the reaction conditions can lead to yields >70% and enantiomeric ratios as high as 99:1. Spectroscopic and kinetic mechanistic studies demonstrate an exchange process leading to a reactive dioxoborolane intermediate leading to enantioselective addition to the pyrylium generated from the chromene acetal. PMID:20721997

  6. Nanoparticle-enhanced fluorescence emission for non-separation assays of carbohydrates using a boronic acid-alizarin complex.

    PubMed

    Li, Qianjin; Kamra, Tripta; Ye, Lei

    2016-03-04

    Addition of crosslinked polymer nanoparticles into a solution of a 3-nitrophenylboronic acid-alizarin complex leads to significant enhancement of fluorescence emission. Using the nanoparticle-enhanced boronic acid-alizarin system has improved greatly the sensitivity and extended the dynamic range of separation-free fluorescence assays for carbohydrates.

  7. Selectivity of boron carriers for boron neutron capture therapy: pharmacological studies with borocaptate sodium, L-boronophenylalanine and boric acid in murine tumors.

    PubMed

    Gregoire, V; Begg, A C; Huiskamp, R; Verrijk, R; Bartelink, H

    1993-04-01

    Borocaptate sodium (BSH) and L-boronophenylalanine (L-BPA) are two boron carriers used for boron neutron capture therapy (BNCT) in the treatment of glioblastoma and melanoma, respectively. The suitability of these two compounds was evaluated on the basis of pharmacokinetic studies aiming at characterizing their biodistribution, tumor uptake and tumor selectivity. Boric acid was also used as a reference compound since it is nonselective and relatively freely diffusible. The compounds were investigated in two tumor models, a B16 pigmented melanoma and the RIF1 sarcoma. Mice were sacrificed after different boron doses at various post-injection times and tissue and plasma levels measured using inductively coupled plasma atomic emission spectroscopy (ICP-AES). The proposed minimum effective tumor boron concentration of 15 ppm was achieved in both tumor models for the three compounds tested, although only for L-BPA in the melanoma was this achieved when tumor-plasma ratios were above 1. In the RIF1 model, maximum tumor concentrations of 44 and 31 ppm B were reached after administration of 50 micrograms B/g body weight for boric acid and BSH, respectively. After administration of 12.5 micrograms B/g of L-BPA, maximum concentrations of 15 and 21 ppm were found in the RIF1 and B16 models, respectively. Tumor-plasma ratios (TPR) for BSH remained close to or below unity at all times studied in both tumors. Brain levels of BSH were very low, however, leading to tumor-brain ratios markedly greater than 1 at all times. L-BPA and boric acid showed TPR values above unity in both tumor models, reaching 3.2 in B16.(ABSTRACT TRUNCATED AT 250 WORDS)

  8. The role of boronic acids in accelerating condensation reactions of α-effect amines with carbonyls.

    PubMed

    Gillingham, Dennis

    2016-08-10

    A broad palette of bioconjugation reactions are available for chemical biologists, but an area that still requires investigation is high-rate constant reactions. These are indispensable in certain applications, particularly for in vivo labelling. Appropriately positioned boronic acids accelerate normally sluggish Schiff base condensations of α-effect nucleophiles by five orders of magnitude - providing a new entry to the rare set of reactions that have a rate constant above 100 M(-1) s(-1) under physiological conditions. I summarize here a number of recent reports, including work from my own group, and outline a mechanistic picture that explains the differing behaviour of seemingly similar substrate classes.

  9. Catalyzed asymmetric aryl transfer reactions to aldehydes with boronic acids as aryl source.

    PubMed

    Bolm, Carsten; Rudolph, Jens

    2002-12-18

    Chiral diaryl methanols are important intermediates for the synthesis of biologically active compounds. Here, we describe a flexible method for their catalyzed asymmetric synthesis from readily available starting materials. Noteworthy is the fact that with a single catalyst both enantiomers of the product are accessible simply by choosing the appropriate combination of aryl boronic acid or aldehyde as aryl donor and acceptor, respectively. The catalysis with a planar-chiral ferrocene is easy to perform and yields a broad range of products with excellent enantioselectivities (up to 98% ee).

  10. Not all boronic acids with a five-membered cycle induce tremor, neuronal damage and decreased dopamine.

    PubMed

    Pérez-Rodríguez, Maribel; García-Mendoza, Esperanza; Farfán-García, Eunice D; Das, Bhaskar C; Ciprés-Flores, Fabiola J; Trujillo-Ferrara, José G; Tamay-Cach, Feliciano; Soriano-Ursúa, Marvin A

    2017-06-06

    Several striatal toxins can be used to induce motor disruption. One example is MPTP (1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine), whose toxicity is accepted as a murine model of parkinsonism. Recently, 3-Thienylboronic acid (3TB) was found to produce motor disruption and biased neuronal damage to basal ganglia in mice. The aim of this study was to examine the toxic effects of four boronic acids with a close structural relationship to 3TB (all having a five-membered cycle), as well as boric acid and 3TB. These boron-containing compounds were compared to MPTP regarding brain access, morphological disruption of the CNS, and behavioral manifestations of such disruption. Data was collected through acute toxicity evaluations, motor behavior tests, necropsies, determination of neuronal survival by immunohistochemistry, Raman spectroscopic analysis of brain tissue, and HPLC measurement of dopamine in substantia nigra and striatum tissue. Each compound showed a distinct profile for motor disruption. For example, motor activity was not disrupted by boric acid, but was decreased by two boronic acids (caused by a sedative effect). 3TB, 2-Thienyl and 2-furanyl boronic acid gave rise to shaking behavior. The various manifestations generated by these compounds can be linked, in part, to different levels of dopamine (measured by HPLC) and degrees of neuronal damage in the basal ganglia and cerebellum. Clearly, motor disruption is not induced by all boronic acids with a five-membered cycle as substituent. Possible explanations are given for the diverse chemico-morphological changes and degrees of disruption of the motor system, considering the role of boron and the structure-toxicity relationship. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Stilbene Boronic Acids Form a Covalent Bond with Human Transthyretin and Inhibit Its Aggregation.

    PubMed

    Smith, Thomas P; Windsor, Ian W; Forest, Katrina T; Raines, Ronald T

    2017-09-28

    Transthyretin (TTR) is a homotetrameric protein. Its dissociation into monomers leads to the formation of fibrils that underlie human amyloidogenic diseases. The binding of small molecules to the thyroxin-binding sites in TTR stabilizes the homotetramer and attenuates TTR amyloidosis. Herein, we report on boronic acid-substituted stilbenes that limit TTR amyloidosis in vitro. Assays of affinity for TTR and inhibition of its tendency to form fibrils were coupled with X-ray crystallographic analysis of nine TTR·ligand complexes. The ensuing structure-function data led to a symmetrical diboronic acid that forms a boronic ester reversibly with serine 117. This diboronic acid inhibits fibril formation by both wild-type TTR and a common disease-related variant, V30M TTR, as effectively as does tafamidis, a small-molecule drug used to treat TTR-related amyloidosis in the clinic. These findings establish a new modality for covalent inhibition of fibril formation and illuminate a path for future optimization.

  12. Highly sensitive detection of cancer cells with an electrochemical cytosensor based on boronic acid functional polythiophene.

    PubMed

    Dervisevic, Muamer; Senel, Mehmet; Sagir, Tugba; Isik, Sevim

    2017-04-15

    The detection of cancer cells through important molecular recognition target such as sialic acid is significant for the clinical diagnosis and treatment. There are many electrochemical cytosensors developed for cancer cells detection but most of them have complicated fabrication processes which results in poor reproducibility and reliability. In this study, a simple, low-cost, and highly sensitive electrochemical cytosensor was designed based on boronic acid-functionalized polythiophene. In cytosensors fabrication simple single-step procedure was used which includes coating pencil graphite electrode (PGE) by means of electro-polymerization of 3-Thienyl boronic acid and Thiophen. Electrochemical impedance spectroscopy and cyclic voltammetry were used as an analytical methods to optimize and measure analytical performances of PGE/P(TBA0.5Th0.5) based electrode. Cytosensor showed extremely good analytical performances in detection of cancer cells with linear rage of 1×10(1) to 1×10(6) cellsmL(-1) exhibiting low detection limit of 10 cellsmL(-1) and incubation time of 10min. Next to excellent analytical performances, it showed high selectivity towards AGS cancer cells when compared to HEK 293 normal cells and bone marrow mesenchymal stem cells (BM-hMSCs). This method is promising for future applications in early stage cancer diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. N-Substituted Imines by the Copper-Catalyzed N-Imination of Boronic Acids and Organostannanes with O-Acyl Ketoximes

    PubMed Central

    Liu, Songbai; Yu, Ying; Liebeskind, Lanny S.

    2009-01-01

    Catalytic quantities of copper (I) or copper (II) sources catalyze the N-imination of boronic acids and organostannanes through reaction with oxime O-carboxylates under non-basic conditions. This method tolerates various functional groups and takes place efficiently using aryl, heteroaryl, and alkenyl boronic acids and stannanes. PMID:17444649

  14. Crystal structure of the boronic acid-based proteasome inhibitor bortezomib in complex with the yeast 20S proteasome.

    PubMed

    Groll, Michael; Berkers, Celia R; Ploegh, Hidde L; Ovaa, Huib

    2006-03-01

    The dipeptide boronic acid bortezomib, also termed VELCADE, is a proteasome inhibitor now in use for the treatment of multiple myeloma, and its use for the treatment of other malignancies is being explored. We determined the crystal structure of the yeast 20S proteasome in complex with bortezomib to establish the specificity and binding mode of bortezomib to the proteasome's different catalytically active sites. This structure should enable the rational design of new boronic acid derivatives with improved affinities and specificities for individual active subunits.

  15. Electrochemical incineration of sulfanilic acid at a boron-doped diamond anode.

    PubMed

    El-Ghenymy, Abdellatif; Arias, Conchita; Cabot, Pere Lluís; Centellas, Francesc; Garrido, José Antonio; Rodríguez, Rosa María; Brillas, Enric

    2012-06-01

    The anodic oxidation of sulfanilic acid solutions has been studied in acidic medium using a divided cell with a boron-doped diamond (BDD) anode and a stainless steel cathode. Overall mineralization was achieved under all experimental conditions tested due to the efficient destruction of sulfanilic acid and all its by-products with hydroxyl radicals generated at the BDD anode from water oxidation. The alternative use of an undivided cell with the same electrodes gave rise to the coating of the cathode with polymeric compounds, thus preventing the complete electrochemical incineration of sulfanilic acid. The solutions treated in the anodic compartment of the divided cell were degraded at similar rate under pH regulation within the pH interval 2.0-6.0. The mineralization current efficiency was enhanced when the applied current decreased and the initial substrate concentration increased. The decay of sulfanilic acid was followed by reversed-phase HPLC, showing a pseudo first-order kinetics. Hydroquinone and p-benzoquinone were identified as aromatic intermediates by gas chromatography-mass spectrometry and/or reversed-phase HPLC. Maleic, acetic, formic, oxalic and oxamic acids were detected as generated carboxylic acids by ion-exclusion HPLC. Ionic chromatographic analysis of electrolyzed solutions revealed that the N content of sulfanilic acid was mainly released as NH(4)(+) ion and in much smaller proportion as NO(3)(-) ion. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Universal solid-phase approach for the immobilization, derivatization, and resin-to-resin transfer reactions of boronic acids.

    PubMed

    Gravel, Michel; Thompson, Kim A; Zak, Mark; Bérubé, Christian; Hall, Dennis G

    2002-01-11

    Boronic acid-containing molecules are employed in a broad range of biological, medicinal, and synthetic applications. These compounds, however, tend to be difficult to handle by solution-phase methods. Herein, this problem is addressed with the development of the first general solid-phase approach for the derivatization of functionalized boronic acids. This approach is based on the use of a diethanolamine resin anchor that facilitates boronic acid immobilization by avoiding the need for exhaustive removal of water in the esterification process. The immobilization of a wide variety of boronic acids onto N,N-diethanolaminomethyl polystyrene (DEAM-PS, 1) can be performed within minutes by simple stirring in anhydrous solvents at room temperature. Evidence for the formation of a bicyclic diethanolamine boronate with putative N-B coordination was shown by (1)H NMR analysis of DEAM-PS-supported p-tolylboronic acid. The hydrolytic cleavage of the same model boronic acid from the DEAM-PS resin was studied by UV spectroscopy. Hydrolysis and attachment were shown to occur under a rapidly attained equilibrium, and a large excess of water (>32 equiv) is required to effect a practically quantitative release of boronic acids from DEAM-PS. Despite their relative sensitivity to water and alcohols, DEAM-PS-bound arylboronic acids functionalized with a formyl, a bromomethyl, a carboxyl, or an amino group can be transformed in good to excellent yields into a wide variety of amines, amides, anilides, and ureas, respectively. Ugi multicomponent reactions on DEAM-PS-supported aminobenzeneboronic acids, derivatization of multifunctional arylboronic acids, and sequential reactions can also be carried out efficiently. These new DEAM-PS-supported arylboronic acids can be employed directly into resin-to-resin transfer reactions (RRTR). This type of multiresin process helps eliminate time-consuming cleavage and transfer operations, thereby considerably simplifying the outlook of combinatorial

  17. Crystal structure of 4-(meth-oxy-carbon-yl)phenyl-boronic acid.

    PubMed

    Flanagan, Keith J; Senge, Mathias O

    2015-10-01

    In the title compound, C8H9BO4, the meth-oxy-carbonyl group is rotated out of the plane of the benzene ring by 7.70 (6)°. In the crystal, mol-ecules are linked via pairs of O-H⋯O hydrogen bonds, involving the boronic acid OH groups, forming inversion dimers. The dimers are linked via O-H⋯O hydrogen bonds, involving a boronic acid OH group and the carbonyl O atom, forming undulating sheets parallel to (10-2). Within the sheets there are also C-H⋯O hydrogen bonds present, also involving the carbonyl O atom. The sheets are linked via C-H⋯π and offset face-to-face π-inter-actions between inversion-related mol-ecules [inter-centroid distance = 3.7843 (16) Å, inter-planar distance = 3.3427 (4) Å and offset = 1.744 Å], forming a three-dimensional structure.

  18. Detection of glycoprotein using fiber optic surface plasmon resonance sensors with boronic acid

    NASA Astrophysics Data System (ADS)

    Wang, Fang; Zhang, Yang; Liu, Zigeng; Qian, Siyu; Gu, Yiying; Jing, Zhenguo; Sun, Changsen; Peng, Wei

    2017-04-01

    In this paper, we present a tilted fiber Bragg gratings (TFBG) based surface Plasmon resonance (SPR) label-free sensors with boronic acid derivative (ABA-PBA) as receptor molecule to detect glycoprotein with high sensitivity and selectivity. Tilted fiber Bragg gratings (TFBG) as a near infrared wavelengths detecting element can be able to excite a number of cladding modes whose properties can be detected accurately by measuring the variation of transmitted spectra. A 10° TFBG coated by 50nm gold film was manufactured to stimulate surface plasmon resonance on the surface of the sensor. The sensor was loaded with boronic acid derivative as the recognition molecule which has been widely used in various areas for the recognition matrix of diol-containing biomolecules. The proposed TFBG-SPR sensors exhibit good selectivity and repeatability with the protein concentration sensitivity up to 2.867dB/ (mg/ml) and the limit of detection was 2*10-5g/ml.

  19. Arginase-boronic acid complex highlights a physiological role in erectile function.

    PubMed

    Cox, J D; Kim, N N; Traish, A M; Christianson, D W

    1999-11-01

    The crystal structure of the complex between the binuclear manganese metalloenzyme arginase and the boronic acid analog of L-arginine, 2(S)-amino-6-boronohexanoic acid (ABH), has been determined at 1.7 A resolution from a crystal perfectly twinned by hemihedry. ABH binds as the tetrahedral boronate anion, with one hydroxyl oxygen symmetrically bridging the binuclear manganese cluster and a second hydroxyl oxygen coordinating to Mn2+A. This binding mode mimics the transition state of a metal-activated hydroxide mechanism. This transition state structure differs from that occurring in NO biosynthesis, thereby explaining why ABH does not inhibit NO synthase. We also show that arginase activity is present in the penis. Accordingly, the tight binding and specificity of ABH allows us to probe the physiological role of arginase in modulating the NO-dependent smooth muscle relaxation required for erection. Strikingly, ABH causes significant enhancement of nonadrenergic, noncholinergic nerve-mediated relaxation of penile corpus cavernosum smooth muscle, suggesting that arginase inhibition sustains L-arginine concentrations for NO synthase activity. Therefore, human penile arginase is a potential target for therapeutic intervention in the treatment of erectile dysfunction.

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

    PubMed

    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

  1. Synthesis and Evaluation of Aryl Boronic Acids as Fluorescent Artificial Receptors for Biological Carbohydrates

    PubMed Central

    Craig, Sandra

    2011-01-01

    Carbohydrates in various forms play a vital role in numerous critical biological processes. The detection of such saccharides can give insight into the progression of such diseases such as cancer. Boronic acids react with 1,2 and 1,3 diols of saccharides in non-aqueous or basic aqueous media. Herein, we describe the design, synthesis and evaluation of three bisboronic acid fluorescent probes, each having about ten linear steps in its synthesis. Among these compounds that were evaluated, 9b was shown to selectively label HepG2, liver carcinoma cell line within a concentration range of 0.5–10 μM in comparison to COS-7, a normal fibroblast cell line. PMID:22177855

  2. Accumulation of boron in malignant and normal cells incubated in vitro with boronophenylalanine, mercaptoborane or boric acid.

    PubMed

    Capala, J; Makar, M S; Coderre, J A

    1996-11-01

    The short (< 10 microns) ranges of alpha and 7Li particles produced during boron neutron capture therapy (BNCT) make the partitioning of the boronated drug within and without the cell of critical importance. The evaluation of the potential usefulness of a boron-containing substance for BNCT requires information about its intracellular accumulation. In the present report, an in vitro method is described for direct measurement of intracellular boron based on rapid centrifugation of cells through a layer of mineral oil and silicon oil to strip away extracellular growth medium. The intracellular concentrations of boronophenylalanine (BPA), mercaptoborane (BSH) and horic acid in malignant cells and in normal cells have been compared. The accumulation ratio is defined as the ratio of the intracellular to the extracellular boron concentration. Boric acid showed an accumulation ratio of 1 while the ratios for BSH and BPA were dependent on cell type and tended to be greater for BPA than for BSH in malignant but not in normal cells.

  3. Boron removal by a composite sorbent: Polyethylenimine/tannic acid derivative immobilized in alginate hydrogel beads.

    PubMed

    Bertagnolli, Caroline; Grishin, Andrey; Vincent, Thierry; Guibal, Eric

    2017-03-21

    A novel composite material was prepared by the grafting of tannic acid on polyethylenimine (PEI), which allows an efficient sorption of boron (sorption capacity close to 0.89 mmol B g(-1)). The encapsulation of this chelating sorbent (finely crushed) facilitates its use (readily solid/liquid separation, use in fixed-bed columns) at the expense of a loss in sorption capacity (proportionally decreased by the introduction of alginate having poor efficiency for boron uptake). Sorption isotherms are modeled using the Langmuir equation, while the kinetic profiles are presented a good fit by pseudo-second order rate equation. In addition, the encapsulating matrix introduces supplementary resistance to intraparticle diffusion, especially when the resin is dried without control: freeze-drying partially limits this effect. The stability (at long-term storage) of the sorbent is improved when the sorbent is stored under nitrogen atmosphere. The presence of an excess of NaCl was investigated. The degradation of the hydrogel (by ion-exchange of Ca(II) with Na(I)) leads to a decrease in the sorption performance of composite material but the action of Ca(II) ions in the solutions re-stabilizes the hydrogel.

  4. Enantioselective α-Alkenylation of Aldehydes with Boronic Acids via the Synergistic Combination of Copper(II) and Amine Catalysis

    PubMed Central

    Stevens, Jason M.

    2013-01-01

    The enantioselective α-alkenylation of aldehydes has been accomplished using boronic acids via the synergistic combination of copper and chiral amine catalysis. The merger of two highly utilized and robust catalytic systems has allowed for the development of a mild and operationally trivial protocol for the direct formation of α-formyl olefins employing common building blocks for organic synthesis. PMID:23889497

  5. Effect of water stress and foliar boron application on seed protein oil fatty acids and nitrogen metabolism in soybean

    USDA-ARS?s Scientific Manuscript database

    Effects of water stress and foliar boron (FB) application on soybean (Glycine max (L) Merr.) seed composition and nitrogen metabolism have not been well investigated. Therefore, the objective of this study was to investigate the effects of water stress and FB on seed protein, oil, fatty acids, nitra...

  6. Boronic acid chemistry in MALDI MS: a step forward in designing a reactive matrix with molecular recognition capabilities.

    PubMed

    Monopoli, A; Calvano, C D; Nacci, A; Palmisano, F

    2014-04-28

    A boronic analogue of the archetype matrix α-cyano-4-hydroxycinnamic acid (CHCA) has been synthesised providing a new "reactive matrix" that possesses molecular recognition properties. This matrix selectively recognizes vic-diols, α-hydroxyacids, aminols and first allowed the detection of anions as fluoride (unaffordable by usual matrices).

  7. Efficient boron abstraction using honeycomb-like porous magnetic hybrids: Assessment of techno-economic recovery of boric acid.

    PubMed

    Oladipo, Akeem Adeyemi; Gazi, Mustafa

    2016-12-01

    Porous magnetic hybrids were synthesized and functionalized with glycidol to produce boron-selective adsorbent. The magnetic hybrid (MH) comparatively out-performed the existing expensive adsorbents. MH had a saturation magnetisation of 63.48 emu/g and average pore diameter ranging from meso to macropores. The magnetic hybrids showed excellent selectivity towards boron and resulted in 79-93% boron removal even in the presence of competing metal ions (Na(+) and Cr(2+)). Experiments were performed in a column system, and breakthrough time was observed to increase with bed depths and decreased with flow rates. The batch experiments revealed that 60 min was enough to achieve equilibrium, and the level of boron sorption was 108.5 mg/g from a synthetic solution. Several adsorption-desorption cycles were performed using a simple acid-water treatment and evaluated using various kinetic models. The spent adsorbents could be separated easily from the mixture by an external magnetic field. The cost-benefit analysis was performed for the treatment of 72 m(3)/year boron effluent, including five years straight line depreciation charges of equipment. The net profit and standard percentage confirmed that the recovery process is economically feasible. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Wu, Zhongyu; Zhang, Yufeng; Meng, Jianqiang

    2017-04-01

    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.

  9. Potent inhibitors of HCV-NS3 protease derived from boronic acids

    SciTech Connect

    Venkatraman, Srikanth; Wu, Wanli; Prongay, Andrew; Girijavallabhan, Viyyoor; Njoroge, F. George

    2009-07-23

    Chronic hepatitis C infection is the leading causes for cirrhosis of the liver and hepatocellular carcinoma, leading to liver failure and liver transplantation. The etiological agent, HCV virus produces a single positive strand of RNA that is processed with the help of serine protease NS3 to produce mature virus. Inhibition of NS3 protease can be potentially used to develop effective drugs for HCV infections. Numerous efforts are now underway to develop potent inhibitors of HCV protease that contain ketoamides as serine traps. Herein we report the synthesis of a series of potent inhibitors that contain a boronic acid as a serine trap. The activity of these compounds were optimized to 200 pM. X-ray structure of compound 17 bound to NS3 protease is also discussed.

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

    PubMed Central

    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

  11. Design, synthesis and biological evaluation of novel non-peptide boronic acid derivatives as proteasome inhibitors.

    PubMed

    Ge, Ying; Li, Aibo; Wu, Jianwei; Feng, Haiwei; Wang, Letian; Liu, Hongwu; Xu, Yungen; Xu, Qingxiang; Zhao, Li; Li, Yuyan

    2017-03-10

    A novel series of non-peptide proteasome inhibitors bearing the 1, 4-naphthoquinone scaffold and boronic acid warhead was developed. In the biological evaluation on the chymotrypsin-like activity of human 20S proteasome, five compounds showed IC50 values in the nanomolar range. Docking experiments into the yeast 20S proteasome rationalized their biological activities and allowed further optimization of this interesting class of inhibitors. Within the cellular proliferation inhibition assay and western blot analysis, compound 3e demonstrated excellent anti-proliferative activity against solid tumor cells and clear accumulation of ubiquitinated cellular proteins. Furthermore, in the microsomal stability assay compound 3e demonstrated much improved metabolic stability compared to bortezomib, emerging as a promising lead compound for further design of non-peptide proteasome inhibitors.

  12. Correlating Physicochemical Properties of Boronic Acid-Chitosan Conjugates to Glucose Adsorption Sensitivity

    PubMed Central

    Asantewaa, Yaa; Aylott, Jonathan; Burley, Jonathan C.; Billa, Nashiru; Roberts, Clive J.

    2012-01-01

    Phenyl boronic acid (PBA), which is known to interact with glucose, was covalently bonded to chitosan by direct reductive N-alkylation of chitosan with 4-formylphenylboronic acid (4-FPBA). Evidence of PBA bonding on chitosan was assessed by FTIR, ToF-SIMS, SEM, DSC and glucose adsorption sensitivity measurements. FTIR spectra showed strong signals at 1560 and 630 cm−1 indicating the formation of p-substituted benzene. Similarly, ToF-SIMS analyses on the conjugates registered fragments of boron ion (B−) at 11.0 m/z whose intensity increased in proportion to 4-FPBA loading. The degree to which PBA was bonded to chitosan was related to the 4-FPBA load used in the reaction (termed F1 through to F6 with increasing 4-FPBA load). Glucose adsorption sensitivity to PBA-bonded chitosan was directly related to the amount of PBA functionality within the conjugates and the physical nature of the matrices (porous or crystalline). Topographic analysis by SEM revealed that PBA-chitosan conjugates F1, F2 and F3 have porous matrices and their sensitivity to glucose adsorption was directly proportional to the degree of PBA substitution onto chitosan. Conversely, conjugates F4, F5 and F6 appeared crystalline under SEM and glucose adsorption sensitivity decreased in proportion to amount of PBA bonded to chitosan. The crystalline nature of the conjugates was confirmed by DSC, where the exothermic event related to the melting of the bonded PBA moiety, occurred at 338 °C. Thus, decreased sensitivity to glucose adsorption by the conjugates can be ascribed to the crystallinity imparted by increased content of the bonded PBA moiety, providing an optimal loading of PBA in terms of maximizing response to glucose. PMID:24300397

  13. Electrochemical oxidation of oxalic acid at highly boron-doped diamond electrodes.

    PubMed

    Ivandini, Tribidasari A; Rao, Tata N; Fujishima, Akira; Einaga, Yasuaki

    2006-05-15

    Electrochemical oxidation of oxalic acid has been investigated at bare, highly boron-doped diamond electrodes. Cyclic voltammetry and flow injection analysis with amperometric detection were used to study the electrochemical reaction. Hydrogen-terminated diamonds exhibited well-defined peaks of oxalic acid oxidation in a wide pH range. A good linear response was observed for a concentration range from 50 nM to 10 microM, with an estimated detection limit of approximately 0.5 nM (S/N = 3). In contrast, oxygen-terminated diamonds showed no response for oxalic acid oxidation inside the potential window, indicating that surface termination contributed highly to the control of the oxidation reaction. An investigation with glassy carbon electrodes was conducted to confirm the surface termination effect on oxalic acid oxidation. Although a hydrogen-terminated glassy carbon electrode showed an enhancement of signal-to-background ratio in comparison with untreated glassy carbon, less stability of the current responses was observed than that at hydrogen-terminated diamond.

  14. The ever-surprising chemistry of boron: enhanced acidity of phosphine.boranes.

    PubMed

    Hurtado, Marcela; Yánez, Manuel; Herrero, Rebeca; Guerrero, Andrés; Dávalos, Juan Z; Abboud, José-Luis M; Khater, Brahim; Guillemin, Jean-Claude

    2009-01-01

    The acidity-enhancing effect of BH(3) in gas-phase phosphineboranes compared to the corresponding free phosphines is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. Thus, the enhancement of the acidity of protic acids by Lewis acids usually observed in solution is also observed in the gas phase. For example, the gas-phase acidities (GA) of MePH(2) and MePH(2)BH(3) differ by about 118 kJ mol(-1) (see picture).The gas-phase acidity of a series of phosphines and their corresponding phosphineborane derivatives was measured by FT-ICR techniques. BH(3) attachment leads to a substantial increase of the intrinsic acidity of the system (from 80 to 110 kJ mol(-1)). This acidity-enhancing effect of BH(3) is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. This indicates that the enhancement of the acidity of protic acids by Lewis acids usually observed in solution also occurs in the gas phase. High-level DFT calculations reveal that this acidity enhancement is essentially due to stronger stabilization of the anion with respect to the neutral species on BH(3) association, due to a stronger electron donor ability of P in the anion and better dispersion of the negative charge in the system when the BH(3) group is present. Our study also shows that deprotonation of ClCH(2)PH(2) and ClCH(2)PH(2)BH(3) is followed by chloride departure. For the latter compound deprotonation at the BH(3) group is found to be more favorable than PH(2) deprotonation, and the subsequent loss of Cl(-) is kinetically favored with respect to loss of Cl(-) in a typical S(N)2 process. Hence, ClCH(2)PH(2)BH(3) is the only phosphineborane adduct included in this study which behaves as a boron acid rather than as a phosphorus acid.

  15. In vivo percutaneous absorption of boron as boric acid, borax, and disodium octaborate tetrahydrate in humans: a summary.

    PubMed

    Wester, R C; Hui, X; Maibach, H I; Bell, K; Schell, M J; Northington, D J; Strong, P; Culver, B D

    1998-01-01

    Literature from the first half of this century reports concern for toxicity from topical use of boric acid, but assessment of percutaneous absorption has been impaired by lack of analytical sensitivity. Analytical methods in this study included inductively coupled plasma-mass spectrometry, which now allows quantitation of percutaneous absorption of 10B in 10B-enriched boric acid, borax, and disodium octaborate tetrahydrate (DOT) in biological matrices. This made it possible, in the presence of comparatively large natural dietary boron intakes for the in vivo segment of this study, to quantify the boron passing through skin. Human volunteers were dosed with 10B-enriched boric acid, 5.0%, borax, 5.0%, or disodium octaborate tetrahydrate, 10% in aqueous solutions. Urinalysis, for boron and changes in boron isotope ratios, was used to measure absorption. Boric acid in vivo percutaneous absorption was 0.226 (SD = 0.125) mean percent dose, with flux and permeability constant (Kp) calculated at 0.009 microg/cm2/h and 1.9 x 10(-7) cm/h, respectively. Borax absorption was 0.210 (SD = 0.194) mean percent dose, with flux and Kp calculated at 0.009 microg/cm2/h and 1.8 x 10(-7) cm/h, respectively. DOT absorption was 0.122 (SD = 0.108) mean percent, with flux and Kp calculated at 0.01 microg/cm2/h and 1.0 x 10(-7) cm/h, respectively. Pretreatment with the potential skin irritant 2% sodium lauryl sulfate had no effect on boron skin absorption. These in vivo results show that percutaneous absorption of boron, as boric acid, borax, and disodium octaborate tetrahydrate, through intact human skin is low and is significantly less than the average daily dietary intake. This very low boron skin absorption makes it apparent that, for the borates tested, the use of gloves to prevent systemic uptake is unnecessary. These findings do not apply to abraded or otherwise damaged skin.

  16. Strategies for the design and synthesis of boronated nucleic acid and protein components as potential delivery agents for neutron capture therapy

    SciTech Connect

    Wyzlic, I.M.; Tjarks, W.; Soloway, A.H.; Anisuzzaman, A.K.M.; Rong, Feng-Guang; Barth, R.F. )

    1994-03-30

    Strategies for the design and synthesis of boronated nucleosides, amino acids, and peptides as potential delivery agents for boron neutron capture therapy (BNCT) are described. For BNCT to be a useful treatment modality, there is a need to design and synthesize nontoxic boron compounds that selectively target tumor cells, accumulate in sufficient amounts (20-30 [mu]g [sup 10]B/g of tumor) and persist at therapeutic levels for a sufficient time prior to neutron irradiation. Boronated nucleosides, amino acids and peptides are such promising target compounds. Such structures may be selectively used by proliferating neoplastic cells compared with mitotically less active normal cells and therefore achieve the tissue differentials necessary for BNCT. The rationale for synthesis of boronated nucleic acid and protein components is discussed. Results of biological and clinical studies of some boronated nucleosides, nucleotides, amino acids and peptides are presented. Boronated nucleosides, amino acids and peptides can be considered as potential targeting agents for BNCT. 96 refs., 4 figs.

  17. A General Protocol for the Polycondensation of Thienyl N-Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers

    PubMed Central

    2016-01-01

    Thienyl di-N-methyliminodiacetic acid (MIDA) boronate esters are readily synthesized by electrophilic C–H borylation producing bench stable crystalline solids in good yield and excellent purity. Optimal conditions for the slow release of the boronic acid using KOH as the base in biphasic THF/water mixtures enables the thienyl MIDA boronate esters to be extremely effective homo-bifunctionalized (AA-type) monomers in Suzuki–Miyaura copolymerizations with dibromo-heteroarenes (BB-type monomers). A single polymerization protocol is applicable for the formation of five alternating thienyl copolymers that are (or are close analogues of) state of the art materials used in organic electronics. The five polymers were produced in excellent yields and with high molecular weights comparable to those produced using Stille copolymerization protocols. Therefore, thienyl di-MIDA boronate esters represent bench stable and low toxicity alternatives to highly toxic di-trimethylstannyl AA-type monomers that are currently ubiquitous in the synthesis of these important alternating copolymers. PMID:27636745

  18. A General Protocol for the Polycondensation of Thienyl N-Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers.

    PubMed

    Carrillo, Josue Ayuso; Turner, Michael L; Ingleson, Michael J

    2016-10-12

    Thienyl di-N-methyliminodiacetic acid (MIDA) boronate esters are readily synthesized by electrophilic C-H borylation producing bench stable crystalline solids in good yield and excellent purity. Optimal conditions for the slow release of the boronic acid using KOH as the base in biphasic THF/water mixtures enables the thienyl MIDA boronate esters to be extremely effective homo-bifunctionalized (AA-type) monomers in Suzuki-Miyaura copolymerizations with dibromo-heteroarenes (BB-type monomers). A single polymerization protocol is applicable for the formation of five alternating thienyl copolymers that are (or are close analogues of) state of the art materials used in organic electronics. The five polymers were produced in excellent yields and with high molecular weights comparable to those produced using Stille copolymerization protocols. Therefore, thienyl di-MIDA boronate esters represent bench stable and low toxicity alternatives to highly toxic di-trimethylstannyl AA-type monomers that are currently ubiquitous in the synthesis of these important alternating copolymers.

  19. Corrosion resistance of inconel 690 to borax, boric acid, and boron nitride at 1100{degrees}C

    SciTech Connect

    Imrich, K.J.

    1996-12-12

    Significant general and localized corrosion was observed on Inconel 690 coupons following exposure to borax, boric acid and boron nitride at 1100{degrees}C. Severe localized attack at and below the melt line was observed on coupons exposed to borax. An intergranular attack at and below the melt line was observed on coupons exposed to borax. An intergranular attack (IGA) of the Inconel 690 was also observed. Severe internal void formation and IGA (30 mils penetration after 3 days) was observed in the coupon exposed to boric acid. Both borax and boric acid remove the protective chromium oxide; however, this layer can be reestablished by heating the Inconel 690 to 975 {degrees}C in air for several hours. Inconel 690 in direct contact with boron nitride resulted in the formation of a thick chromium borate layer, a general corrosion rate of 50 to 90 mils per year, and internal void formation of 1 mil per day.

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

    PubMed

    Zhang, Yang; Wang, Fang; Qian, Siyu; Liu, Zexu; Wang, Qiao; Gu, Yiying; Wu, Zhenlin; Jing, Zhenguo; Sun, Changsen; Peng, Wei

    2017-10-01

    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.

  1. Determination of boron in blood, urine and bone by electrothermal atomic absorption spectrometry using zirconium and citric acid as modifiers

    NASA Astrophysics Data System (ADS)

    Burguera, Marcela; Burguera, José Luis; Rondón, Carlos; Carrero, Pablo

    2001-10-01

    A comparative study of various potential chemical modifiers (Au, Ba, Be, Ca, Cr, Ir, La, Lu, Mg, Ni, Pd, Pt, Rh, Ru, Sr, V, W, and Zr), and different 'coating' treatments (Zr, W, and W+Rh) of the pyrolytic graphite platform of a longitudinally heated graphite tube atomizer for thermal stabilization and determination of boron was undertaken. The use of Au, Ba, Be, Cr, Ir, Pt, Rh, Ru, Sr and V as modifiers, and of W+Rh coating produced erratic, and noisy signals, while the addition of La, Ni and Pd as modifiers, and the W coating had positive effects, but with too high background absorption signals, rendering their use unsuitable for boron determination even in aqueous solutions. The atomic absorption signal for boron was increased and stabilized when the platform was coated with Zr, and by the addition of Ca, Mg, Lu, W or Zr as modifiers. Only the addition of 10 μg of Zr as a modifier onto Zr-treated platforms allowed the use of a higher pyrolysis temperature without analyte losses. The memory effect was minimized by incorporating a cleaning step with 10 μl of 50 g l -1 NH 4F HF after every three boron measurements. The addition of 10 μl of 15 g l -1 citric acid together with Zr onto Zr-treated platforms significantly improved the characteristic mass to m0=282 pg, which is adequate for biological samples such as urine and bone, although the sensitivity was still inadequate for the determination of boron in blood of subjects without supplementary diet. Under optimized conditions, the detection limit (3σ) was 60 μg l -1. The amount of boron found in whole blood, urine and femur head samples from patients with osteoporosis was in agreement with values previously reported in the literature.

  2. Process for microwave sintering boron carbide

    DOEpatents

    Holcombe, Cressie E.; Morrow, Marvin S.

    1993-01-01

    A method of microwave sintering boron carbide comprises leaching boron carbide powder with an aqueous solution of nitric acid to form a leached boron carbide powder. The leached boron carbide powder is coated with a glassy carbon precursor to form a coated boron carbide powder. The coated boron carbide powder is consolidated in an enclosure of boron nitride particles coated with a layer of glassy carbon within a container for microwave heating to form an enclosed coated boron carbide powder. The enclosed coated boron carbide powder is sintered within the container for microwave heating with microwave energy.

  3. Process for microwave sintering boron carbide

    DOEpatents

    Holcombe, C.E.; Morrow, M.S.

    1993-10-12

    A method of microwave sintering boron carbide comprises leaching boron carbide powder with an aqueous solution of nitric acid to form a leached boron carbide powder. The leached boron carbide powder is coated with a glassy carbon precursor to form a coated boron carbide powder. The coated boron carbide powder is consolidated in an enclosure of boron nitride particles coated with a layer of glassy carbon within a container for microwave heating to form an enclosed coated boron carbide powder. The enclosed coated boron carbide powder is sintered within the container for microwave heating with microwave energy.

  4. Tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization between vinyl ether boronates and vinyl halides: a concise approach to polysubstituted furans.

    PubMed

    Butkevich, Alexey N; Meerpoel, Lieven; Stansfield, Ian; Angibaud, Patrick; Corbu, Andrei; Cossy, Janine

    2013-08-02

    Polysubstituted 2-(ω-hydroxyalkyl)furans were prepared by tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization starting from appropriately substituted 3-haloallylic alcohols and dihydrofuran-, dihydropyran- or glycal-derived pinacol boronates.

  5. Homogeneous and heterogenized Au(III) Schiff base-complexes as selective and general catalysts for self-coupling of aryl boronic acids.

    PubMed

    González-Arellano, C; Corma, A; Iglesias, M; Sánchez, F

    2005-04-21

    A series of homogeneous and heterogenized gold metal complexes show high activity and selectivity for the homocoupling of a large variety of aryl boronic acids, being of general utility for the synthesis of C2-symmetric biaryls.

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

    PubMed Central

    Siddiqui, Nabil A.; Billa, Nashiru; Roberts, Clive J.; Asantewaa Osei, Yaa

    2016-01-01

    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. PMID:27740594

  7. A Three‐Component Assembly Promoted by Boronic Acids Delivers a Modular Fluorophore Platform (BASHY Dyes)†

    PubMed Central

    Santos, Fábio M. F.; Rosa, João N.; Candeias, Nuno R.; Carvalho, Cátia Parente; Matos, Ana I.; Ventura, Ana E.; Florindo, Helena F.; Silva, Liana C.

    2015-01-01

    Abstract The modular assembly of boronic acids with Schiff‐base ligands enabled the construction of innovative fluorescent dyes [boronic acid salicylidenehydrazone (BASHY)] with suitable structural and photophysical properties for live cell bioimaging applications. This reaction enabled the straightforward synthesis (yields up to 99 %) of structurally diverse and photostable dyes that exhibit a polarity‐sensitive green‐to‐yellow emission with high quantum yields of up to 0.6 in nonpolar environments. These dyes displayed a high brightness (up to 54 000 m −1 cm−1). The promising structural and fluorescence properties of BASHY dyes fostered the preparation of non‐cytotoxic, stable, and highly fluorescent poly(lactide‐co‐glycolide) nanoparticles that were effectively internalized by dendritic cells. The dyes were also shown to selectively stain lipid droplets in HeLa cells, without inducing any appreciable cytotoxicity or competing plasma membrane labeling; this confirmed their potential as fluorescent stains. PMID:26691630

  8. Innovative method for boron extraction from iron ore containing boron

    NASA Astrophysics Data System (ADS)

    Wang, Guang; Wang, Jing-song; Yu, Xin-yun; Shen, Ying-feng; Zuo, Hai-bin; Xue, Qing-guo

    2016-03-01

    A novel process for boron enrichment and extraction from ludwigite based on iron nugget technology was proposed. The key steps of this novel process, which include boron and iron separation, crystallization of boron-rich slag, and elucidation of the boron extraction behavior of boron-rich slag by acid leaching, were performed at the laboratory. The results indicated that 95.7% of the total boron could be enriched into the slag phase, thereby forming a boron-rich slag during the iron and slag melting separation process. Suanite and kotoite were observed to be the boron-containing crystalline phases, and the boron extraction properties of the boron-rich slag depended on the amounts and grain sizes of these minerals. When the boron-rich slag was slowly cooled to 1100°C, the slag crystallized well and the efficiency of extraction of boron (EEB) of the slag was the highest observed in the present study. The boron extraction property of the slow-cooled boron-rich slag obtained in this study was much better than that of szaibelyite ore under the conditions of 80% of theoretical sulfuric acid amount, leaching time of 30 min, leaching temperature of 40°C, and liquid-to-solid ratio of 8 mL/g.

  9. Boronate-Phenolic Network Capsules with Dual Response to Acidic pH and cis-Diols.

    PubMed

    Guo, Junling; Sun, Huanli; Alt, Karen; Tardy, Blaise L; Richardson, Joseph J; Suma, Tomoya; Ejima, Hirotaka; Cui, Jiwei; Hagemeyer, Christoph E; Caruso, Frank

    2015-08-26

    Dual-responsive boronate-phenolic network (BPN) capsules are fabricated by the complexation of phenylborate and phenolic materials. The BPN capsules are stable in the presence of competing carbohydrates, but dissociate at acidic pH or in the presence of competing cis-diols at physiological pH. This engineered capsule system provides a platform for a wide range of biological and biomedical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Potential of boronic acid functionalized magnetic particles in the adsorption of human antibodies under mammalian cell culture conditions.

    PubMed

    Borlido, L; Azevedo, A M; Roque, A C A; Aires-Barros, M R

    2011-10-28

    In this work, we systematically evaluated the potential of using boronic acid functionalized magnetic particles in the capturing of human immunoglobulin G under typical mammalian cell culture conditions. For comparison, Protein A coated magnetic particles were also used. The binding pH was found to significantly influence the adsorption isotherms of boronic acid particles with the higher capacities (0.216 g IgG/g support) being observed at pH 7.4. Comparatively, this value was 0.109 g IgG/g support, for Protein A particles under the same conditions. Both particles revealed very fast adsorption kinetics with more than 70% of the maximum binding capacity being achieved in a few seconds. The effect of glucose and lactate, which are known to interact with boronic acid, was evaluated. For glucose, the binding capacity was significantly influenced by the pH and decreased as pH increased. At pH 9.5, a 70% lower binding capacity was observed for glucose concentrations as low as 0.5 g/l. The effect of lactate was less pronounced and almost pH independent reaching at most 20% decrease in binding capacity. Nevertheless, the effect of both molecules was always lower at pH 7.4. The optimization of the elution conditions enabled complete recovery of bound IgG from boronic acid particles using 50mM Tris-HCl, 200 mM sorbitol, 200 mM NaCl at pH 8.5. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Folic acid-conjugated 4-amino-phenylboronate, a boron-containing compound designed for boron neutron capture therapy, is an unexpected agonist for human neutrophils and platelets.

    PubMed

    Achilli, Cesare; Jadhav, Sushilkumar A; Guidetti, Gianni F; Ciana, Annarita; Abbonante, Vittorio; Malara, Alessandro; Fagnoni, Maurizio; Torti, Mauro; Balduini, Alessandra; Balduini, Cesare; Minetti, Giampaolo

    2014-05-01

    Boron neutron capture therapy (BNCT) is an anticancer treatment based on the accumulation in the tumor cells of (10) B-containing molecules and subsequent irradiation with low-energy neutrons, which bring about the decay of (10) B to very toxic (7) Li(3+) and (4) He(2+) ions. The effectiveness of BNCT is limited by the low delivery and accumulation of the used (10) B-containing compounds. Here, we report the development of folic acid-conjugated 4-amino-phenylboronate as a novel possible compound for the selective delivery of (10) B in BNCT. An extensive analysis about its biocompatibility to mature blood cells and platelet progenitors revealed that the compound markedly supports platelet aggregation, neutrophil oxidative burst, and inhibition of megakaryocyte development, while it does not have any manifest effect on red blood cells. © 2013 John Wiley & Sons A/S.

  12. A Metal and Base-Free Chemoselective Primary Amination of Boronic Acids Using Cyanamidyl/Arylcyanamidyl Radical as Aminating Species: Synthesis and Mechanistic Studies by Density Functional Theory.

    PubMed

    Chatterjee, Nachiketa; Arfeen, Minhajul; Bharatam, Prasad V; Goswami, Avijit

    2016-06-17

    An efficient, metal and base-free, chemoselective synthesis of aryl-, heteroaryl-, and alkyl primary amines from the corresponding boronic acids has been achieved at ambient temperature mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) and N-bromosuccinimide (NBS) using cyanamidyl/arylcyanamidyl radicals as the aminating species. The primary amine compounds were initially obtained as their corresponding ammonium trifluoroacetate salts which, on treatment with aq NaOH, provide the free amines. Finally, the primary amines were isolated through column chromatography over silica-gel using hexane-EtOAc solvent system as the eluent. The reactions are sufficiently fast, completing within 1 h. Quantum chemical calculations in combination with experimental observations validate that the ipso amination of substituted boronic acids involves the formation of cyanamidyl/arylcyanamidyl radical, followed by regiospecific interaction of its nitrile-N center with boron atom of the boronic acids, leading to chemoselective primary amination.

  13. Targeting Class A and C Serine β-Lactamases with a Broad-Spectrum Boronic Acid Derivative

    PubMed Central

    2015-01-01

    Production of β-lactamases (BLs) is the most widespread resistance mechanism adopted by bacteria to fight β-lactam antibiotics. The substrate spectrum of BLs has become increasingly broad, posing a serious health problem. Thus, there is an urgent need for novel BL inhibitors. Boronic acid transition-state analogues are able to reverse the resistance conferred by class A and C BLs. We describe a boronic acid analogue possessing interesting and potent broad-spectrum activity vs class A and C serine-based BLs. Starting from benzo(b)thiophene-2-boronic acid (BZBTH2B), a nanomolar non-β-lactam inhibitor of AmpC that can potentiate the activity of a third-generation cephalosporin against AmpC-producing resistant bacteria, we designed a novel broad-spectrum nanomolar inhibitor of class A and C BLs. Structure-based drug design (SBDD), synthesis, enzymology data, and X-ray crystallography results are discussed. We clarified the inhibitor binding geometry responsible for broad-spectrum activity vs serine-active BLs using double mutant thermodynamic cycle studies. PMID:24882105

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

    PubMed

    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.

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

    PubMed

    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.

  16. Boron-Based Drug Design.

    PubMed

    Ban, Hyun Seung; Nakamura, Hiroyuki

    2015-06-01

    The use of the element boron, which is not generally observed in a living body, possesses a high potential for the discovery of new biological activity in pharmaceutical drug design. In this account, we describe our recent developments in boron-based drug design, including boronic acid containing protein tyrosine kinase inhibitors, proteasome inhibitors, and tubulin polymerization inhibitors, and ortho-carborane-containing proteasome activators, hypoxia-inducible factor 1 inhibitors, and topoisomerase inhibitors. Furthermore, we applied a closo-dodecaborate as a water-soluble moiety as well as a boron-10 source for the design of boron carriers in boron neutron capture therapy, such as boronated porphyrins and boron lipids for a liposomal boron delivery system.

  17. Microwave activated electrochemical degradation of 2,4-dichlorophenoxyacetic acid at boron-doped diamond electrode.

    PubMed

    Gao, Junxia; Zhao, Guohua; Shi, Wei; Li, Dongming

    2009-04-01

    A method for improving the oxidation ability of the electrode is proposed by using microwave activation in electrochemical oxidation. The electrochemical degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) with microwave radiation (MW-EC) was carried out in a continuous flow system under atmospheric pressure. In 3 h the removal of COD, ACE (average current efficiency) and Cl(-) concentration was 1.63, 2.25 and 1.67 times as that without microwave radiation, respectively. The high degradation ability was resulted from the more active centers at the electrode surface due to the microwave radiation. The decay kinetics of 2,4-D followed a pseudo first-order reaction. The rate constant was increased to 2.16x10(-4) s(-1) with the microwave radiation, while it was 8.52x10(-5) s(-1) with electrochemical treatment only (EC). Under both conditions, the main intermediates were identified and quantified by High Performance Liquid Chromatography (HPLC). The formation rate of intermediate products and further degradation rate were increased by about 50-120% with the microwave radiation. The activation of electrochemical oxidation by microwave was discussed from the diffusion process, adsorption and the temperature at boron-doped diamond (BDD) electrode.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. The transport of indole-3-acetic Acid in boron- and calcium-deficient sunflower hypocotyl segments.

    PubMed

    Tang, P M; Dela Fuente, R K

    1986-06-01

    Transfer of sunflower (Helianthus annuus L. cv Russian Mammoth) seedlings from complete nutrient solution to solutions deficient in either boron or calcium resulted in a steady decline in the rate of auxin transport, compared to seedlings that remained in the complete solution. In seedlings transferred to solutions deficient in both B and Ca, the decline in auxin transport was greater than seedlings deficient in only one element. The transfer of B- or Ca-deficient seedlings back to the complete solution prevented further decline in auxin transport, but auxin transport did not increase to the same level as seedlings maintained in complete solution. The significant reduction in auxin transport during the early stages of B or Ca deficiency was not related to (a) reduced growth rate of the hypocotyl, (b) increased acropetal movement of auxin, or (c) lack of respiratory substrates in the hypocotyl. In addition, no difference was found in the water-extractable total and ionic Ca in B-deficient and control nondeficient hypocotyls, indicating a direct effect of B on auxin transport, rather than indirectly by affecting Ca absorption. The rate of auxin transport in hypocotyls deficient in either B or Ca, was inversely correlated with K(+) leakage and rate of respiration. The data presented strongly support the view that there are separate sites for B and Ca in the basipetal transport of the plant hormone indoleacetic acid.

  20. Crystal structure of (2-benzyl­oxy­pyrimidin-5-yl)boronic acid

    PubMed Central

    Durka, Krzysztof; Kliś, Tomasz; Serwatowski, Janusz

    2014-01-01

    The boronic acid group in the title compound, C11H11BN2O3, adopts a syn–anti conformation and is almost coplanar with the aromatic rings , making a dihedralangle of 3.8 (2)°. In the crystal, adjacent mol­ecules are linked via pairs of O—H⋯O inter­actions, forming centrosymmetric dimers with an R 2 2(8) motif, which have recently been shown to be energetically very favorable (Durka et al., 2012 ▶, 2014 ▶). The hy­droxy groups in an anti conformation are engaged in lateral hydrogen-bonding inter­actions with N atoms from neighbouring mol­ecules, leading to the formation of chains along [001]. O⋯B [3.136 (2) Å] and C(π)⋯B [3.393 (2) Å] stacking inter­actions in turn link parallel chains of centrosymmetric dimers into layers parallel to (010). PMID:25553032

  1. Highly selective capture of nucleosides with boronic acid functionalized polymer brushes prepared by atom transfer radical polymerization.

    PubMed

    Cheng, Ting; Zhu, Shuqiang; Zhu, Bin; Liu, Xiaoyan; Zhang, Haixia

    2016-04-01

    The nucleoside or modified nucleoside level in biological fluids reflects the pathological or physiological state of the body. Boronate affinity absorbents are widely used to selectively extract nucleosides from complex samples. In this work, a novel functionalized absorbent was synthesized by attaching 4-mercaptophenylboronic acid to gold nanoparticles on modified attapulgite. The surface of the attapulgite was modified by poly(acryloyloxyethyltrimethyl ammonium chloride) by atom transfer radical polymerization, creating many polymer brushes on the surface. The resultant material exhibited superior binding capacity (30.83 mg/g) for adenosine and was able to capture cis-diol nucleosides from 1000-fold interferences. Finally, to demonstrate its potential for biomolecule extraction, this boronate affinity material was used to preconcentrate nucleosides from human urine and plasma. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A new palladium precatalyst allows for the fast Suzuki-Miyaura coupling reactions of unstable polyfluorophenyl and 2-heteroaryl boronic acids.

    PubMed

    Kinzel, Tom; Zhang, Yong; Buchwald, Stephen L

    2010-10-13

    Boronic acids which quickly deboronate under basic conditions, such as polyfluorophenylboronic acid and five-membered 2-heteroaromatic boronic acids, are especially challenging coupling partners for Suzuki-Miyaura reactions. Nevertheless, being able to use these substrates is highly desirable for a number of applications. Having found that monodentate biarylphosphine ligands can promote these coupling processes, we developed a precatalyst that forms the catalytically active species under conditions where boronic acid decomposition is slow. With this precatalyst, Suzuki-Miyaura reactions of a wide range of (hetero)aryl chlorides, bromides, and triflates with polyfluorophenyl, 2-furan, 2-thiophene, and 2-pyrroleboronic acids and their analogues proceed at room temperature or 40 °C in short reaction times to give the desired products in excellent yields.

  3. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    PubMed

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-06

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution.

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

    PubMed

    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.

  5. Kinetics of the electrochemical mineralization of perfluorooctanoic acid on ultrananocrystalline boron doped conductive diamond electrodes.

    PubMed

    Urtiaga, Ane; Fernández-González, Carolina; Gómez-Lavín, Sonia; Ortiz, Inmaculada

    2015-06-01

    This work deals with the electrochemical degradation and mineralization of perfluorooctanoic acid (PFOA). Model aqueous solutions of PFOA (100mg/L) were electro-oxidized under galvanostatic conditions in a flow-by undivided cell provided with a tungsten cathode and an anode formed by a commercial ultrananocrystalline boron doped diamond (BDD) coating on a niobium substrate. A systematic experimental study was conducted in order to analyze the influence of the following operation variables: (i) the supporting electrolyte, NaClO4 (1.4 and 8.4g/L) and Na2SO4 (5g/L); (ii) the applied current density, japp, in the range 50-200 A/m(2) and (iii) the hydrodynamic conditions, in terms of flowrate in the range 0.4×10(-4)-1.7×10(-4)m(3)/s and temperature in the range 293-313K. After 6h of treatment and at japp 200A/m(2), PFOA removal was higher than 93% and the mineralization ratio, obtained from the decrease of the total organic carbon (TOC) was 95%. The electrochemical generation of hydroxyl radicals in the supporting electrolyte was experimentally measured based on their reaction with dimethyl sulfoxide. The enhanced formation of hydroxyl radicals at higher japp was related to the faster kinetics of PFOA removal. The fitting of experimental data to the proposed kinetic model provided the first order rate constants of PFOA degradation, kc(1) that moved from 2.06×10(-4) to 15.58×10(-4)s(-1), when japp varied from 50 to 200A/m(2). Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Validation and scale-up of plasmid DNA purification by phenyl-boronic acid chromatography.

    PubMed

    Gomes, A Gabriela; Azevedo, Ana M; Aires-Barros, M Raquel; Prazeres, D Miguel F

    2012-11-01

    This study addresses the feasibility of scaling-up the removal of host cell impurities from plasmid DNA (pDNA)-containing Escherichia coli lysates by phenyl-boronic (PB) acid chromatography using columns packed with 7.6 and 15.2 cm(3) of controlled porous glass beads (CPG) derivatized with PB ligands. Equilibration was performed with water at 10 cm(3) /min and no conditioning of the lysate feed was required. At a ratio of lysate feed to adsorbent volume of 1.3, 93-96% of pDNA was recovered in the flow through while 66-71% of impurities remained bound (~2.5-fold purification). The entire sequence of loading, washing, elution, and re-equilibration was completed in 20 min. Run-to-run consistency was observed in terms of chromatogram features and performance (yield, purification factor, agarose electrophoresis) across the different amounts of adsorbent (0.75-15.2 cm(3) ) by performing successive injections of lysates prepared independently and containing 3.7 or 6.1 kbp plasmids. The column productivity at large scale was 4 dm(3) of alkaline lysate per hour per dm(3) of PB-CPG resin. The method is rapid, reproducible, simple, and straightforward to scale-up. Furthermore, it is capable of handling heavily contaminated samples, constituting a good alternative to purification techniques such as isopropanol precipitation, aqueous two-phase systems, and tangential flow filtration. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Theoretical Study of the BF3-Promoted Rearrangement of Oxiranyl N-Methyliminodiacetic Acid Boronates.

    PubMed

    Vallejos, Margarita M; Pellegrinet, Silvina C

    2017-06-02

    The mechanism of the rearrangement of oxiranyl N-methyliminodiacetyl (MIDA) boronates in dicholoromethane has been extensively investigated with density functional theory. Several reaction pathways were examined. Our results revealed that the most-favorable mechanisms for the BF3-promoted rearrangement of 2-phenyl oxiranyl MIDA boronate (1) and 1-phenyl oxiranyl MIDA boronate (24) comprise two steps: ring opening of the epoxide to a carbocation intermediate followed by migration of a MIDA-boryl group (for the reaction of 1) and hydrogen (for the reaction of 24), to give the same BF3-coordinated α-boryl aldehyde in both cases. The first step of the ring opening of the epoxide is the rate-determining step of these reactions. In the rearrangement step for the reaction of 1, the MIDA-boryl group migrates easily, probably because of its electron-rich sp(3)-hybridized boron center. For 24, the most-favorable pathway involves a rare boryl-substituted carbocation. The course of these reactions is mainly controlled by electronic effects, although steric effects are also significant. The higher energy barrier calculated for the unsubstituted oxiranyl MIDA boronate (31) explains the lack of reactivity in the studied BF3-promoted rearrangement.

  8. Three-component Pd/Cu-catalyzed cascade reactions of cyclic iodoniums, alkynes, and boronic acids: an approach to methylidenefluorenes.

    PubMed

    Zhu, Daqian; Wu, Yongcheng; Wu, Baojian; Luo, Bingling; Ganesan, A; Wu, Fu-Hai; Pi, Rongbiao; Huang, Peng; Wen, Shijun

    2014-05-02

    Linear diaryliodonium salts are widely used as arylating reagents for C-C and C-X bond formation. Meanwhile, synthetic applications of cyclic iodoniums are relatively rare although they offer the opportunity to set up reaction cascades. We demonstrate an atom and step economical three-component reaction involving cyclic diphenyleneiodoniums, alkynes, and boronic acids, resulting in the construction of methylidenefluorenes in a single operation. Our route enables facile access to both symmetrical and unsymmetrical methylidenefluorene derivatives, compounds that have attracted interest due to their optical properties.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

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

    PubMed

    Hai, Yang; Christianson, David W

    2016-04-01

    Leishmania arginase is a potential drug target for the treatment of leishmaniasis because this binuclear manganese metalloenzyme initiates de novo polyamine 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 of L. mexicana arginase 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.

  11. Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: efficient synthesis of 1,1-diaryl-2,2-difluoroethenes.

    PubMed

    Kim, Ju Hee; Choi, Su Jeong; Jeong, In Howa

    2013-01-01

    The cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate (2) with 2 equiv of boronic acids in the presence of catalytic amounts of Pd(OAc)2 and Na2CO3 afforded the mono-coupled products 3 and 5 in high yields. The use of 4 equiv of boronic acids in the presence of catalytic amount of Pd(PPh3)2Cl2 and Na2CO3 in this reaction resulted in the formation of symmetrical di-coupled products 4 in high yields. Unsymmetrical di-coupled products 4 were obtained in high yields from the reactions of 3 with 2 equiv of boronic acids in the presence of catalytic amounts of Pd(OAc)2 and Na2CO3.

  12. Ferrocene-Boronic Acid-Fructose Binding Based on Dual-Plate Generator-Collector Voltammetry and Square-Wave Voltammetry.

    PubMed

    Li, Meng; Xu, Su-Ying; Gross, Andrew J; Hammond, Jules L; Estrela, Pedro; Weber, James; Lacina, Karel; James, Tony D; Marken, Frank

    2015-06-10

    The interaction of ferrocene-boronic acid with fructose is investigated in aqueous 0.1 m phosphate buffer at pH 7, 8 and 9. Two voltammetric methods, based on 1) a dual-plate generator-collector micro-trench electrode (steady state) and 2) a square-wave voltammetry (transient) method, are applied and compared in terms of mechanistic resolution. A combination of experimental data is employed to obtain new insights into the binding rates and the cumulative binding constants for both the reduced ferrocene-boronic acid (pH dependent and weakly binding) and for the oxidised ferrocene-boronic acid (pH independent and strongly binding).

  13. Development of Sensitive Analytical Approach for the Quantification of α-Lipoic Acid Using Boron Doped Diamond Electrode.

    PubMed

    Stankovic, Dalibor M; Mehmeti, Eda; Kalcher, Kurt

    2016-01-01

    A boron doped diamond (BDD) electrode was investigated for use as an electrochemical sensor for α-lipoic acid (LA) using amperometric and differential pulse voltammetric detection. LA displays a well expressed oxidation peak at +0.9 V vs. Ag/AgCl in solutions with a pH value of 3. It was found that signals obtained are linearly related to the concentration range from 0.3 to 105 μM with detection limit of 0.088 μM. Interferences by common compounds such as ascorbic acid, uric acid and dopamine were tested and the method was successfully applied to the determination of LA in human body fluids where it gave recoveries in the range from 95 to 97%.

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

    PubMed

    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.

  15. On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand

    PubMed Central

    Musaev, Djamaladdin G.; Liebeskind, Lanny S.

    2009-01-01

    Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but it also displaces a phosphine ligand at the palladium center generating a catalytically competent mono-phosphine-palladium intermediate. PMID:20161122

  16. Palladium(II)‐Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox‐Neutral, Phosphine‐Free Transformation

    PubMed Central

    Deeming, Alex S.; Russell, Claire J.

    2015-01-01

    Abstract A redox‐neutral palladium(II)‐catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high‐yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C‐ or N‐based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one‐pot, two‐step process. PMID:26596861

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

    PubMed

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

    2015-01-28

    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 2(nd) 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.

  18. One-pot preparation of conductive composite containing boronic acid derivative for non-enzymatic glucose detection.

    PubMed

    Wang, Wen; Kong, Liyan; Zhu, Jiaming; Tan, Liang

    2017-07-15

    The composite consisting of poly(azure A), gold nanoparticles and 4-mercaptophenylboronic acid (PAA-AuNPs-MPBA) was prepared on the glassy carbon electrode surface by using a one-pot electropolymerization protocol. The generation of poly(azure A) film, the reduction of HAuCl4 and the binding of MPBA on metallic gold were simultaneously achieved in the cyclic voltammetric scan process, which was verified by scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy measurements. MPBA on the composite could capture glucose based on the specific boronic acid-diol binding and form a stable 5-membered cyclic boronate ester, which prevented the penetration and the charge transfer of the ferri-/ferrocyanide couple on the electrode surface. The peak-current change was found to be proportional to the logarithm of the glucose concentration in the range 10nM-10μM with a detection limit of 4nM. The proposed sensor exhibited good immunity from interference of several physiological compounds, reliable reproducibility and satisfying stability and it was successfully used in the determination of glucose in human serum sample. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Boronic Acid: A Bio-Inspired Strategy To Increase the Sensitivity and Selectivity of Fluorescent NADH Probe.

    PubMed

    Wang, Lu; Zhang, Jingye; Kim, Beomsue; Peng, Juanjuan; Berry, Stuart N; Ni, Yong; Su, Dongdong; Lee, Jungyeol; Yuan, Lin; Chang, Young-Tae

    2016-08-24

    Fluorescent probes have emerged as an essential tool in the molecular recognition events in biological systems; however, due to the complex structures of certain biomolecules, it remains a challenge to design small-molecule fluorescent probes with high sensitivity and selectivity. Inspired by the enzyme-catalyzed reaction between biomolecule and probe, we present a novel combination-reaction two-step sensing strategy to improve sensitivity and selectivity. Based on this strategy, we successfully prepared a turn-on fluorescent reduced nicotinamide adenine dinucleotide (NADH) probe, in which boronic acid was introduced to bind with NADH and subsequently accelerate the sensing process. This probe shows remarkably improved sensitivity (detection limit: 0.084 μM) and selectivity to NADH in the absence of any enzymes. In order to improve the practicality, the boronic acid was further modified to change the measurement conditions from alkalescent (pH 9.5) to physiological environment (pH 7.4). Utilizing these probes, we not only accurately quantified the NADH weight in a health care product but also evaluated intracellular NADH levels in live cell imaging. Thus, these bio-inspired fluorescent probes offer excellent tools for elucidating the roles of NADH in biological systems as well as a practical strategy to develop future sensitive and selective probes for complicated biomolecules.

  20. Trans-resveratrol boronic acid exhibits enhanced anti-proliferative activity on estrogen-dependent MCF-7 breast cancer cells

    PubMed Central

    Yenugonda, Venkata Mahidhar; Kong, Yali; Deb, Tushar B.; Yang, Yonghong; Riggins, Rebecca B.; Brown, Milton L.

    2012-01-01

    Resveratrol (RSV), a natural compound present in the skin and seeds of red grapes, is considered a phytoestrogen and has structural similarity to the synthetic estrogen diethylstilbestrol. RSV inhibits tumor cell growth in estrogen receptor-positive (ER+) and negative (ER-) breast cancer cell lines resulting in cell specific regulation of the G1/S and G2/M stages of the cell cycle. However apoptotic cell death was only observed in ER+ MCF-7 cells. In this study, we designed and synthesized boronic acid derivative of RSV and evaluated their biological effects on ER+ MCF-7 breast cancer cells. The trans-4 analog inhibited the growth of MCF-7 cells and is not a substrate for p-glycoprotein. The trans-4 analog induces G1 cell cycle arrest, which coincides with marked inhibition of G1 cell cycle proteins and a greater pro-apoptotic effect. Finally, the trans-4 analog had no effect on the estrogen-stimulated growth of MCF-7 cells. Our results demonstrate that the trans-4 analog inhibits MCF-7 breast cancer cells by a different mechanism of action than that of RSV (S-phase arrest), and provides a new class of novel boronic acids of RSV that inhibit breast cancer cell growth. PMID:22785207

  1. Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

    DOE PAGES

    Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

    2017-04-25

    A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO2 and H2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate to monodentate HCOO conversion.more » Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

  2. Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode.

    PubMed

    Garcia-Segura, Sergi; Brillas, Enric

    2011-04-01

    Oxalic and oxamic acids are the ultimate and more persistent by-products of the degradation of N-aromatics by electrochemical advanced oxidation processes (EAOPs). In this paper, the kinetics and oxidative paths of these acids have been studied for several EAOPs using a boron-doped diamond (BDD) anode and a stainless steel or an air-diffusion cathode. Anodic oxidation (AO-BDD) in the presence of Fe(2+) (AO-BDD-Fe(2+)) and under UVA irradiation (AO-BDD-Fe(2+)-UVA), along with electro-Fenton (EF-BDD), was tested. The oxidation of both acids and their iron complexes on BDD was clarified by cyclic voltammetry. AO-BDD allowed the overall mineralization of oxalic acid, but oxamic acid was removed much more slowly. Each acid underwent a similar decay in AO-BDD-Fe(2+) and EF-BDD, as expected if its iron complexes were not attacked by hydroxyl radicals in the bulk. The faster and total mineralization of both acids was achieved in AO-BDD-Fe(2+)-UVA due to the high photoactivity of their Fe(III) complexes that were continuously regenerated by oxidation of their Fe(II) complexes. Oxamic acid always released a larger proportion of NH(4)(+) than NO(3)(-) ion, as well as volatile NO(x) species. Both acids were independently oxidized at the anode in AO-BDD, but in AO-BDD-Fe(2+)-UVA oxamic acid was more slowly degraded as its content decreased, without significant effect on oxalic acid decay. The increase in current density enhanced the oxidation power of the latter method, with loss of efficiency. High Fe(2+) contents inhibited the oxidation of Fe(II) complexes by the competitive oxidation of Fe(2+) to Fe(3+). Low current densities and Fe(2+) contents are preferable to remove more efficiently these acids by the most potent AO-BDD-Fe(2+)-UVA method. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Synthesis and characterization of a novel boronic acid-functionalized chitosan polymeric nanosphere for highly specific enrichment of glycopeptides.

    PubMed

    Zou, Xiajuan; Liu, Dan; Zhong, Lijun; Yang, Bin; Lou, Yaxin; Yin, Yuxin

    2012-10-01

    In this study we describe a method for highly specific enrichment of glycopeptides with boronic acid-functionalized chitosan polymeric nanospheres and matrix assisted laser desorption-ionization mass spectrometry (MALDI-MS). This is the first time chitosan has been used to create nanosphere support material for selective enrichment of glycopeptides by modification with glycidyl methacrylate (GMA) and derivatization with 3-aminophenylboronic acid (APB). Due to their multifunctional chemical moieties, these 20-100 nm chitosan-GMA-APB nanospheres have unique properties, such as good dispersibility, good biocompatibility and chemical stability, as well as augmented specificity with glycopeptides. Enrichment conditions were optimized by using trypsin digested glycoprotein horseradish peroxidase. The high specificity of chitosan-GMA-APB nanospheres was demonstrated by effectively enriching glycopeptides from a digest mixture of horseradish peroxidase and nonglycoproteins (bovine serum albumin (BSA)).

  4. Palladium-catalyzed difluoroalkylation of aryl boronic acids: a new method for the synthesis of aryldifluoromethylated phosphonates and carboxylic acid derivatives.

    PubMed

    Feng, Zhang; Min, Qiao-Qiao; Xiao, Yu-Lan; Zhang, Bo; Zhang, Xingang

    2014-02-03

    The palladium-catalyzed difluoroalkylation of aryl boronic acids with bromodifluoromethylphosphonate, bromodifluoroacetate, and further derivatives has been developed. This method provides a facile and useful access to a series of functionalized difluoromethylated arenes (ArCF2 PO(OEt)2 , ArCF2 CO2 Et, and ArCF2 CONR(1) R(2) ) that have important applications in drug discovery and development. Preliminary mechanistic studies reveal that a single electron transfer (SET) pathway may be involved in the catalytic cycle.

  5. Discovery of 2-[5-(4-Fluorophenylcarbamoyl)pyridin-2-ylsulfanylmethyl]phenylboronic Acid (SX-517): Noncompetitive Boronic Acid Antagonist of CXCR1 and CXCR2

    PubMed Central

    2015-01-01

    The G protein-coupled chemokine receptors CXCR1 and CXCR2 play key roles in inflammatory diseases and carcinogenesis. In inflammation, they activate and recruit polymorphonuclear cells (PMNs) through binding of the chemokines CXCL1 (CXCR1) and CXCL8 (CXCR1 and CXCR2). Structure–activity studies that examined the effect of a novel series of S-substituted 6-mercapto-N-phenyl-nicotinamides on CXCL1-stimulated Ca2+ flux in whole human PMNs led to the discovery of 2-[5-(4-fluorophenylcarbamoyl)pyridin-2-ylsulfanylmethyl]phenylboronic acid (SX-517), a potent noncompetitive boronic acid CXCR1/2 antagonist. SX-517 inhibited CXCL1-induced Ca2+ flux (IC50 = 38 nM) in human PMNs but had no effect on the Ca2+ flux induced by C5a, fMLF, or PAF. In recombinant HEK293 cells that stably expressed CXCR2, SX-517 antagonized CXCL8-induced [35S]GTPγS binding (IC50 = 60 nM) and ERK1/2 phosphorylation. Inhibition was noncompetitive, with SX-517 unable to compete the binding of [125I]-CXCL8 to CXCR2 membranes. SX-517 (0.2 mg/kg iv) significantly inhibited inflammation in an in vivo murine model. SX-517 is the first reported boronic acid chemokine antagonist and represents a novel pharmacophore for CXCR1/2 antagonism. PMID:25254640

  6. BAD-lectins: boronic acid-decorated lectins with enhanced binding affinity for the selective enrichment of glycoproteins.

    PubMed

    Lu, Ying-Wei; Chien, Chih-Wei; Lin, Po-Chiao; Huang, Li-De; Chen, Chang-Yang; Wu, Sz-Wei; Han, Chia-Li; Khoo, Kay-Hooi; Lin, Chun-Cheng; Chen, Yu-Ju

    2013-09-03

    The weak and variable binding affinities exhibited by lectin-carbohydrate interactions have often compromised the practical utility of lectin in capturing glycoproteins for glycoproteomic applications. We report here the development and applications of a new type of hybrid biomaterial, namely a boronic acid-decorated lectin (BAD-lectin), for efficient bifunctional glycoprotein labeling and enrichment. Our binding studies showed an enhanced affinity by BAD-lectin, likely to be mediated via the formation of boronate ester linkages between the lectin and glycan subsequent to the initial recognition process and thus preserving its glycan-specificity. Moreover, when attached to magnetic nanoparticles (BAD-lectin@MNPs), 2 to 60-fold improvement on detection sensitivity and enrichment efficiency for specific glycoproteins was observed over the independent use of either lectin or BA. Tested at the level of whole cell lysates for glycoproteomic applications, three different types of BAD-lectin@MNPs exhibited excellent specificities with only 6% overlapping among the 295 N-linked glycopeptides identified. As many as 236 N-linked glycopeptides (80%) were uniquely identified by one of the BAD-lectin@MNPs. These results indicated that the enhanced glycan-selective recognition and binding affinity of BAD-lectin@MNPs will facilitate a complementary identification of the under-explored glycoproteome.

  7. Thermodynamic Analysis of the Selectivity Enhancement Obtained by Using Smart Hydrogels That Are Zwitterionic When Detecting Glucose With Boronic Acid Moieties

    PubMed Central

    Horkay, F.; Cho, S. H.; Tathireddy, P.; Rieth, L.; Solzbacher, F.; Magda, J.

    2011-01-01

    Because the boronic acid moiety reversibly binds to sugar molecules and has low cytotoxicity, boronic acid-containing hydrogels are being used in a variety of implantable glucose sensors under development, including sensors based on optical, fluorescence, and swelling pressure measurements. However, some method of glucose selectivity enhancement is often necessary, because isolated boronic acid molecules have a binding constant with glucose that is some forty times smaller than their binding constant with fructose, the second most abundant sugar in the human body. In many cases, glucose selectivity enhancement is obtained by incorporating pendant tertiary amines into the hydrogel network, thereby giving rise to a hydrogel that is zwitterionic at physiological pH. However, the mechanism by which incorporation of tertiary amines confers selectivity enhancement is poorly understood. In order to clarify this mechanism, we use the osmotic deswelling technique to compare the thermodynamic interactions of glucose and fructose with a zwitterionic smart hydrogel containing boronic acid moieties. We also investigate the change in the structure of the hydrogel that occurs when it binds to glucose or to fructose using the technique of small angle neutron scattering. PMID:22190765

  8. Heck-type coupling vs. conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyl compounds: a systematic investigation.

    PubMed

    Zou, Gang; Guo, Jianping; Wang, Zhiyong; Huang, Wen; Tang, Jie

    2007-07-28

    The competition between Heck-type coupling and conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyls has been systematically investigated in a toluene-H(2)O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to alpha,beta-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with alpha,beta-unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems.

  9. Evaluation of a novel sodium borocaptate-containing unnatural amino acid as a boron delivery agent for neutron capture therapy of the F98 rat glioma.

    PubMed

    Futamura, Gen; Kawabata, Shinji; Nonoguchi, Naosuke; Hiramatsu, Ryo; Toho, Taichiro; Tanaka, Hiroki; Masunaga, Shin-Ichiro; Hattori, Yoshihide; Kirihata, Mitsunori; Ono, Koji; Kuroiwa, Toshihiko; Miyatake, Shin-Ichi

    2017-01-23

    Boron neutron capture therapy (BNCT) is a unique particle radiation therapy based on the nuclear capture reactions in boron-10. We developed a novel boron-10 containing sodium borocaptate (BSH) derivative, 1-amino-3-fluorocyclobutane-1-carboxylic acid (ACBC)-BSH. ACBC is a tumor selective synthetic amino acid. The purpose of this study was to assess the biodistribution of ACBC-BSH and its therapeutic efficacy following Boron Neutron Capture Therapy (BNCT) of the F98 rat glioma. We evaluated the biodistribution of three boron-10 compounds, ACBC-BSH, BSH and boronophenylalanine (BPA), in vitro and in vivo, following intravenous (i.v.) administration and intratumoral (i.t.) convection-enhanced delivery (CED) in F98 rat glioma bearing rats. For BNCT studies, rats were stratified into five groups: untreated controls, neutron-irradiation controls, BNCT with BPA/i.v., BNCT with ACBC-BSH/CED, and BNCT concomitantly using BPA/i.v. and ACBC-BSH/CED. In vitro, ACBC-BSH attained higher cellular uptake F98 rat glioma cells compared with BSH. In vivo biodistribution studies following i.v. administration and i.t. CED of ACBC-BSH attained significantly higher boron concentrations than that of BSH, but much lower than that of BPA. However, following convection enhanced delivery (CED), ACBC-BSH attained significantly higher tumor concentrations than BPA. The i.t. boron-10 concentrations were almost equal between the ACBC-BSH/CED group and BPA/i.v. group of rats. The tumor/brain boron-10 concentration ratio was higher with ACBC-BSH/CED than that of BPA/i.v. group. Based on these data, BNCT studies were carried out in F98 glioma bearing rats using BPA/i.v. and ACBC-BSH/CED as the delivery agents. The corresponding mean survival times were 37.4 ± 2.6d and 44.3 ± 8.0d, respectively, and although modest, these differences were statistically significant. Our findings suggest that further studies are warranted to evaluate ACBC-BSH/CED as a boron delivery agent.

  10. Adsorption of boric acid on pure and humic acid coated am-Al(OH)3: A boron K-edge XANES study.

    PubMed

    Xu, Dani; Peak, Derek

    2007-02-01

    The fate and mobility of boric acid in the environment is largely controlled by adsorption reactions with soil organic matter and soil minerals to form surface complexes (Soil Sci Soc. Am. J. 1991, 55, 1582; Geochim. Cosmochim. Acta 2002, 67, 2551; Soil Sci. Soc. Am. J. 1995, 59, 405; Environ. Sci. Technol. 1995, 29, 302). In this study, boric acid adsorption on pure am-Al(OH)3 and 5% (w/w) humic acid (HA) coated am-Al(OH)3 were investigated both as a function of pH (4.5-11) and initial boric acid concentration (0-4.5 mmol L(-1)). Batch adsorption isotherm experiments were also conducted with samples exposed to atmospheric CO2 and anaerobic (N2) conditions to examine the effects of dissolved CO2 on boric acid adsorption. Boron (B) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to investigate the coordination of boric acid adsorbed at mineral/water interfaces. The XANES spectra of boric acid adsorption samples showed that both trigonally and tetrahedrally coordinated B complexes were present on the mineral surface. Both macroscopic and spectroscopic experiments revealed that the combination of HA coating on am-Al(OH)3 and dissolved CO2 decreased boric acid adsorption compared to adsorption on pure am-Al(OH)3.

  11. Carbohydrate-interactive pDNA and siRNA gene vectors based on boronic acid functionalized poly(amido amine)s.

    PubMed

    Piest, Martin; Ankoné, Marc; Engbersen, Johan F J

    2013-08-10

    In order to evaluate the influence of incorporation of boronic acid groups on the properties of poly(amido amine)s as gene vectors, a novel poly(amido amine) copolymer p(CBA-ABOL/2AMPBA) containing ortho-aminomethylphenylboronic acid (2AMPBA) moieties was prepared by Michael-type polyaddition of a mixture of 1,4-aminobutanol (ABOL) and 2-((4-aminobutylamino)methyl)phenyl boronic acid to N,N'-cystamine bisacrylamide (CBA). It appeared that the presence of the boronic acid moieties as side groups along the polymer chain strongly enhances the stability of the self-assembled nanoparticles and nanosized polyplexes formed from this polymer; no aggregation was observed after storage for 6days at 37°C. This strong stabilization can be attributed to intermolecular Lewis acid-base interactions between the 2AMPBA groups and the alcohol and amine groups present in the polymer, leading to dynamical (reversible) crosslinking in the nanoparticles. Moreover, since the boronic acids can reversibly form boronic esters with vicinal diol groups, the presence of the 2AMPBA groups add carbohydrate-interactive properties to these polymers that strongly influence their behavior as gene delivery vectors. DNA transfection with p(CBA-ABOL/2AMPBA) polyplexes gave transfection efficiencies that were approximately similar to commercial PEI in different cell lines (COS-7, HUH-6 and H1299-Fluc), but lower than those obtained with reference polyplexes from p(CBA-ABOL). It is hypothesized that the uptake of the boronated polyplexes is suppressed by binding to the glycocalyx of the cells. This is supported by the observation that addition of sorbitol or dextran to the transfection medium significantly enhances the transfection efficiency, which can be attributed to increased cellular uptake of the polyplexes due to boronic ester formation with these agents. AFM, SEM and confocal microscopy showed that polyplexes of p(CBA-ABOL/2AMPBA) become decorated with a dextran layer in the presence of 0.9% (w

  12. Tribological properties of boric acid and boric-acid-forming surfaces: Part 2, Formation and self-lubrication mechanisms of boric acid films on boron- and boric-oxide-containing surfaces

    SciTech Connect

    Erdemir, A.; Fenske, G.R.; Erck, R.A.; Nichols, F.A.; Busch, D.

    1990-01-01

    This paper describes the formation and self-lubricating mechanisms of boric acid films on boron- and boric oxide-containing surfaces. As reported in part I, boric acid, owing to a layered triclinic crystal structure and weak interlayer bonds, enjoys an unusual lubrication capability. RF-magnetron sputtering and vacuum evaporation techniques were used to produce thin coatings of boron and boric oxides on steel substrates. The results of tribological experiments indicate that the room temperature friction coefficient of tribosystems that include boron and/or boric oxide coatings ranges from 0.05 to 0.07, depending on the coating type. Laser-Raman spectroscopy of these surfaces revealed that this low friction is associated with a thin boric acid film that forms on the surfaces of these coatings. The fabrication and potential importance of boric acid and boric acid-forming surfaces for practical applications are enumerated. Surface engineering of tribomaterials, such as these demonstrated in this paper, is suggested as a new lubrication concept for use in present and future tribological industries. 16 refs.

  13. Spectroscopic studies on 9H-carbazole-9-(4-phenyl) boronic acid pinacol ester by DFT method

    NASA Astrophysics Data System (ADS)

    Sas, E. B.; Kurt, M.; Can, M.; Horzum, N.; Atac, A.

    2016-08-01

    9H-Carbazole-9-(4-phenyl) boronic acid pinacol ester (9-CPBAPE) molecule was investigated by FT-IR, Raman, UV-vis, 1H and 13C NMR spectra. FT-IR, FT-Raman and dispersive Raman spectra were recorded in the solid phase. 1H, 13C NMR and UV-vis spectra were recorded in dimethyl sulfoxide (DMSO) solution. The results of theoretical calculations for the spectra of the title molecule were compared with the experimental spectra. The highest occupied molecular orbital (HOMO) the lowest unoccupied molecular orbital (LUMO) and molecular electrostatic potential (MEP) analyses were performed. The theoretical calculations for the molecular structure and spectroscopic studies were performed with DFT (B3LYP) and 6-311G (d,p) basis set calculations using the Gaussian 09 program. The total (TDOS), partial (PDOS) density of state and overlap population density of state (OPDOS) diagrams analyses were performed using GaussSum 2.2 program.

  14. Chemometric study on the electrochemical incineration of nitrilotriacetic acid using platinum and boron-doped diamond anode.

    PubMed

    Zhang, Chunyong; He, Zhenzhu; Wu, Jingyu; Fu, Degang

    2015-07-01

    This study investigated the electrochemical incineration of nitrilotriacetic acid (NTA) at boron-doped diamond (BDD) and platinum (Pt) anodes. Trials were performed in the presence of sulfate electrolyte media under recirculation mode. The parameters that influence the degradation efficiency were investigated, including applied current density, flow rate, supporting electrolyte concentration and reaction time. To reduce the number of experiments, the system had been managed under chemometric technique named Doehlert matrix. As a consequence, the mineralization of NTA demonstrated similar behavior upon operating parameters on these two anodes. Further kinetic study indicated that the degradations followed pseudo-first-order reactions for both BDD and Pt anodes, and the reaction rate constant of the former was found to be higher than that of the latter. Such difference could be interpreted by results from fractal analysis. In addition, a reaction sequence for NTA mineralization considering all the detected intermediates was also proposed.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Qi, Yao; Long, Hangyu; Ma, Li; Wei, Quiping; Li, Site; Yu, Zhiming; Hu, Jingyuan; Liu, Peizhi; Wang, Yijia; Meng, Lingcong

    2016-12-01

    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 [Fe3 (CN) 6]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.

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

    NASA Astrophysics Data System (ADS)

    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

  18. Sequencing and characterization of oligosaccharides using infrared multiphoton dissociation and boronic acid derivatization in a quadrupole ion trap.

    PubMed

    Pikulski, Michael; Hargrove, Amanda; Shabbir, Shagufta H; Anslyn, Eric V; Brodbelt, Jennifer S

    2007-12-01

    A simplified method for determining the sequence and branching of oligosaccharides using infrared multiphoton dissociation (IRMPD) in a quadrupole ion trap (QIT) is described. An IR-active boronic acid (IRABA) reagent is used to derivatize the oligosaccharides before IRMPD analysis. The IRABA ligand is designed to both enhance the efficiency of the derivatization reaction and to facilitate the photon absorption process. The resulting IRMPD spectra display oligosaccharide fragments that are formed from primarily one type of diagnostic cleavage, thus making sequencing straightforward. The presence of sequential fragment ions, a phenomenon of IRMPD, permit the comprehensive sequencing of the oligosaccharides studied in a single stage of activation. We demonstrate this approach for two series of oligosaccharides, the lacto-N-fucopentaoses (LNFPs) and the lacto-N-difucohexaoses (LNDFHs).

  19. Rhenium hydride/boron Lewis acid cocatalysis of alkene hydrogenations: activities comparable to those of precious metal systems.

    PubMed

    Jiang, Yanfeng; Hess, Jeannine; Fox, Thomas; Berke, Heinz

    2010-12-29

    Dibromonitrosyl(dihydrogen)rhenium(I) complexes [ReBr(2)(NO)(PR(3))(2)(η(2)-H(2))] (1; R = iPr, a; Cy, b) and Me(2)NH·BH(3) (DMAB) catalyze at either 90 °C or ambient temperature under 10 bar of H(2) the hydrogenation of various terminal and cyclic alkenes (1-hexene, 1-octene, cyclooctene, styrene, 1,5-cyclooctadiene, 1,7-octadiene, α-methylstyrene). Maximum turnover frequency (TOF) values of 3.6 × 10(4) h(-1) at 90 °C and 1.7 × 10(4) h(-1) at 23 °C were achieved in the hydrogenation of 1-hexene. The extraordinary catalytic performance of the 1/DMAB system is attributed to the formation of five-coordinate rhenium(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (2; R = iPr, a; Cy, b) and the action of the Lewis acid BH(3) originating from DMAB. The related 2/BH(3)·THF catalytic system also exhibits under the same conditions high activity in the hydrogenation of various alkenes with a maximum turnover number (TON) of 1.2 × 10(4) and a maximum TOF of 4.0 × 10(4) h(-1). For the hydrogenations of 1-hexene with 2a and 2b, the effect of the strength of the boron Lewis acid was studied, the acidity being in the following order: BCl(3) > BH(3) > BEt(3) ≈ BF(3) > B(C(6)F(5))(3) > BPh(3) ≫ B(OMe)(3). The order in catalytic activity was found to be B(C(6)F(5))(3) > BEt(3) ≈ BH(3)·THF > BPh(3) ≫ BF(3)·OEt(2) > B(OMe)(3) ≫ BCl(3). The stability of the catalytic systems was checked via TON vs time plots, which revealed the boron Lewis acids to cause an approximate inverse order with the Lewis acid strength: BPh(3) > BEt(3) ≈ BH(3)·THF > B(C(6)F(5))(3). For the 2a/BPh(3) system a maximum TON of 3.1 × 10(4) and for the 2a/B(C(6)F(5))(3) system a maximum TOF of 5.6 × 10(4) h(-1) were obtained in the hydrogenation of 1-hexene. On the basis of kinetic isotope effect determinations, H(2)/D(2) scrambling, halide exchange experiments, Lewis acid variations, and isomerization of terminal alkenes, an Osborn-type catalytic cycle is proposed with olefin before H(2

  20. Highly Luminescent Microporous Organic Polymer with Lewis Acidic Boron Sites on the Pore Surface: Ratiometric Sensing and Capture of F(-) Ions.

    PubMed

    Suresh, Venkata M; Bandyopadhyay, Arkamita; Roy, Syamantak; Pati, Swapan K; Maji, Tapas Kumar

    2015-07-20

    Reversible and selective capture/detection of F(-) ions in water is of the utmost importance, as excess intake leads to adverse effects on human health. Highly robust Lewis acidic luminescent porous organic materials have potential for efficient sequestration and detection of F(-) ions. Herein, the rational design and synthesis of a boron-based, Lewis acidic microporous organic polymer (BMOP) derived from tris(4-bromo-2,3,5,6-tetramethylphenyl)boron nodes and diethynylbiphenyl linkers with a pore size of 1.08 nm for selective turn-on sensing and capture of F(-) ion are reported. The presence of a vacant pπ orbital on the boron center of BMOP results in intramolecular charge transfer (ICT) from the linker to boron. BMOP shows selective turn-on blue emission for F(-) ions in aqueous mixtures with a detection limit of 2.6 μM. Strong B-F interactions facilitate rapid sequestration of F(-) by BMOP. The ICT emission of BMOP can be reversibly regenerated by addition of an excess of water, and the polymer can be reused several times.

  1. Efficient nuclear drug translocation and improved drug efficacy mediated by acidity-responsive boronate-linked dextran/cholesterol nanoassembly.

    PubMed

    Zhu, Jing-Yi; Lei, Qi; Yang, Bin; Jia, Hui-Zhen; Qiu, Wen-Xiu; Wang, Xuli; Zeng, Xuan; Zhuo, Ren-Xi; Feng, Jun; Zhang, Xian-Zheng

    2015-06-01

    The present study reported a lysosome-acidity-targeting bio-responsive nanovehicle self-assembled from dextran (Dex) and phenylboronic acid modified cholesterol (Chol-PBA), aiming at the nucleus-tropic drug delivery. The prominent advantage of this assembled nanoconstruction arose from its susceptibility to acidity-labile dissociation concurrently accompanied with the fast liberation of encapsulated drugs, leading to efficient nuclear drug translocation and consequently favorable drug efficacy. By elaborately exploiting NH4Cl pretreatment to interfere with the cellular endosomal acidification progression, this study clearly evidenced at a cellular level the strong lysosomal-acidity dependency of nuclear drug uptake efficiency, which was shown to be the main factor influencing the drug efficacy. The boronate-linked nanoassembly displayed nearly no cytotoxicity and can remain structural stability under the simulated physiological conditions including 10% serum and the normal blood sugar concentration. The cellular exposure to cholesterol was found to bate the cellular uptake of nanoassembly in a dose-dependent manner, suggesting a cholesterol-associated mechanism of the intracellular internalization. The in vivo antitumor assessment in xenograft mouse models revealed the significant superiority of DOX-loaded Dex/Chol-PBA nanoassembly over the controls including free DOX and the DOX-loaded non-sensitive Dex-Chol, as reflected by the more effective tumor-growth inhibition and the better systematic safety. In terms of the convenient preparation, sensitive response to lysosomal acidity and efficient nuclear drug translocation, Dex/Chol-PBA nanoassembly derived from natural materials shows promising potentials as the nanovehicle for nucleus-tropic drug delivery especially for antitumor agents. More attractively, this study offers a deeper insight into the mechanism concerning the contribution of acidity-responsive delivery to the enhanced chemotherapy performance.

  2. Simultaneous voltammetric determination of paracetamol and ascorbic acid using a boron-doped diamond electrode modified with Nafion and lead films.

    PubMed

    Tyszczuk-Rotko, Katarzyna; Bęczkowska, Ilona; Wójciak-Kosior, Magdalena; Sowa, Ireneusz

    2014-11-01

    The paper describes the fabrication and application of a novel sensor (a boron-doped diamond electrode modified with Nafion and lead films) for the simultaneous determination of paracetamol and ascorbic acid by differential pulse voltammetry. The main advantage of the lead film and polymer covered boron-doped diamond electrode is that the sensitivity of the stripping responses is increased and the separation of paracetamol and ascorbic acid signals is improved due to the modification of the boron-doped diamond surface by the lead layer. Additionally, the repeatability of paracetamol and ascorbic acid signals is improved by the application of the Nafion film coating. In the presence of oxygen, linear calibration curves were obtained in a wide concentration range from 5×10(-7) to 2×10(-4) mol L(-1) for paracetamol and from 1×10(-6) to 5×10(-4) mol L(-1) for ascorbic acid. The analytical utility of the differential pulse voltammetric method elaborated was tested in the assay of paracetamol and ascorbic acid in commercially available pharmaceutical formulations and the method was validated by high performance liquid chromatography coupled with diode array detector.

  3. Boronizing protects metals against wear

    SciTech Connect

    Stewart, K.

    1997-03-01

    Boronizing is a thermochemical surface treatment that involves diffusion of boron into a base metal at a high temperature. The resulting metallic boride provides high hardness and resistance to acid corrosion, and lengthens service life by a factor of three to ten. Boronizing fills a gap between conventional surface treatments and the more exotic chemical and physical vapor deposition. In a number of applications, boronizing has replaced such processes as carburizing, nitriding, and nitrocarburizing. It has even replaced hard chrome plating in some cases, while achieving similar service life improvements. Boron can be uniformly applied to irregular surfaces, and can be applied to specific areas of a surface. It is also suitable for high-volume production applications, as first demonstrated in the European automotive industry. This article describes the boronizing process, provides material selection/preparation criteria, and lists industrial applications.

  4. The B(C6F5)3 boron Lewis acid route to arene-annulated pentalenes.

    PubMed

    Chen, Chao; Harhausen, Marcel; Fukazawa, Aiko; Yamaguchi, Shigehiro; Fröhlich, Roland; Daniliuc, Constantin G; Petersen, Jeffrey L; Kehr, Gerald; Erker, Gerhard

    2014-06-01

    4,5-Dimethyl-1,2-bis(1-naphthylethynyl)benzene (12) undergoes a rapid multiple ring-closure reaction upon treatment with the strong boron Lewis acid B(C6F5)3 to yield the multiply annulated, planar conjugated π-system 13 (50 % yield). In the course of this reaction, a C6F5 group was transferred from boron to carbon. Treatment of 12 with CH3B(C6F5)2 proceeded similarly, giving a mixture of 13 (C6F5-transfer) and the product 15, which was formed by CH3-group transfer. 1,2-Bis(phenylethynyl)benzene (8 a) reacts similarly with CH3B(C6F5)2 to yield a mixture of the respective C6F5- and CH3-substituted dibenzopentalenes 10 a and 16. The reaction is thought to proceed through zwitterionic intermediates that exhibit vinyl cation reactivities. Some B(C6F5)3-substituted species (26, 27) consequently formed by in situ deprotonation upon treatment of the respective 1,2-bis(alkynyl)benzene starting materials (24, 8) with the frustrated Lewis pair B(C6F5)3/P(o-tolyl)3. The overall formation of the C6F5-substituted products formally require HB(C6F5)2 cleavage in an intermediate dehydroboration step. This was confirmed in the reaction of a thienylethynyl-containing starting material 21 with B(C6F5)3, which gave the respective annulated pentalene product 23 that had the HB(C6F5)2 moiety 1,4-added to its thiophene ring. Compounds 12-14, 23, and 26 were characterized by X-ray diffraction.

  5. A disc diffusion assay for detection of class A, B and OXA-48 carbapenemases in Enterobacteriaceae using phenyl boronic acid, dipicolinic acid and temocillin.

    PubMed

    van Dijk, K; Voets, G M; Scharringa, J; Voskuil, S; Fluit, A C; Rottier, W C; Leverstein-Van Hall, M A; Cohen Stuart, J W T

    2014-04-01

    Class A and B carbapenemases in Enterobacteriaceae may be detected using carbapenemase inhibition tests with boronic acid derivatives (BA) and dipicolinic acid (DPA)/EDTA, respectively. However, for OXA-48 (like) carbapenemases, no specific inhibitor is available. Because OXA-48 confers high-level temocillin resistance, a disc diffusion assay using temocillin as well as BA and DPA inhibition tests was evaluated for detection of class A, B and OXA-48 carbapenemases. The test collection included 128 well-characterized non-repeat Enterobacteriaceae isolates suspected of carbapenemase production; that is, with meropenem MICs ≥ 0.5 mg/L, including 99 carbapenemase producers (36 KPC, one GES, 31 MBL, four KPC plus VIM, 25 OXA-48, two OXA-162), and 29 ESBL and/or AmpC-producing isolates. PCR and sequencing of beta-lactamase genes was used as a reference test. Phenotypic carbapenemase detection was performed with discs (Rosco) containing meropenem (10 μg), temocillin (30 μg), meropenem + phenyl boronic acid (PBA), meropenem + DPA, meropenem + BA + DPA, and meropenem + cloxacillin (CL). Absence of synergy between meropenem and BA and/or DPA and a temocillin zone ≤10 mm was used to identify OXA-48. The sensitivity for identification of class A, B and OXA-48 carbapenemases was 95%, 90% and 100%, with 96-100% specificity. In non-Proteus species, the sensitivity for class B carbapenemase detection was 97%. All isolates without PBA or DPA synergy and a temocillin disc zone ≤10 mm were OXA-48 (like) positive. In conclusion, carbapenemase inhibition tests with PBA and DPA combined with a temocillin disc provide a reliable phenotypic confirmation method for class A, B and OXA-48 carbapenemases in Enterobacteriaceae.

  6. Site and chirality selective chemical modifications of boron nitride nanotubes (BNNTs) via Lewis acid-base interactions.

    PubMed

    Sundaram, Rajashabala; Scheiner, Steve; Roy, Ajit K; Kar, Tapas

    2015-02-07

    The pristine BNNTs contain both Lewis acid (boron) and Lewis base (nitrogen) centers at their surface. Interactions of ammonia and borane molecules, representatives of Lewis base and acid as adsorbates respectively, with matching sites at the surface of BNNTs, have been explored in the present DFT study. Adsorption energies suggest stronger chemisorption (about 15-20 kcal mol(-1)) of borane than ammonia (about 5-10 kcal mol(-1)) in both armchair (4,4) and zigzag (8,0) variants of the tube. NH3 favors (8,0) over the (4,4) tube, whereas BH3 exhibits the opposite preference, indicating some chirality dependence on acid-base interactions. A new feature of bonding is found in BH3/AlH3-BNNTs (at the edge site) complexes, where one hydrogen of the guest molecule is involved in three-center two-electron bonding, in addition to dative covalent bond (N: → B). This interaction causes a reversal of electron flow from borane/alane to BNNT, making the tube an electron acceptor, suggesting tailoring of electronic properties could be possible by varying strength of incoming Lewis acids. On the contrary, BNNTs always behave as electron acceptor in ammonia complexes. IR, XPS and NMR spectra show some characteristic features of complexes and can help experimentalists to identify not only structures of such complexes but also the location of the guest molecules and design second functionalizations. Interaction with several other neutral BF3, BCl3, BH2CH3 and ionic CH3(+) acids as well as amino group (CH3NH2 and NH2COOH) were also studied. The strongest interaction (>100 kcal mol(-1)) is found in BNNT-CH3(+) complexes and H-bonds are the only source of stability of NH2COOH-BNNT complexes.

  7. Minerals Yearbook 1989: Boron

    SciTech Connect

    Lyday, P.A.

    1990-08-01

    U.S. production and sales of boron minerals and chemicals decreased during the year. Domestically, glass fiber insulation was the largest use for borates, followed by sales to distributors, textile-grade glass fibers, and borosilicate glasses. California was the only domestic source of boron minerals. The United States continued to provide essentially all of its own supply while maintaining a strong position as a source of sodium borate products and boric acid exported to foreign markets. Supplementary U.S. imports of Turkish calcium borate and calcium-sodium borate ores, borax, and boric acid, primarily for various glass uses, continued.

  8. Epoxy resin composition containing metal tetrafluoroborate and boron ester

    SciTech Connect

    Morehead, G.T.

    1990-06-12

    This patent describes a curable composition. It comprises: a polyepoxide; a metal tetrafluoroborate; and at least one boron ester selected from the group consisting of triesters of boric acid and diesters of boronic acid.

  9. Boron cosmochemistry

    NASA Technical Reports Server (NTRS)

    Curtis, D. B.; Gladney, E. S.

    1985-01-01

    The abundances of boron, silicon, sulfur, and sodium were determined in 50 pieces of 28 chondritic meteorites. Boron abundances are found to define compositionally distinct domains within type C2M carbonaceous chondrites and petrologic type 5 and 6 ordinary chondrites. These domains may manifest the redistribution of boron within meteorites in response to low-temperature hydrous processes in C2M chondrites and high-temperature metamorphic processes in high petrologic type ordinary chondrites. Assuming that the redistribution was limited to regions comparable in size to the mass of the available meteorites, the boron abundance in unaltered material is determined. The depletion factors for boron in chondritic subgroups correlate with those for sulfur in the same subgroups. This correlation indicates that boron, like sulfur, is a moderately volatile element with a condensation temperature between 400 and 900 K.

  10. Boron supercapacitors

    DOE PAGES

    Zhan, Cheng; Zhang, Pengfei; Dai, Sheng; ...

    2016-11-16

    Supercapacitors based on the electric double-layer mechanism use porous carbons or graphene as electrodes. To move beyond this paradigm, we propose boron supercapacitors to leverage two-dimensional (2D) boron sheets’ metallicity and low weight. Six 2D boron sheets from both previous theoretical design and experimental growth are chosen as test electrodes. By applying joint density functional theory (JDFT) to the electrode–electrolyte system, we examine how the 2D boron sheets charge up against applied potential. JDFT predicts that these 2D boron sheets exhibit specific capacitance on the order of 400 F/g, about four times that of graphene. As a result, our workmore » suggests that 2D boron sheets are promising electrodes for supercapacitor applications.« less

  11. Boron supercapacitors

    SciTech Connect

    Zhan, Cheng; Zhang, Pengfei; Dai, Sheng; Jiang, De -en

    2016-11-16

    Supercapacitors based on the electric double-layer mechanism use porous carbons or graphene as electrodes. To move beyond this paradigm, we propose boron supercapacitors to leverage two-dimensional (2D) boron sheets’ metallicity and low weight. Six 2D boron sheets from both previous theoretical design and experimental growth are chosen as test electrodes. By applying joint density functional theory (JDFT) to the electrode–electrolyte system, we examine how the 2D boron sheets charge up against applied potential. JDFT predicts that these 2D boron sheets exhibit specific capacitance on the order of 400 F/g, about four times that of graphene. As a result, our work suggests that 2D boron sheets are promising electrodes for supercapacitor applications.

  12. Regioselective cross-coupling reactions of boronic acids with dihalo heterocycles.

    PubMed

    Houpis, Ioannis N; Liu, Renmao; Wu, Yanfei; Yuan, Yukuan; Wang, Youchu; Nettekoven, Ulrike

    2010-10-15

    The carboxylic acid anion moiety has been used as a tunable directing group in the cross-coupling reaction of 2,6-dichloronicotinic acid and 2,5-dibromo-1,2,4-triazole derivatives producing selectively the 2- or 6-substituted nicotinic acids, while only the 5-substituted triazoles were obtained under a variety of conditions.

  13. Ligand-Accelerated ortho-C–H Alkylation of Arylcarboxylic Acids Using Alkyl Boron Reagents

    PubMed Central

    Thuy-Boun, Peter S.; Villa, Giorgio; Dang, Devin; Richardson, Paul; Su, Shun; Yu, Jin-Quan

    2013-01-01

    A protocol for the Pd(II)-catalyzed ortho-C–H alkylation of phenylacetic and benzoic acids using alkylboron reagents is disclosed. Mono-protected amino acid ligands (MPAA) were found to significantly promote reactivity. Both potassium alkyltrifluoroborates and alkylboronic acids were compatible coupling partners. The possibility of a radical alkyl transfer to Pd(II) was also investigated. PMID:24124892

  14. A boron phosphate-phosphoric acid composite membrane for medium temperature proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Mamlouk, M.; Scott, K.

    2015-07-01

    A composite membrane based on a non-stoichiometric composition of BPO4 with excess of PO4 (BPOx) was synthesised and characterised for medium temperature fuel cell use (120-180 °C). The electrolyte was characterised by FTIR, SS-NMR, TGA and XRD and showed that the B-O is tetrahedral, in agreement with reports in the literature that boron phosphorus oxide compounds at B:P < 1 are exclusively built of borate and phosphate tetrahedra. Platinum micro electrodes were used to study the electrolyte compatibility and stability towards oxygen reduction at 150 °C and to obtain kinetic and mass transport parameters. The conductivities of the pure BPOx membrane electrolyte and a Polybenzimidazole (PBI)-4BPOx composite membrane were 7.9 × 10-2 S cm-1 and 4.5 × 10-2 S cm-1 respectively at 150 °C, 5%RH. Fuel cell tests showed a significant enhancement in performance of BPOx over that of typical 5.6H3PO4-PBI membrane electrolyte. The enhancement is due to the improved ionic conductivity (3×), a higher exchange current density of the oxygen reduction (30×) and a lower membrane gas permeability (10×). Fuel cell current densities at 0.6 V were 706 and 425 mA cm-2 for BPOx and 5.6H3PO4-PBI, respectively, at 150 °C with O2 (atm).

  15. Asymmetric Ring-Opening Reactions of Aza- and Oxa-bicyclic Alkenes with Boronic Acids Using a Palladium/Zinc Co-catalytic System.

    PubMed

    Zhang, Wei; Chen, Jingchao; Zeng, Guangzhi; Yang, Fan; Xu, Jianbin; Sun, Weiqing; Shinde, Madhuri Vikas; Fan, Baomin

    2017-03-03

    The asymmetric ring opening reactions of bicyclic alkenes with boronic acids were accomplished by using a highly active palladium/zinc co-catalytic system that was suitable for both azabenzonorbornadienes and oxabenzonorbornadienes, which were transformed to the corresponding chiral hydronaphthalene products in high yields (up to 99%) and high optical purities (up to 98% ee). The reaction protocol is general and mild and displays good functional group tolerance.

  16. Detection of KPC Carbapenemase in Pseudomonas aeruginosa Isolated From Clinical Samples Using Modified Hodge Test and Boronic Acid Phenotypic Methods and Their Comparison With the Polymerase Chain Reaction

    PubMed Central

    Falahat, Saeed; Shojapour, Mana; Sadeghi, Abdorrahim

    2016-01-01

    Background Bacterial resistance to antibiotics has become a major source of concern for public health. Pseudomonas aeruginosa strains are important opportunistic pathogens. These bacteria have a high resistance to a wide range of existing antimicrobials and antibiotics. Objectives The present study was performed to evaluate the frequency of KPC in P. aeruginosa isolated from clinical samples of educational hospitals of Arak University of Medical Sciences, using the mentioned phenotypic and genotypic methods. Materials and Methods One hundred and eight non-duplicate clinical isolates of P. aeruginosa were collected from hospitals of Arak University of Medical Sciences, Arak, Iran. Antibacterial susceptibility was determined by the disk diffusion method. KPC production was confirmed by the Modified Hodge Test (MHT), which is a phenotypic test, and combined-disk test with boronic acid and the Polymerase Chain Reaction (PCR). Results In the present study, 13 isolates (12%) of P. aeruginosa were positive for KPC, using PCR. Comparison of the two phenotypic methods used in this study showed that boronic acid is more sensitive than MHT in identification of KPC-producing strains (84.6% vs. 77%). Conclusions Utilization of reliable methods for identifying carbapenemase-producing strains and determining their antibiotic resistance pattern could have a very important role in treatment of infections caused by these strains. A substantial amount of P. aeruginosa isolated from clinical samples of hospitals in Arak (Iran) produce KPC carbapenemase. Due to their low specificity, MHT and boronic acid phenotypic methods could not completely identify KPC-producing P. aeruginosa. However, the sensitivity of boronic acid phenotypic method in detection of KPC was higher than MHT. PMID:27800140

  17. Rh-Catalyzed Conjugate Addition of Aryl and Alkenyl Boronic Acids to α-Methylene-β-lactones: Stereoselective Synthesis of trans-3,4-Disubstituted β-Lactones.

    PubMed

    Malapit, Christian A; Luvaga, Irungu K; Caldwell, Donald R; Schipper, Nicholas K; Howell, Amy R

    2017-09-01

    A one-step preparation of 3,4-disubstituted β-lactones through Rh-catalyzed conjugate addition of aryl or alkenyl boronic acids to α-methylene-β-lactones is described. The operationally simple, stereoselective transformation provides a broad range of β-lactones from individual α-methylene-β-lactone templates. This methodology allowed for a direct, final-step C-3 diversification of nocardiolactone, an antimicrobial natural product.

  18. Fine-Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors.

    PubMed

    Jaiswal, Kuldeep; Prashanth, Billa; Singh, Sanjay

    2016-07-25

    Reactions of bis(phosphinimino)amines LH and L'H with Me2 S⋅BH2 Cl afforded chloroborane complexes LBHCl (1) and L'BHCl (2), and the reaction of L'H with BH3 ⋅Me2 S gave a dihydridoborane complex L'BH2 (3) (LH=[{(2,4,6-Me3 C6 H2 N)P(Ph2 )}2 N]H and L'H=[{(2,6-iPr2 C6 H3 N)P(Ph2 )}2 N]H). Furthermore, abstraction of a hydride ion from L'BH2 (3) and LBH2 (4) mediated by Lewis acid B(C6 F5 )3 or the weakly coordinating ion pair [Ph3 C][B(C6 F5 )4 ] smoothly yielded a series of borenium hydride cations: [L'BH](+) [HB(C6 F5 )3 ](-) (5), [L'BH](+) [B(C6 F5 )4 ](-) (6), [LBH](+) [HB(C6 F5 )3 ](-) (7), and [LBH](+) [B(C6 F5 )4 ](-) (8). Synthesis of a chloroborenium species [LBCl](+) [BCl4 ](-) (9) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH2 (4) with three equivalents of BCl3 . It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three-coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl4 (-) can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4-dimethylaminopyridine (DMAP), [LBH⋅(DMAP)](+) [B(C6 F5 )4 ](-) (10). The solid-state structures of complexes 1, 5, and 9 were investigated by means of single-crystal X-ray structural analysis.

  19. Synthesis of sulfonamide- and sulfonyl-phenylboronic acid-modified silica phases for boronate affinity chromatography at physiological pH.

    PubMed

    Li, Xiaobao; Pennington, Justin; Stobaugh, John F; Schöneich, Christian

    2008-01-15

    Two new types of boronate affinity solid phases were synthesized and characterized. The materials were prepared by silylation of porous silica gel with monochlorosilane derivatives containing synthetic sulfonyl- and sulfonamide-substituted phenylboronic acids. The new solid phases were evaluated for boronate affinity chromatography with aryl and alkyl cis-diol compounds and were found to be suitable for the retention of cis-diols under acidic conditions. Significant correlations between the retention factor (K) and the pH of the mobile phase demonstrate that the binding of cis-diols to the solid phases is best rationalized by chelation. Based on the lower pKa, caused by the electron-withdrawing effects of the sulfonyl and sulfonamide groups, these media display an enhanced affinity for cis-diols as compared with unsubstituted phenylboronic acid. Using isocratic elution, a mixture of various biologically relevant l-tyrosines, l-DOPA, and several catecholamines were resolved with a mobile phase composed of 0.05M phosphate buffer (pH 5.5). Mono-, di-, and triphosphates of adenosine were also separated at pH 6.0. Hence, the new boronate solid phase offers efficient affinity separation and purification of cis-diol-containing molecules under rather mild pH conditions.

  20. Atomically Thin Layers of Graphene and Hexagonal Boron Nitride Made by Solvent Exfoliation of Their Phosphoric Acid Intercalation Compounds.

    PubMed

    Kovtyukhova, Nina I; Perea-López, Nestor; Terrones, Mauricio; Mallouk, Thomas E

    2017-07-25

    The development of scalable and reliable techniques for the production of the atomically thin layers of graphene and hexagonal boron nitride (h-BN) in bulk quantities could make these materials a powerful platform for devices and composites that impact a wide variety of technologies (Nature 2012, 490, 192-200). To date a number of practical exfoliation methods have been reported that are based on sonicating or stirring powdered graphite or h-BN in common solvents. However, the products of these experiments consist mainly of few-layer sheets and contain only a small fraction of monolayers. A possible reason for this is that splitting the crystals into monolayers starts from solvent intercalation, which must overcome the substantial interlayer cohesive energy (120-720 mJ/m(2)) of the van der Waals solids. Here we show that the yield of the atomically thin layers can be increased to near unity when stage-1 intercalation compounds of phosphoric acid are used as starting materials. The exfoliation to predominantly monolayers was achieved by stirring them in medium polarity organic solvents that can form hydrogen bonds. The exfoliation process does not disrupt the sp(2) π-system of graphene and is gentle enough to allow the preparation of graphene and h-BN monolayers that are tens of microns in their lateral dimensions.

  1. Therapeutic efficacy for hepatocellular carcinoma by boric acid-mediated boron neutron capture therapy in a rat model.

    PubMed

    Lin, Sy-Yu; Lin, Chen-Jou; Liao, Jiunn-Wang; Peir, Jinn-Jer; Chen, Wei-Lin; Chi, Chin-Wen; Lin, Yung-Chang; Liu, Yu-Ming; Chou, Fong-In

    2013-11-01

    Hepatocellular carcinoma (HCC) is a common malignant tumor with poor prognosis. Boron neutron capture therapy (BNCT) may provide an alternative therapy for HCC. This study investigated the therapeutic efficacy of boric acid (BA)-mediated BNCT for HCC in a rat model. The pharmacokinetic and biodistribution of BA in N1S1 tumor-bearing rats were analyzed. Rats were injected with 25 mg B/kg body weight via tail veins before neutron irradiation at the Tsing Hua Open-pool Reactor, and the efficacy of BNCT was evaluated from the tumor size, tumor blood flow, and biochemical analyses. HCC-bearing rats administered BNCT showed reductions in tumor size on ultrasound imaging, as well as an obvious reduction in the distribution of tumor blood flow. The lesion located in livers had disappeared on the 80th day after BNCT; a recovery of values to normal levels was also recorded. BA-mediated BNCT is a promising alternative for liver cancer therapy since the present study demonstrated the feasibility of curing a liver tumor and restoring liver function in rats. Efforts are underway to investigate the histopathological features and the detailed mechanisms of BA-mediated BNCT.

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

    PubMed

    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.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27457924

  4. Crystal structure of (2′,3,6′-tri­chloro­biphenyl-2-yl)boronic acid tetra­hydro­furan monosolvate

    PubMed Central

    Durka, Krzysztof; Kliś, Tomasz; Serwatowski, Janusz

    2015-01-01

    The title compound, C12H8BCl3O2·C4H8O, crystallizes as a tetra­hydro­furan monosolvate. The boronic acid group adopts a syn–anti conformation and is significantly twisted along the carbon–boron bond by 69.2 (1)°, due to considerable steric hindrance from the 2′,6′-di­chloro­phenyl group that is located ortho to the boronic acid substituent. The phenyl rings of the biphenyl are almost perpendicular to one another, with a dihedral angle of 87.9 (1)° between them. In the crystal, adjacent mol­ecules are linked via O—H⋯O inter­actions to form centrosymmetric dimers with R 2 2(8) motifs, which have recently been shown to be energetically very favourable. The hy­droxy groups are in an anti conformation and are also engaged in hydrogen-bonding inter­actions with the O atom of the tetra­hydro­furan solvent mol­ecule. Cl⋯Cl halogen-bonding inter­actions [Cl⋯Cl = 3.464 (1) Å] link neigbouring dimers into chains running along [010]. Further aggregation occurs due to an additional Cl⋯Cl halogen bond [Cl⋯Cl = 3.387 (1) Å]. PMID:26870407

  5. Autoradiographic and histopathological studies of boric acid-mediated BNCT in hepatic VX2 tumor-bearing rabbits: Specific boron retention and damage in tumor and tumor vessels.

    PubMed

    Yang, C H; Lin, Y T; Hung, Y H; Liao, J W; Peir, J J; Liu, H M; Lin, Y L; Liu, Y M; Chen, Y W; Chuang, K S; Chou, F I

    2015-12-01

    Hepatoma is a malignant tumor that responds poorly to conventional therapies. Boron neutron capture therapy (BNCT) may provide a better way for hepatoma therapy. In this research, (10)B-enriched boric acid (BA, 99% (10)B) was used as the boron drug. A multifocal hepatic VX2 tumor-bearing rabbit model was used to study the mechanisms of BA-mediated BNCT. Autoradiography demonstrated that BA was selectively targeted to tumors and tumor vessels. Histopathological examination revealed the radiation damage to tumor-bearing liver was concentrated in the tumor regions during BNCT treatment. The selective killing of tumor cells and the destruction of the blood vessels in tumor masses may be responsible for the success of BA-mediated BNCT for liver tumors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes.

    PubMed

    Malpass, Geoffroy R P; Salazar-Banda, Giancarlo R; Miwa, Douglas W; Machado, Sérgio A S; Motheo, Artur J

    2013-01-01

    The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

  7. Electroextraction of boron from boron carbide scrap

    SciTech Connect

    Jain, Ashish; Anthonysamy, S.; Ghosh, C.; Ravindran, T.R.; Divakar, R.; Mohandas, E.

    2013-10-15

    Studies were carried out to extract elemental boron from boron carbide scrap. The physicochemical nature of boron obtained through this process was examined by characterizing its chemical purity, specific surface area, size distribution of particles and X-ray crystallite size. The microstructural characteristics of the extracted boron powder were analyzed by using scanning electron microscopy and transmission electron microscopy. Raman spectroscopic examination of boron powder was also carried out to determine its crystalline form. Oxygen and carbon were found to be the major impurities in boron. Boron powder of purity ∼ 92 wt. % could be produced by the electroextraction process developed in this study. Optimized method could be used for the recovery of enriched boron ({sup 10}B > 20 at. %) from boron carbide scrap generated during the production of boron carbide. - Highlights: • Recovery of {sup 10}B from nuclear grade boron carbide scrap • Development of process flow sheet • Physicochemical characterization of electroextracted boron • Microscopic examination of electroextracted boron.

  8. Boronic Acid vs. Folic Acid: A Comparison of the bio-recognition performances by Impedimetric Cytosensors based on Ferrocene cored dendrimer.

    PubMed

    Dervisevic, Muamer; Şenel, Mehmet; Sagir, Tugba; Isik, Sevim

    2017-05-15

    A comparative study is reported where folic acid (FA) and boronic acid (BA) based cytosensors and their analytical performances in cancer cell detection were analyzed by using electrochemical impedance spectroscopy (EIS) method. Cytosensors were fabricated using self-assembled monolayer principle by modifying Au electrode with cysteamine (Cys) and immobilization of ferrocene cored polyamidiamine dendrimers second generation (Fc-PAMAM (G2)), after which electrodes were modified with FA and BA. Au/Fc-PAMAM(G2)/FA and Au/Fc-PAMAM(G2)/BA based cytosensors showed extremely good analytical performances in cancer cell detection with linear range of 1×10(2) to 1×10(6)cellsml(-1), detection limit of 20cellsml(-1) with incubation time of 20min for FA based electrode, and for BA based electrode detection limit was 28cellsml(-1) with incubation time of 10min. Next to excellent analytical performances, cytosensors showed high selectivity towards cancer cells which was demonstrated in selectivity study using human embryonic kidney 293 cells (HEK 293) as normal cells and Au/Fc-PAMAM(G2)/FA electrode showed two times better selectivity than BA modified electrode. These cytosensors are promising for future applications in cancer cell diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Contrasting Frustrated Lewis Pair Reactivity with Selenium- and Boron-Based Lewis Acids.

    PubMed

    Wilkins, Lewis C; Günther, Benjamin A R; Walther, Melanie; Lawson, James R; Wirth, Thomas; Melen, Rebecca L

    2016-09-05

    The activation of π-bonds in diynyl esters has been investigated by using soft and hard Lewis acids. In the case of the soft selenium Lewis acid PhSeCl, sequential activation of the alkyne bonds leads initially to an isocoumarin (1 equiv PhSeCl) and then to a tetracyclic conjugated structure with the isocoumarin subunit fused to a benzoselenopyran (3 equiv PhSeCl). Conversely, the reaction with the hard Lewis acidic borane B(C6 F5 )3 initiates a cascade reaction to yield a complex π-conjugated system containing phthalide and indene subunits. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide.

    PubMed

    Guinea, Elena; Arias, Conchita; Cabot, Pere Lluís; Garrido, José Antonio; Rodríguez, Rosa María; Centellas, Francesc; Brillas, Enric

    2008-01-01

    Solutions containing 164 mg L(-1) salicylic acid of pH 3.0 have been degraded by electrochemical advanced oxidation processes such as anodic oxidation, anodic oxidation with electrogenerated H(2)O(2), electro-Fenton, photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Their oxidation power has been comparatively studied in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and a graphite or O(2)-diffusion cathode. In the three latter procedures, 0.5mM Fe(2+) is added to the solution to form hydroxyl radical (()OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the O(2)-diffusion cathode. Total mineralization is attained for all methods with BDD and for photoelectro-Fenton and solar photoelectro-Fenton with Pt. The poor decontamination achieved in anodic oxidation and electro-Fenton with Pt is explained by the slow removal of most pollutants by ()OH formed from water oxidation at the Pt anode in comparison to their quick destruction with ()OH produced at BDD. ()OH generated from Fenton's reaction oxidizes rapidly all aromatic pollutants, but it cannot destroy final Fe(III)-oxalate complexes. Solar photoelectro-Fenton treatments always yield quicker degradation rate due to the very fast photodecarboxylation of these complexes by UVA irradiation supplied by solar light. The effect of current density on the degradation rate, efficiency and energy cost of all methods is examined. The salicylic acid decay always follows a pseudo-first-order kinetics. 2,3-Dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic, alpha-ketoglutaric, glycolic, glyoxylic, maleic, fumaric, malic, tartronic and oxalic acids are detected as oxidation products. A general reaction sequence for salicylic acid mineralization considering all these intermediates is proposed.

  11. Molecular tectonics. Use of the hydrogen bonding of boronic acids to direct supramolecular construction.

    PubMed

    Fournier, Jean-Hugues; Maris, Thierry; Wuest, James D; Guo, Wenzhuo; Galoppini, Elena

    2003-01-29

    Tetraboronic acids 1 and 2 have four -B(OH)(2) groups oriented tetrahedrally by cores derived from tetraphenylmethane and tetraphenylsilane. Crystallization produces isostructural diamondoid networks held together by hydrogen bonding of the -B(OH)(2) groups, in accord with the tendency of simple arylboronic acids to form cyclic hydrogen-bonded dimers in the solid state. Five-fold interpenetration of the networks is observed, but 60% and 64% of the volumes of crystals of tetraboronic acids 1 and 2, respectively, remain available for the inclusion of disordered guests. Guests occupy two types of interconnected channels aligned with the a and b axes; those in crystals of tetraphenylmethane 1 measure approximately 5.9 x 5.9 A(2) and 5.2 x 8.6 A(2) in cross section at the narrowest points, whereas those in crystals of tetraphenylsilane 2 are approximately 6.4 x 6.4 A(2) and 6.4 x 9.0 A(2). These channels provide access to the interior and permit guests to be exchanged quantitatively without loss of crystallinity. Because the Si-C bonds at the core of tetraboronic acid 2 are longer (1.889(3) A) than the C-C bonds at the core of tetraboronic acid 1 (1.519(6) A), the resulting network is expanded rationally. By associating to form robust isostructural networks with predictable architectures and properties of porosity, compounds 1 and 2 underscore the usefulness of molecular tectonics as a strategy for making ordered materials.

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

    SciTech Connect

    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.

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

    DOEpatents

    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.

  14. Highly boron deficiency-tolerant plants generated by enhanced expression of NIP5;1, a boric acid channel.

    PubMed

    Kato, Yuichi; Miwa, Kyoko; Takano, Junpei; Wada, Motoko; Fujiwara, Toru

    2009-01-01

    Boron (B) is an essential element for plants, and B deficiency is a worldwide agricultural problem. In B-deficient areas, B is often supplied as fertilizer, but excess B can be toxic to both plants and animals. Generation of B deficiency-tolerant plants could reduce B fertilizer use. Improved fertility under B-limiting conditions in Arabidopsis thaliana by overexpression of BOR1, a B transporter, has been reported, but the root growth was not improved by the BOR1 overexpression. In this study, we report that enhanced expression of NIP5;1, a boric acid channel for efficient B uptake, resulted in improved root elongation under B-limiting conditions in A. thaliana. An NIP5;1 activation tag line, which has a T-DNA insertion with enhancer sequences near the NIP5;1 gene, showed improved root elongation under B limitation. We generated a construct which mimics the tag line: the cauliflower mosaic virus 35S RNA promoter was inserted at 1,357 bp upstream of the NIP5;1 transcription initiation site. Introduction of this construct into the nip5;1-1 mutant and the BOR1 overexpresser resulted in enhanced expression of NIP5;1 and improved root elongation under low B supply. Furthermore, one of the transgenic lines exhibited improved fertility and short-term B uptake. Our results demonstrate successful improvement of B deficiency tolerance and the potential of enhancing expression of a mineral nutrient channel gene to improve growth under nutrient-limiting conditions.

  15. Preparation and responsive behaviors of chitosan-functionalized nanoparticles via a boronic acid-related reaction.

    PubMed

    Wang, Yanxia; Chai, Zhihua; Wang, Na; Ren, Xuejun; Gao, Ming

    2015-01-01

    We presented here a facile strategy for constructing chitosan-functionalized nanoparticles through the coordinating interaction between phenylboronic acids in poly(3-methacrylamido phenylboronic acid) and amine groups in chitosan. The formation of nanoparticles was confirmed by Fourier transform infrared spectrometer, thermal analysis, dynamic light scattering, and transmission electron micrographs, and the nanoparticles were stable over three days in aqueous solution. The pH-sensitivity of the nanoparticles was revealed by the light scattering intensity ratio (I/I0) at different pH values. I/I0 kept constant at pH 7.0 and 8.0. When the pH value was further increased in the range of 8.0-10, I/I0 reduced. As the pH value increased above 10, I/I0 kept constant. The nanoparticles were also sensitive to glucose, and the glucose-responsive behavior was dependent on the pH values, nanoparticle concentrations, and nanoparticle compositions.

  16. Design and Exploration of Novel Boronic Acid Inhibitors Reveals Important Interactions with a Clavulanic Acid-Resistant Sulfhydryl-Variable (SHV) β-Lactamase

    PubMed Central

    Winkler, Marisa L.; Rodkey, Elizabeth A.; Taracila, Magdalena A.; Drawz, Sarah M.; Bethel, Christopher R.; Papp-Wallace, Krisztina M.; Smith, Kerri M.; Xu, Yan; Dwulit-Smith, Jeffrey R.; Romagnoli, Chiara; Caselli, Emilia; Prati, Fabio; van den Akker, Focco; Bonomo, Robert A.

    2014-01-01

    Inhibitor resistant (IR) class A β-lactamases pose a significant threat to many current antibiotic combinations. The K234R substitution in the SHV β-lactamase, from Klebsiella pneumoniae, results in resistance to ampicillin/clavulanate. After site-saturation mutagenesis of Lys-234 in SHV, microbiological and biochemical characterization of the resulting β-lactamases revealed that only –Arg conferred resistance to ampicillin/clavulanate. X-ray crystallography revealed two conformations of Arg-234 and Ser-130 in SHV K234R. The movement of Ser-130 is the principal cause of the observed clavulanate resistance. A panel of boronic acid inhibitors was designed and tested against SHV-1 and SHV K234R. A chiral ampicillin analogue was discovered to have a 2.4 ± 0.2 nM Ki for SHV K234R; the chiral ampicillin analogue formed a more complex hydrogen-bonding network in SHV K234R vs SHV-1. Consideration of the spatial position of Ser-130 and Lys-234 and this hydrogen-bonding network will be important in the design of novel antibiotics targeting IR β-lactamases. PMID:23252553

  17. Oxidative palladium catalysis in S(N)Ar reactions leading to heteroaryl ethers from pyridotriazol-1-yloxy heterocycles with aryl boronic acids.

    PubMed

    Wacharasindhu, Sumrit; Bardhan, Sujata; Wan, Zhao-Kui; Tabei, Keiko; Mansour, Tarek S

    2009-04-01

    The palladium-catalyzed oxidative coupling of pyrido- and benzotriazol-1-yloxyquinazolines and -thienopyrimidines with aryl boronic acids in the presence of Pd(PPh(3))(4) and Cs(2)CO(3) under oxygen in DME containing 0.4-0.8% water for the preparation of heteroaryl ethers is described. These transformations of triazol-1-yloxy reagents demonstrate excellent O-chemoselective control under mild conditions and good yields. Mechanistic studies based on (18)O labeling indicate that phenols as intermediates in S(N)Ar reactions with ethers are formed in oxidative and nonoxidative pathways.

  18. Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing.

    PubMed

    Huang, Yi; Wang, Wen; Li, Zou; Qin, Xiaoli; Bu, Lijuan; Tang, Zhiyong; Fu, Yingchun; Ma, Ming; Xie, Qingji; Yao, Shouzhuo; Hu, Jiming

    2013-06-15

    We report here on a facile enzymatic polymerization protocol to prepare enzyme-poly(thiophene-3-boronic acid) (PTBA) polymeric biocomposites (PBCs) for high-performance mono-/bi-enzyme amperometric biosensing. Horseradish peroxidase (HRP)-catalyzed polymerization of thiophene-3-boronic acid (TBA) monomer was conducted in aqueous solution containing HRP (or plus glucose oxidase (GOx)) by either directly added or GOx-glucose generated oxidant H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting the dialysis-isolated PBCs on Au-plated Au electrode (Auplate/Au), followed by coating with an outer-layer chitosan (CS) film. The boronic acid residues are capable of covalent bonding with enzyme at the glycosyl sites (boronic acid-diols interaction), which should less affect the enzymatic activity as compared with the common cases of covalent bonding at the peptide chains, and UV-vis spectrophotometric tests confirmed that the encapsulated HRP almost possesses its pristine enzymatic specific activity. The enzyme electrodes were studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry in the presence of Fe(CN)6(4-) mediator. The CS/HRP-PTBA/Auplate/Au electrode responded linearly to H2O2 concentration from 1 to 300 μM with a sensitivity of 390 μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1 μM. The bienzyme CS/GOx-HRP-PTBA(H2O2)/Auplate/Au electrode responded linearly to glucose concentration from 5 μM to 0.83 mM with a sensitivity of 75.1 μA mM(-1)cm(-2) and a LOD of 1 μM, and it is found here that the use of Fe(CN)6(4-) that can only efficiently mediate HRP favorably avoids the "unusual amperometric responses" observed when other mediators that can efficiently turn over both HRP and GOx are used. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Cross-coupling reaction of saccharide-based alkenyl boronic acids with aryl halides: the synthesis of bergenin.

    PubMed

    Parkan, Kamil; Pohl, Radek; Kotora, Martin

    2014-04-07

    A convenient synthetic pathway enabling D-glucal and D-galactal pinacol boronates to be prepared in good isolated yields was achieved. Both pinacol boronates were tested in a series of cross-coupling reactions under Suzuki-Miyaura cross-coupling conditions to obtain the corresponding aryl, heteroaryl, and alkenyl derivatives in high isolated yields. This methodology was applied to the formal synthesis of the glucopyranoside moiety of papulacandin D and the first total synthesis of bergenin. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    SciTech Connect

    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.

  1. A pH-responsive drug nanovehicle constructed by reversible attachment of cholesterol to PEGylated poly(l-lysine) via catechol-boronic acid ester formation.

    PubMed

    Yang, Bin; Lv, Yin; Zhu, Jing-Yi; Han, Yun-Tao; Jia, Hui-Zhen; Chen, Wei-Hai; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2014-08-01

    The present work reports the construction of a drug delivery nanovehicle via a pH-sensitive assembly strategy for improved cellular internalization and intracellular drug liberation. Through spontaneous formation of boronate linkage in physiological conditions, phenylboronic acid-modified cholesterol was able to attach onto catechol-pending methoxypoly(ethylene glycol)-block-poly(l-lysine). This comb-type polymer can self-organize into a micellar nanoconstruction that is able to effectively encapsulate poorly water-soluble agents. The blank micelles exhibited negligible in vitro cytotoxicity, yet doxorubicin (DOX)-loaded micelles could effectively induce cell death at a level comparable to free DOX. Owing to the acid-labile feature of the boronate linkage, a reduction in environmental pH from pH 7.4 to 5.0 could trigger the dissociation of the nanoconstruction, which in turn could accelerate the liberation of entrapped drugs. Importantly, the blockage of endosomal acidification in HeLa cells by NH4Cl treatment significantly decreased the nuclear uptake efficiency and cell-killing effect mediated by the DOX-loaded nanoassembly, suggesting that acid-triggered destruction of the nanoconstruction is of significant importance in enhanced drug efficacy. Moreover, confocal fluorescence microscopy and flow cytometry assay revealed the effective internalization of the nanoassemblies, and their cellular uptake exhibited a cholesterol dose-dependent profile, indicating the contribution of introduced cholesterol functionality to the transmembrane process of the nanoassembly.

  2. Boronic acid functionalized core-satellite composite nanoparticles for advanced enrichment of glycopeptides and glycoproteins.

    PubMed

    Zhang, Lijuan; Xu, Yawei; Yao, Hailiang; Xie, Liqi; Yao, Jun; Lu, Haojie; Yang, Pengyuan

    2009-10-05

    A core-satellite-structured composite material has been successfully synthesized for capturing glycosylated peptides or proteins. This novel hybrid material is composed of a silica-coated ferrite "core" and numerous "satellites" of gold nanoparticles with lots of "anchors". The anchor, 3-aminophenylboronic acid, designed for capturing target molecules, is highly specific toward glycosylated species. The long organic chains bridging the gold surface and the anchors could reduce the steric hindrance among the bound molecules and suppress nonspecific bindings. Due to the excellent structure of the current material, the trap-and-release enrichment of glycosylated samples is quite simple, specific, and effective. Indeed, the composite nanoparticles could be used for enriching glycosylated peptides and proteins with very low concentrations, and the enriched samples can be easily separated from bulk solution by a magnet. By using this strategy, the recovery of glycopeptides and glycoproteins after enrichment were found to be 85.9 and 71.6% separately, whereas the adsorption capacity of the composite nanoparticles was proven to be more than 79 mg of glycoproteins per gram of the material. Moreover, the new composite nanoparticles were applied to enrich glycosylated proteins from human colorectal cancer tissues for identification of N-glycosylation sites. In all, 194 unique glycosylation sites mapped to 155 different glycoproteins have been identified, of which 165 sites (85.1%) were newly identified.

  3. A structure-function relationship for the optical modulation of phenyl boronic acid-grafted, polyethylene glycol-wrapped single-walled carbon nanotubes.

    PubMed

    Mu, Bin; McNicholas, Thomas P; Zhang, Jingqing; Hilmer, Andrew J; Jin, Zhong; Reuel, Nigel F; Kim, Jong-Ho; Yum, Kyungsuk; Strano, Michael S

    2012-10-24

    Phenyl boronic acids (PBA) are important binding ligands to pendant diols useful for saccharide recognition. The aromatic ring can also function to anchor an otherwise hydrophilic polymer backbone to the surface of hydrophobic graphene or carbon nanotube. In this work, we demonstrate both functions using a homologous series of seven phenyl boronic acids conjugated to a polyethylene glycol, eight-membered, branched polymer (PPEG8) that allows aqueous dispersion of single-walled carbon nanotubes (SWNT) and quenching of the near-infrared fluorescence in response to saccharide binding. We compare the 2-carboxyphenylboronic acid (2CPBA); 3-carboxy- (3CPBA) and 4-carboxy- (4CPBA) phenylboronic acids; N-(4-phenylboronic)succinamic acid (4SCPBA); 5-bromo-3-carboxy- (5B3CPBA), 3-carboxy-5-fluoro- (5F3CPBA), and 3-carboxy-5-nitro- (5N3CPBA) phenylboronic acids, demonstrating a clear link between SWNT photoluminescence quantum yield and boronic acid structure. Surprisingly, quantum yield decreases systematically with both the location of the BA functionality and the inclusion of electron-withdrawing or -donating substituents on the phenyl ring. For three structural isomers (2CPBA, 3CPBA, and 4CPBA), the highest quantum yields were measured for para-substituted PBA (4CPBA), much higher than ortho- (2CPBA) and meta- (3CPBA) substituted PBA, indicating the first such dependence on molecular structure. Electron-withdrawing substituents such as nitro groups on the phenyl ring cause higher quantum yield, while electron-donating groups such as amides and alkyl groups cause a decrease. The solvatochromic shift of up to 10.3 meV was used for each case to estimate polymer surface coverage on an areal basis using a linear dielectric model. Saccharide recognition using the nIR photoluminescence of SWNT is demonstrated, including selectivity toward pentoses such as arabinose, ribose, and xylose to the exclusion of the expected fructose, which has a high selectivity on PBA due to the

  4. JAGUAR Procedures for Detonation Behavior of Explosives Containing Boron

    NASA Astrophysics Data System (ADS)

    Stiel, Leonard; Baker, Ernest; Capellos, Christos

    2009-06-01

    The JAGUAR product library was expanded to include boron and boron containing products. Relationships of the Murnaghan form for molar volumes and derived properties were implemented in JAGUAR. Available Hugoniot and static volumertic data were analyzed to obtain constants of the Murnaghan relationship for solid boron, boron oxide, boron nitride, boron carbide, and boric acid. Experimental melting points were also utilized with optimization procedures to obtain the constants of the volumetric relationships for liquid boron and boron oxide. Detonation velocities for HMX - boron mixtures calculated with these relationships using JAGUAR are in closer agreement with literature values at high initial densities for inert (unreacted) boron than with the completely reacted metal. These results indicate that boron mixtures may exhibit eigenvalue detonation behavior, as observed by aluminized combined effects explosives, with higher detonation velocities than would be achieved by a classical Chapman-Jouguet detonation. Analyses of calorimetric measurements for RDX - boron mixtures indicate that at high boron contents the formation of side products, including boron nitride and boron carbide, inhibits the energy output obtained from the detonation of the formulation.

  5. Crystal Structures of KPC-2 and SHV-1 β-Lactamases in Complex with the Boronic Acid Transition State Analog S02030

    PubMed Central

    Nguyen, Nhu Q.; Krishnan, Nikhil P.; Rojas, Laura J.; Prati, Fabio; Caselli, Emilia; Romagnoli, Chiara; Bonomo, Robert A.

    2016-01-01

    Resistance to expanded-spectrum cephalosporins and carbapenems has rendered certain strains of Klebsiella pneumoniae the most problematic pathogens infecting patients in the hospital and community. This broad-spectrum resistance to β-lactamases emerges in part via the expression of KPC-2 and SHV-1 β-lactamases and variants thereof. KPC-2 carbapenemase is particularly worrisome, as the genetic determinant encoding this β-lactamase is rapidly spread via plasmids. Moreover, KPC-2, a class A enzyme, is difficult to inhibit with mechanism-based inactivators (e.g., clavulanate). In order to develop new β-lactamase inhibitors (BLIs) to add to the limited available armamentarium that can inhibit KPC-2, we have structurally probed the boronic acid transition state analog S02030 for its inhibition of KPC-2 and SHV-1. S02030 contains a boronic acid, a thiophene, and a carboxyl triazole moiety. We present here the 1.54- and 1.87-Å resolution crystal structures of S02030 bound to SHV-1 and KPC-2 β-lactamases, respectively, as well as a comparative analysis of the S02030 binding modes, including a previously determined S02030 class C ADC-7 β-lactamase complex. S02030 is able to inhibit vastly different serine β-lactamases by interacting with the conserved features of these active sites, which includes (i) forming the bond with catalytic serine via the boron atom, (ii) positioning one of the boronic acid oxygens in the oxyanion hole, and (iii) utilizing its amide moiety to make conserved interactions across the width of the active site. In addition, S02030 is able to overcome more distantly located structural differences between the β-lactamases. This unique feature is achieved by repositioning the more polar carboxyl-triazole moiety, generated by click chemistry, to create polar interactions as well as reorient the more hydrophobic thiophene moiety. The former is aided by the unusual polar nature of the triazole ring, allowing it to potentially form a unique C

  6. Crystal Structures of KPC-2 and SHV-1 β-Lactamases in Complex with the Boronic Acid Transition State Analog S02030.

    PubMed

    Nguyen, Nhu Q; Krishnan, Nikhil P; Rojas, Laura J; Prati, Fabio; Caselli, Emilia; Romagnoli, Chiara; Bonomo, Robert A; van den Akker, Focco

    2016-01-04

    Resistance to expanded-spectrum cephalosporins and carbapenems has rendered certain strains of Klebsiella pneumoniae the most problematic pathogens infecting patients in the hospital and community. This broad-spectrum resistance to β-lactamases emerges in part via the expression of KPC-2 and SHV-1 β-lactamases and variants thereof. KPC-2 carbapenemase is particularly worrisome, as the genetic determinant encoding this β-lactamase is rapidly spread via plasmids. Moreover, KPC-2, a class A enzyme, is difficult to inhibit with mechanism-based inactivators (e.g., clavulanate). In order to develop new β-lactamase inhibitors (BLIs) to add to the limited available armamentarium that can inhibit KPC-2, we have structurally probed the boronic acid transition state analog S02030 for its inhibition of KPC-2 and SHV-1. S02030 contains a boronic acid, a thiophene, and a carboxyl triazole moiety. We present here the 1.54- and 1.87-Å resolution crystal structures of S02030 bound to SHV-1 and KPC-2 β-lactamases, respectively, as well as a comparative analysis of the S02030 binding modes, including a previously determined S02030 class C ADC-7 β-lactamase complex. S02030 is able to inhibit vastly different serine β-lactamases by interacting with the conserved features of these active sites, which includes (i) forming the bond with catalytic serine via the boron atom, (ii) positioning one of the boronic acid oxygens in the oxyanion hole, and (iii) utilizing its amide moiety to make conserved interactions across the width of the active site. In addition, S02030 is able to overcome more distantly located structural differences between the β-lactamases. This unique feature is achieved by repositioning the more polar carboxyl-triazole moiety, generated by click chemistry, to create polar interactions as well as reorient the more hydrophobic thiophene moiety. The former is aided by the unusual polar nature of the triazole ring, allowing it to potentially form a unique C-H…O 2

  7. Sol-gel-modified boron-doped diamond surfaces for methanol and ethanol electro-oxidation in acid medium

    NASA Astrophysics Data System (ADS)

    Salazar-Banda, G. R.; Suffredini, H. B.; Calegaro, M. L.; Tanimoto, S. T.; Avaca, L. A.

    Studies of the methanol and ethanol electro-oxidation reactions on boron-doped diamond (BDD) electrode surfaces modified with Pt, Pt-RuO 2 and Pt-RuO 2-RhO 2 by the sol-gel method are reported here. The materials were initially characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The XRD analyses indicate that the sol-gel method produces nano-sized deposits on the BDD surfaces. These deposits also form nano-clusters with a size of ca. 100 nm as observed by SEM and AFM. The EDX maps showed that the metals are homogeneously distributed on the BDD surface and have a composition close to the expected one. Cyclic voltammetry experiments in acid medium revealed that the CO poisoning effect for the methanol and the ethanol oxidation reactions is largely inhibited on the Pt-RuO 2-RhO 2/BDD electrode showing the positive contribution of the rhodium oxide to the electrocatalysts performance in these reactions. Potentiostatic polarization curves and the corresponding Tafel plots showed that the addition of RuO 2 and RhO 2 to Pt/BDD produces a more reactive electrocatalyst that adsorbs methanol and ethanol more efficiently and changes the reactions onsets by 120 or 180 mV towards less positive potentials, respectively. Moreover, the stationary current density measured at a fixed potential for ethanol oxidation on the Pt-RuO 2-RhO 2/BDD composite electrode is more than one order of magnitude larger than on a Pt/BDD surface. In addition, chronoamperometric experiments indicate that on those composite electrodes the effect of CO poisoning only appears after a considerable amount of charge has passed through the interface. Consequently, the catalyst containing Pt, RuO 2 and RhO 2 deposited on BDD by the sol-gel method is a very promising composite material to be used in fuel cell anodes.

  8. Multilayer Hydrophilic Poly(phenol-formaldehyde resin)-Coated Magnetic Graphene for Boronic Acid Immobilization as a Novel Matrix for Glycoproteome Analysis.

    PubMed

    Wang, Jiaxi; Wang, Yanan; Gao, Mingxia; Zhang, Xiangmin; Yang, Pengyuan

    2015-07-29

    Capturing glycopeptides selectively and efficiently from mixed biological samples has always been critical for comprehensive and in-depth glycoproteomics analysis, but the lack of materials with superior capture capacity and high specificity still makes it a challenge. In this work, we introduce a way first to synthesize a novel boronic-acid-functionalized magnetic graphene@phenolic-formaldehyde resin multilayer composites via a facile process. The as-prepared composites gathered excellent characters of large specific surface area and strong magnetic responsiveness of magnetic graphene, biocompatibility of resin, and enhanced affinity properties of boronic acid. Furthermore, the functional graphene composites were shown to have low detection limit (1 fmol) and good selectivity, even when the background nonglycopeptides has a concentration 100 fold higher. Additionally, enrichment efficiency of the composites was still retained after being used repeatedly (at least three times). Better yet, the practical applicability of this approach was evaluated by the enrichment of human serum with a low sample volume of 1 μL. All the results have illustrated that the magG@PF@APB has a great potential in glycoproteome analysis of complex biological samples.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Sensitive determination of four camptothecins by solid-phase microextraction-HPLC based on a boronic acid contained polymer monolithic layer.

    PubMed

    Chen, Jishun; Min, Xinwen; Li, Peng; Chen, Wu; Tian, Dawei; Chen, Qinhua

    2015-06-16

    Camptothecin (CPT) and its derivative have been revealed to possess special anti-cancer activity, extraction methods are necessary for trace determination of CPTs in complex samples. In this work, we prepared a high efficient boronic acid-based polymer monolithic layer for microextraction of CPTs. A disposable membrane filter-based extraction device was developed, and boronic acid groups were co-polymerized into a polyporous polymer skeleton and served as the monolithic sorbent. The prepared poly(4-VB-MA-TRIM) showed good stability and great extraction efficiency toward four CPTs. After optimization of extraction conditions, poly(4-VB-MA-TRIM)-based solid-phase microextraction was coupled HPLC for determination of CPTs in biological samples. The method exhibited low limits of detection of 0.05-0.2 ng mL(-1), which is significantly more sensitive than reported HPLC methods. The method also showed wide linear range (0.1-100 and 0.5-200 ng mL(-1)), good linearity (R(2)≥0.9981) and good reproducibility (RSD ≤3.76%). The method has been applied in plasma samples, with good selectivity and good recoveries ranging from 85.1 to 104.7%.

  11. Mass spectrometry signal amplification for ultrasensitive glycoprotein detection using gold nanoparticle as mass tag combined with boronic acid based isolation strategy.

    PubMed

    Liu, Minbo; Zhang, Lijuan; Xu, Yawei; Yang, Pengyuan; Lu, Haojie

    2013-07-25

    We describe a novel method for rapid and ultrasensitive detection of intact glycoproteins without enzymatic pretreatment which was commonly used in proteomic research. This method is based on using gold nanoparticle (AuNP) as signal tag in laser desorption/ionization mass spectrometry (LDI-MS) analysis combined with boronic acid assisted isolation strategy. Briefly speaking, target glycoproteins were firstly isolated from sample solution with boronic acid functionalized magnetic microparticles, and then the surface modified gold nanoparticles were added to covalently bind to the glycoproteins. After that, these AuNP tagged glycoproteins were eluted from magnetic microparticles and applied to LDI-MS analysis. The mass signal of AuNP rather than that of glycoprotein was detected and recorded in this strategy. Through data processing of different standard glycoproteins, we have demonstrated that the signal of AuNP could be used to quantitatively represent glycoprotein. This method allows femtomolar detection of intact glycoproteins. We believe that the successful validation of this method on three different kinds of glycoproteins suggests the potential use for tracking trace amount of target glycoproteins in real biological samples in the near future.

  12. Direct current sputtering of boron from boron/boron mixtures

    DOEpatents

    Timberlake, J.R.; Manos, D.; Nartowitz, E.

    1994-12-13

    A method for coating a substrate with boron by sputtering includes lowering the electrical resistance of a boron-containing rod to allow electrical conduction in the rod; placing the boron-containing rod inside a vacuum chamber containing substrate material to be coated; applying an electrical potential between the boron target material and the vacuum chamber; countering a current avalanche that commences when the conduction heating rate exceeds the cooling rate, and until a steady equilibrium heating current is reached; and, coating the substrate material with boron by sputtering from the boron-containing rod. 2 figures.

  13. Chronic boron exposure and human semen parameters.

    PubMed

    Robbins, Wendie A; Xun, Lin; Jia, Juan; Kennedy, Nola; Elashoff, David A; Ping, Liu

    2010-04-01

    Boron found as borates in soil, food, and water has important industrial and medical applications. A panel reviewing NTP reproductive toxicants identified boric acid as high priority for occupational studies to determine safe versus adverse reproductive effects. To address this, we collected boron exposure/dose measures in workplace inhalable dust, dietary food/fluids, blood, semen, and urine from boron workers and two comparison worker groups (n=192) over three months and determined correlations between boron and semen parameters (total sperm count, sperm concentration, motility, morphology, DNA breakage, apoptosis and aneuploidy). Blood boron averaged 499.2 ppb for boron workers, 96.1 and 47.9 ppb for workers from high and low environmental boron areas (p<0.0001). Boron concentrated in seminal fluid. No significant correlations were found between blood or urine boron and adverse semen parameters. Exposures did not reach those causing adverse effects published in animal toxicology work but exceeded those previously published for boron occupational groups.

  14. Boron Heterocycle High-Fidelity Estrogen Mimics as Novel Antiestrogens for the Treatment of Breast Cancer

    DTIC Science & Technology

    2001-10-01

    design fragments because of their charge, the carbon-substituted forms of boric Pharmaceutical Discovery Division, SRI International, Menlo acid B(OH...the boron-based therapeutics currently on the hori- Boric acid (LDo of 3450 mg/kg orally in the mouse zon are either boronic acids themselves or...31 BIOLOGICAL ASPECTS OF BORON Serious poisoning of humans with boric acid is un- likely to result from a single acute ingestion,3 2 and Boronic acids

  15. Ambient Temperature Synthesis of High Enantiopurity N-Protected Peptidyl Ketones by Peptidyl Thiol Ester–Boronic Acid Cross-Coupling

    PubMed Central

    Yang, Hao; Li, Hao; Wittenberg, Rüdiger; Egi, Masahiro; Huang, Wenwei; Liebeskind, Lanny S.

    2009-01-01

    α-Amino acid thiol esters derived from N-protected mono-, di-, and tripeptides couple with aryl, π-electron-rich heteroaryl, or alkenyl boronic acids in the presence of stoichiometric Cu(I) thiophene-2-carboxylate (CuTC) and catalytic Pd2(dba)3/triethylphosphite to generate the corresponding N-protected peptidyl ketones in good to excellent yields and in high enantiopurity. Triethylphosphite plays a key role as a supporting ligand by mitigating an undesired palladium-catalyzed decarbonylation-β-elimination of the α-amino thiol esters. The peptidyl ketone synthesis proceeds at room temperature under non-basic conditions and demonstrates a high tolerance to functionality. PMID:17263394

  16. TEM and SEM observations of super-structures constructed in organogel systems from a combination of boronic-acid-appended bola-amphiphiles with chiral diols

    NASA Astrophysics Data System (ADS)

    Koumoto, Kazuya; Yamashita, Tadahiro; Kimura, Taro; Luboradzki, Roman; Shinkai, Seiji

    2001-03-01

    Two bola-amphiphilic α,ω-diboronic acids separated by a (CH2)11 or (CH2)12 group were synthesized. Complexation with chiral diols readily gave new amphiphiles end-capped with the chiral substituents. Some of these acted as good gelators of organic solvents. Transmission electron microscope and scanning electron microscope observations established that a variety of super-structures are created in the organogels, depending on the solvents and the structure of the chiral end-cap groups. In most cases, the fibrous aggregates, the network structure which is the driving-force for gelation, showed a helical higher-order structure reflecting the chirality of the end-cap groups. The results indicate that the combinatorial approach utilizing boronic acid functions and diol compounds is useful in creating a variety of new super-structures in the gel phase.

  17. Stereoselective Csp(3) -Csp(2) Bond-Forming Reactions by Transition-Metal-Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids.

    PubMed

    Plaza, Manuel; Pérez-Aguilar, M Carmen; Valdés, Carlos

    2016-04-25

    The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio- and stereoselectivity. In these transition-metal-free processes, a Csp(3) -Csp(2) and Csp(3) -H bond are formed on the same carbon atom. The stereoselective reaction is general for 2-, 3-, and 4-substituted cyclohexanone tosylhydrazones, as well as for 2-substituted cyclopentanones. However, no stereoselectivity is observed for acyclic derivatives. DFT computational modeling suggests that the stereoselectivity of the reaction is determined by the approach of the boronic acid to the diazocyclohexane on its most stable chair conformation through an equatorial trajectory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Boron doping a semiconductor particle

    DOEpatents

    Stevens, Gary Don; Reynolds, Jeffrey Scott; Brown, Louanne Kay

    1998-06-09

    A method (10,30) of boron doping a semiconductor particle using boric acid to obtain a p-type doped particle. Either silicon spheres or silicon powder is mixed with a diluted solution of boric acid having a predetermined concentration. The spheres are dried (16), with the boron film then being driven (18) into the sphere. A melt procedure mixes the driven boron uniformly throughout the sphere. In the case of silicon powder, the powder is metered out (38) into piles and melted/fused (40) with an optical furnace. Both processes obtain a p-type doped silicon sphere with desired resistivity. Boric acid is not a restricted chemical, is inexpensive, and does not pose any special shipping, handling, or disposal requirements.

  19. Boron doping a semiconductor particle

    DOEpatents

    Stevens, G.D.; Reynolds, J.S.; Brown, L.K.

    1998-06-09

    A method of boron doping a semiconductor particle using boric acid to obtain a p-type doped particle. Either silicon spheres or silicon powder is mixed with a diluted solution of boric acid having a predetermined concentration. The spheres are dried, with the boron film then being driven into the sphere. A melt procedure mixes the driven boron uniformly throughout the sphere. In the case of silicon powder, the powder is metered out into piles and melted/fused with an optical furnace. Both processes obtain a p-type doped silicon sphere with desired resistivity. Boric acid is not a restricted chemical, is inexpensive, and does not pose any special shipping, handling, or disposal requirements. 2 figs.

  20. Molecular design of boronic acid-functionalized squarylium cyanine dyes for multiple discriminant analysis of sialic acid in biological samples: selectivity toward monosaccharides controlled by different alkyl side chain lengths.

    PubMed

    Ouchi, Kazuki; Colyer, Christa L; Sebaiy, Mahmoud; Zhou, Jin; Maeda, Takeshi; Nakazumi, Hiroyuki; Shibukawa, Masami; Saito, Shingo

    2015-02-03

    We designed a new series of boronic acid-functionalized squarylium cyanine dyes (SQ-BA) with different lengths of alkyl chain residues, suitable for multiple discriminant analysis (MDA) of sialic acid (Neu5Ac) in biological samples. The SQ-BA dyes form aggregates based on hydrophobic interactions, which result in quenched fluorescence in aqueous solutions. When the boronic acid binds with saccharides, the fluorescence intensity increases as a result of dissociation to the emissive monomeric complex. We inferred that different dye aggregate structures (H-aggregates and J-aggregates) were induced depending on the alkyl chain length, so that monosaccharides would be recognized in different ways (especially, multipoint interaction with J-aggregates). A distinctive emission enhancement of SQ-BA dyes with shorter-alkyl-chains in the presence of Neu5Ac was observed (2.4-fold fluorescence enhancement; with formation constant 10(1.7) M(-1)), with no such enhancement for SQ-BA dyes with longer-alkyl-chain. In addition, various enhancement factors for other monosaccharides were observed depending on the alkyl chain length. Detailed thermodynamic and NMR studies of the SQ-BA complexes revealed the unique recognition mechanism: the dye aggregate with a shorter-alkyl-chain causes the slipped parallel structure and forms a stable 2:1 complex with Neu5Ac, as distinct from longer-alkyl-chain dyes, which form a 1:1 monomeric complex. MDA using the four SQ-BA dyes was performed for human urine samples, resulting in the successful discrimination between normal and abnormal Neu5Ac levels characteristic of disease. Thus, we successfully controlled various responses to similar monosaccharides with a novel approach that chemically modified not the boronic acid moiety itself but the length of the alkyl chain residue attached to the dye in order to generate specificity.

  1. Characterization of electrodeposited elemental boron

    SciTech Connect

    Jain, Ashish; Anthonysamy, S. Ananthasivan, K.; Ranganathan, R.; Mittal, Vinit; Narasimhan, S.V.; Vasudeva Rao, P.R.

    2008-07-15

    Elemental boron was produced through electrowinning from potassium fluoroborate dissolved in a mixture of molten potassium fluoride and potassium chloride. The characteristics of the electrodeposited boron (raw boron) as well as the water and acid-leached product (processed boron) were studied. The chemical purity, specific surface area, size distribution of particles and X-ray crystallite size of the boron powders were investigated. The morphology of the deposits was examined using scanning electron microscopy (SEM). The chemical state of the matrix, as well as the impurity phases present in them, was established using X-ray photoelectron spectroscopy (XPS). In order to interpret and understand the results obtained, a thermodynamic analysis was carried out. The gas-phase corrosion in the head space as well as the chemistry behind the leaching process were interpreted using this analysis. The ease of oxidation of these powders in air was investigated using differential thermal analysis (DTA) coupled with thermogravimetry (TG). From the results obtained in this study it was established that elemental boron powder with a purity of 95-99% could be produced using a high temperature molten salt electrowinning process. The major impurities were found to be oxygen, carbon, iron and nickel.

  2. Mechanistic Insights into the Aerobic Cu(I)-Catalyzed Cross-Coupling of S-Acyl Thiosalicylamide Thiol Esters and Boronic Acids

    PubMed Central

    Varela-Álvarez, Adrián; Liebeskind, Lanny S.; Musaev, Djamaladdin G.

    2012-01-01

    The Density Functional Theory (DFT) method is used to elucidate the nature of the active species and the mechanism of the aerobic CuI-catalyzed cross-coupling of S-acyl thiosalicylamide thiol esters and boronic acids reported previously (J. Am. Chem. Soc. 2007, 129, 15734–15735; Angew. Chem., Int. Ed. 2009, 48, 1417-1421). The energetically lowest isomer of the proposed active species [LC(O)R1]Cu-(O2)-Cu[LC(O)R1]2+, 2a, (where L = thiolatosalicylamide) is found to be I1(OO,OO) with a μ-η2:η2-peroxo Cu2O2-core, while its isomers I2(OO,OO) with a bis-(μ-O) Cu2O2-core and I3(OO,OO) with a (μ-η1:η1) Cu2O2-core lie only a few kcal/mol higher and separated by 4–7kcal/mol energy barriers. In all these isomers, the thiol ester is coordinated to the Cu-centers via its two O-ends. Isomers with (SO,OO) and (SO,SO) coordination modes of the thiol esters lie slightly higher and are separated with moderate energy barriers. We found the latter isomers to be vital for the reported CuI-templated cross-coupling of S-acyl thiosalicylamide thiol esters and boronic acids under aerobic conditions. The presence of an anion (halide, carboxylate modeled as formate) in the reaction medium is found to be necessary. Its coordination to the active catalyst I1(SO,SO) is the first step of the proposed anion-assisted transmetalation by boronic acid. Overall the transmetalation reaction requires 34.0 kcal/mol and is 24.0 kcal/mol exergonic. This conclusion is in reasonable agreement with available experiments. The C-C bond formation in the transmetalation product requires a 6.3 kcal/mol lower energy barrier and is highly exergonic. PMID:23565023

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

    SciTech Connect

    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

    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.

  4. Electro-fenton and photoelectro-fenton degradation of sulfanilic acid using a boron-doped diamond anode and an air diffusion cathode.

    PubMed

    El-Ghenymy, Abdellatif; Garrido, José Antonio; Centellas, Francesc; Arias, Conchita; Cabot, Pere Lluís; Rodríguez, Rosa María; Brillas, Enric

    2012-04-05

    The mineralization of sulfanilic acid has been studied by electro-Fenton (EF) and photoelectro-Fenton (PEF) reaction with UVA light using an undivided electrochemical cell with a boron-doped diamond (BDD) anode and an air diffusion cathode able to generate H(2)O(2). Organics were then oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between generated H(2)O(2) and added Fe(2+). The UVA irradiation in PEF enhanced the production of hydroxyl radicals in the bulk, accelerating the removal of organics and photodecomposed intermediates like Fe(III)-carboxylate complexes. Partial decontamination of 1.39 mM sulfanilic acid solutions was achieved by EF until 100 mA cm(-2) at optimum conditions of 0.4 mM Fe(2+) and pH 3.0. The increase in current density and substrate content led to an almost total mineralization. In contrast, the PEF process was more powerful, yielding almost complete mineralization in less electrolysis time under comparable conditions. The kinetics for sulfanilic acid decay always followed a pseudo-first-order reaction. Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic, and oxamic acids were identified as generated carboxylic acids. NH(4)(+) ion was preferentially released in both treatments, along with NO(3)(-) ion in smaller proportion.

  5. Biodistribution and subcellular localization of an unnatural boron-containing amino acid (cis-ABCPC) by imaging secondary ion mass spectrometry for neutron capture therapy of melanomas and gliomas.

    PubMed

    Chandra, Subhash; Barth, Rolf F; Haider, Syed A; Yang, Weilian; Huo, Tianyao; Shaikh, Aarif L; Kabalka, George W

    2013-01-01

    The development of new boron-delivery agents is a high priority for improving the effectiveness of boron neutron capture therapy. In the present study, 1-amino-3-borono-cyclopentanecarboxylic acid (cis-ABCPC) as a mixture of its L- and D-enantiomers was evaluated in vivo using the B16 melanoma model for the human tumor and the F98 rat glioma as a model for human gliomas. A secondary ion mass spectrometry (SIMS) based imaging instrument, CAMECA IMS 3F SIMS Ion Microscope, was used for quantitative imaging of boron at 500 nm spatial resolution. Both in vivo and in vitro studies in melanoma models demonstrated that boron was localized in the cytoplasm and nuclei with some cell-to-cell variability. Uptake of cis-ABCPC in B16 cells was time dependent with a 7.5:1 partitioning ratio of boron between cell nuclei and the nutrient medium after 4 hrs. incubation. Furthermore, cis-ABCPC delivered boron to cells in all phases of the cell cycle, including S-phase. In vivo SIMS studies using the F98 rat glioma model revealed an 8:1 boron partitioning ratio between the main tumor mass and normal brain tissue with a 5:1 ratio between infiltrating tumor cells and contiguous normal brain. Since cis-ABCPC is water soluble and can cross the blood-brain-barrier via the L-type amino acid transporters (LAT), it may accumulate preferentially in infiltrating tumor cells in normal brain due to up-regulation of LAT in high grade gliomas. Once trapped inside the tumor cell, cis-ABCPC cannot be metabolized and remains either in a free pool or bound to cell matrix components. The significant improvement in boron uptake by both the main tumor mass and infiltrating tumor cells compared to those reported in animal and clinical studies of p-boronophenylalanine strongly suggest that cis-ABCPC has the potential to become a novel new boron delivery agent for neutron capture therapy of gliomas and melanomas.

  6. Biodistribution and Subcellular Localization of an Unnatural Boron-Containing Amino Acid (Cis-ABCPC) by Imaging Secondary Ion Mass Spectrometry for Neutron Capture Therapy of Melanomas and Gliomas

    PubMed Central

    Chandra, Subhash; Barth, Rolf F.; Haider, Syed A.; Yang, Weilian; Huo, Tianyao; Shaikh, Aarif L.; Kabalka, George W.

    2013-01-01

    The development of new boron-delivery agents is a high priority for improving the effectiveness of boron neutron capture therapy. In the present study, 1-amino-3-borono-cyclopentanecarboxylic acid (cis-ABCPC) as a mixture of its L- and D- enantiomers was evaluated in vivo using the B16 melanoma model for the human tumor and the F98 rat glioma as a model for human gliomas. A secondary ion mass spectrometry (SIMS) based imaging instrument, CAMECA IMS 3F SIMS Ion Microscope, was used for quantitative imaging of boron at 500 nm spatial resolution. Both in vivo and in vitro studies in melanoma models demonstrated that boron was localized in the cytoplasm and nuclei with some cell-to-cell variability. Uptake of cis-ABCPC in B16 cells was time dependent with a 7.5:1 partitioning ratio of boron between cell nuclei and the nutrient medium after 4 hrs. incubation. Furthermore, cis-ABCPC delivered boron to cells in all phases of the cell cycle, including S-phase. In vivo SIMS studies using the F98 rat glioma model revealed an 8:1 boron partitioning ratio between the main tumor mass and normal brain tissue with a 5:1 ratio between infiltrating tumor cells and contiguous normal brain. Since cis-ABCPC is water soluble and can cross the blood-brain-barrier via the L-type amino acid transporters (LAT), it may accumulate preferentially in infiltrating tumor cells in normal brain due to up-regulation of LAT in high grade gliomas. Once trapped inside the tumor cell, cis-ABCPC cannot be metabolized and remains either in a free pool or bound to cell matrix components. The significant improvement in boron uptake by both the main tumor mass and infiltrating tumor cells compared to those reported in animal and clinical studies of p-boronophenylalanine strongly suggest that cis-ABCPC has the potential to become a novel new boron delivery agent for neutron capture therapy of gliomas and melanomas. PMID:24058680

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

    SciTech Connect

    Doo Seong Hwang; Hei Min Choi; Kune Woo Lee; Jei Kwon Moon

    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)

  8. 2-Meth­oxy-3-(tri­methyl­sil­yl)phenyl­boronic acid

    PubMed Central

    Durka, Krzysztof; Luliński, Sergiusz; Serwatowski, Janusz

    2013-01-01

    The mol­ecular structure of the title compound, C10H17BO3Si, features an intra­molecular O—H⋯O hydrogen bond; the boronic group group has an exo–endo conformation. In the crystal, the mol­ecules inter­act with each other by O—H⋯O hydrogen bonds, producing centrosymmetric dimers that are linked by weak π–π stacking inter­actions featuring specific short B⋯C contacts [e.g. 3.372 (2) Å], forming an infinite columnar structure aligned along the a-axis direction. PMID:24860295

  9. Boronic acid-containing CXCR1/2 antagonists: Optimization of metabolic stability, in vivo evaluation, and a proposed receptor binding model.

    PubMed

    Maeda, Dean Y; Peck, Angela M; Schuler, Aaron D; Quinn, Mark T; Kirpotina, Liliya N; Wicomb, Winston N; Auten, Richard L; Gundla, Rambabu; Zebala, John A

    2015-06-01

    Blockade of undesired neutrophil migration to sites of inflammation remains an area of substantial pharmaceutical interest. To effect this blockade, a validated therapeutic target is antagonism of the chemokine receptor CXCR2. Herein we report the discovery of 6-(2-boronic acid-5-trifluoromethoxy-benzylsulfanyl)-N-(4-fluoro-phenyl)-nicotinamide 6, an antagonist with activity at both CXCR1 and CXCR2 receptors (IC50 values 31 and 21 nM, respectively). Compound 6 exhibited potent inhibition of neutrophil influx in a rat model of pulmonary inflammation, and is hypothesized to interact with a unique intracellular binding site on CXCR2. Compound 6 (SX-576) is undergoing further investigation as a potential therapy for pulmonary inflammation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. RADIATION PROTECTION THROUGH BORON-CONTAINING CEMENTS AND CONCRETES

    DTIC Science & Technology

    WATER-SOLUBLE BORON COMPOUNDS, SUCH AS BORIC ACID OR BORAX , RETARDS THE SETTING OF CEMENT AND IMPAIRS THE MECHANICAL STRENGTH OF CONCRETE. The...deterioration was found to depend on the quantity of boron introduced, regardless of whether it is in the acid form ( boric acid ) or the alkaline form ( borax

  11. Synthesis, characterization, and antifungal activity of boron-containing thiosemicarbazones.

    PubMed

    Hicks, Justin W; Kyle, Christian B; Vogels, Christopher M; Wheaton, Susan L; Baerlocher, Felix J; Decken, Andreas; Westcott, Stephen A

    2008-11-01

    Addition of thiosemicarbazide, 4-allylthiosemicarbazide, and 4-phenylthiosemicarbazide to (formylphenyl)boronic acids affords a series of thiosemicarbazones containing boronic acids. Addition of 2-formylphenylboronic acid to the thiosemicarbazides gave the corresponding cyclic 2,3,1-benzodiazaborines. All new compounds have been investigated for potential antifungal activity.

  12. Synthesis, Chemical and Enzymatic Hydrolysis, and Aqueous Solubility of Amino Acid Ester Prodrugs of 3-Carboranyl Thymidine Analogues for Boron Neutron Capture Therapy of Brain Tumors

    PubMed Central

    Hasabelnaby, Sherifa; Goudah, Ayman; Agarwal, Hitesh K.; Abd alla, Mosaad S. M.; Tjarks, Werner

    2012-01-01

    Various water-soluble L-valine-, L-glutamate-, and glycine ester prodrugs of two 3-Carboranyl Thymidine Analogues (3-CTAs), designated N5 and N5-2OH, were synthesized for Boron Neutron Capture Therapy (BNCT) of brain tumors since the water solubilities of the parental compounds proved to be insufficient in preclinical studies. The amino acid ester prodrugs were prepared and stored as hydrochloride salts. The water solubilities of these amino acid ester prodrugs, evaluated in phosphate buffered saline (PBS) at pH 5, pH 6 and pH 7.4, improved 48 to 6600 times compared with parental N5 and N5-2OH. The stability of the amino acid ester prodrugs was evaluated in PBS at pH 7.4, Bovine serum, and Bovine cerebrospinal fluid (CSF). The rate of the hydrolysis in all three incubation media depended primarily on the amino acid promoiety and, to a lesser extend, on the site of esterification at the deoxyribose portion of the 3-CTAs. In general, 3'-amino acid ester prodrugs were less sensitive to chemical and enzymatic hydrolysis than 5'-amino acid ester prodrugs and the stabilities of the latter decreased in the following order: 5'-valine > 5'-glutamate > 5'-glycine. The rate of the hydrolysis of the 5'-amino acid ester prodrugs in Bovine CSF was overall higher than in PBS and somewhat lower than in Bovine serum. Overall, 5'-glutamate ester prodrug of N5 and the 5'-glycine ester prodrugs of N5 and N5-2OH appeared to be the most promising candidates for preclinical BNCT studies. PMID:22889558

  13. Crystalline boron nitride aerogels

    DOEpatents

    Zettl, Alexander K.; Rousseas, Michael; Goldstein, Anna P.; Mickelson, William; Worsley, Marcus A.; Woo, Leta

    2017-04-04

    This disclosure provides methods and materials related to boron nitride aerogels. In one aspect, a material comprises an aerogel comprising boron nitride. The boron nitride has an ordered crystalline structure. The ordered crystalline structure may include atomic layers of hexagonal boron nitride lying on top of one another, with atoms contained in a first layer being superimposed on atoms contained in a second layer.

  14. Boron Nitride Nanotubes

    NASA Technical Reports Server (NTRS)

    Smith, Michael W. (Inventor); Jordan, Kevin (Inventor); Park, Cheol (Inventor)

    2012-01-01

    Boron nitride nanotubes are prepared by a process which includes: (a) creating a source of boron vapor; (b) mixing the boron vapor with nitrogen gas so that a mixture of boron vapor and nitrogen gas is present at a nucleation site, which is a surface, the nitrogen gas being provided at a pressure elevated above atmospheric, e.g., from greater than about 2 atmospheres up to about 250 atmospheres; and (c) harvesting boron nitride nanotubes, which are formed at the nucleation site.

  15. Boron nitride nanotubes

    DOEpatents

    Smith, Michael W [Newport News, VA; Jordan, Kevin [Newport News, VA; Park, Cheol [Yorktown, VA

    2012-06-06

    Boron nitride nanotubes are prepared by a process which includes: (a) creating a source of boron vapor; (b) mixing the boron vapor with nitrogen gas so that a mixture of boron vapor and nitrogen gas is present at a nucleation site, which is a surface, the nitrogen gas being provided at a pressure elevated above atmospheric, e.g., from greater than about 2 atmospheres up to about 250 atmospheres; and (c) harvesting boron nitride nanotubes, which are formed at the nucleation site.

  16. Boron nitride composites

    DOEpatents

    Kuntz, Joshua D.; Ellsworth, German F.; Swenson, Fritz J.; Allen, Patrick G.

    2017-02-21

    According to one embodiment, a composite product includes: a matrix material including hexagonal boron nitride and one or more borate binders; and a plurality of cubic boron nitride particles dispersed in the matrix material. According to another embodiment, a composite product includes: a matrix material including hexagonal boron nitride and amorphous boron nitride; and a plurality of cubic boron nitride particles dispersed in the matrix material.

  17. NIP6;1 Is a Boric Acid Channel for Preferential Transport of Boron to Growing Shoot Tissues in Arabidopsis[W

    PubMed Central

    Tanaka, Mayuki; Wallace, Ian S.; Takano, Junpei; Roberts, Daniel M.; Fujiwara, Toru

    2008-01-01

    Boron (B) in soil is taken up by roots through NIP5;1, a boric acid channel, and is loaded into the xylem by BOR1, a borate exporter. Here, the function of Arabidopsis thaliana NIP6;1, the most similar gene to NIP5;1, was studied. NIP6;1 facilitates the rapid permeation of boric acid across the membrane but is completely impermeable to water. NIP6;1 transcript accumulation is elevated in response to B deprivation in shoots but not in roots. NIP6;1 promoter–β-glucuronidase is predominantly expressed in nodal regions of shoots, especially the phloem region of vascular tissues. Three independently identified T-DNA insertion lines for the NIP6;1 gene exhibited reduced expansion of young rosette leaves only under low-B conditions. B concentrations are reduced in young rosette leaves but not in the old leaves of these mutants. Taken together, these data strongly suggest that NIP6;1 is a boric acid channel required for proper distribution of boric acid, particularly among young developing shoot tissues. We propose that NIP6;1 is involved in xylem–phloem transfer of boric acid at the nodal regions and that the water-tight property of NIP6;1 is important for this function. It is proposed that during evolution, NIP5;1 and NIP6;1 were diversified in terms of both the specificity of their expression in plant tissues and their water permeation properties, while maintaining their ability to be induced under low B and their boric acid transport activities. PMID:18952773

  18. Synthesis of heteroboroxines with MB₂O₃ core (M = Sb, Bi, Sn)--an influence of the substitution of parent boronic acids.

    PubMed

    Kořenková, Monika; Mairychová, Barbora; Růžička, Aleš; Jambor, Roman; Dostál, Libor

    2014-05-21

    The synthesis and structure of stiba-, stanna- and bismaheteroboroxines of a general formula L(E)M[(OBR)2O] supported by a N,C,N-chelating ligand L [where L = C6H3-2,6-(CH2NMe2)2, M, E = Sb, lone pair or Sn, Ph or Bi, lone pair] is reported. The target compounds are prepared by straightforward one-step reactions between oxides (LMO)2 (M = Sb or Bi) or organotin(iv) carbonate L(Ph)Sn(CO3) with four or two molar equivalents of corresponding organoboronic acid. All compounds were characterized with the help of elemental analysis, multinuclear NMR spectroscopy and on several occasions the molecular structure was determined using single-crystal X-ray diffraction analysis. The influence of both the substitution of the parent organoboronic acid and the central atom used on the feasibility of the condensation reaction was addressed. Furthermore, several heteroboroxines containing nitrogen donor functionality (i.e. NH2, NMe2, CN or 4-pyridyl) included in the boronic acid residue were synthesized and characterized with the aim to prepare boroxine-based covalent frameworks (through intermolecular N→B interactions) containing metal atoms in their structures. Although no such intermolecular bonding was detected in solution of these compounds, it was shown that the organotin(iv) heteroboroxine substituted by 4-pyridyl group forms an infinite polymeric chains via N→B interactions in the solid state. This polymer collapsed back to monomeric units upon dissolution.

  19. High sensitive detection of cancer cell with a folic acid-based boron-doped diamond electrode using an AC impedimetric approach.

    PubMed

    Weng, Jian; Zhang, Zhaowu; Sun, Liping; Wang, Jin An

    2011-01-15

    An electrochemical impedance method at a fixed frequency (10Hz) is used to detect folate receptor-rich cancer cells with the interaction between folic acid immobilized on gold nanoparticles deposited on boron-doped diamond (BDD) electrode surface and its receptor over-expressed on cancer cell membrane without additional labeling. Experimental results have shown that the BDD electrode modified with folic acid can clearly denote folate receptor-rich cancer cells, such as HeLa cells, at a concentration down to 10 cells mL(-1). The high sensitivity of BDD electrode is resulted from the change of field effect and surface charge density of BDD after cancer cells attachment. The BDD electrodes can be regenerated with 0.1M citric acid/glycine/HC1 at pH 3.0 and used seven times again. Therefore, electrochemical technique with BDD electrode has been introduced for cancer cells detection and a simple method to detect folate receptor-rich cancer cells without additional labeling has been developed. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. Methods of forming boron nitride

    DOEpatents

    Trowbridge, Tammy L; Wertsching, Alan K; Pinhero, Patrick J; Crandall, David L

    2015-03-03

    A method of forming a boron nitride. The method comprises contacting a metal article with a monomeric boron-nitrogen compound and converting the monomeric boron-nitrogen compound to a boron nitride. The boron nitride is formed on the same or a different metal article. The monomeric boron-nitrogen compound is borazine, cycloborazane, trimethylcycloborazane, polyborazylene, B-vinylborazine, poly(B-vinylborazine), or combinations thereof. The monomeric boron-nitrogen compound is polymerized to form the boron nitride by exposure to a temperature greater than approximately 100.degree. C. The boron nitride is amorphous boron nitride, hexagonal boron nitride, rhombohedral boron nitride, turbostratic boron nitride, wurzite boron nitride, combinations thereof, or boron nitride and carbon. A method of conditioning a ballistic weapon and a metal article coated with the monomeric boron-nitrogen compound are also disclosed.

  1. Synthesis of Cyclic and Cage Borosilicates Based on Boronic Acids and Acetoxysilylalkoxides. Experimental and Computational Studies of the Stability Difference of Six- and Eight-Membered Rings.

    PubMed

    Torres-Huerta, Aarón; Velásquez-Hernández, Miriam de J; Ramírez-Palma, Lillian G; Cortés-Guzmán, Fernando; Martínez-Otero, Diego; Hernández-Balderas, Uvaldo; Jancik, Vojtech

    2017-08-21

    A series of borosilicates was synthesized, where the structure of the borosilicate core was easily modulated using two strategies: blocking of condensation sites and controlling the stoichiometry of the reaction. Thus, on the one hand, the condensation of phenylboronic or 3-hydroxyphenylboronic acid with diacetoxysilylalkoxide [((t)BuO)(Ph3CO)Si(OAc)2] led to the formation of borosilicates ((t)BuO)(Ph3CO)Si{(μ-O)BPh}2(μ-O) (1), [{((t)BuO)(Ph3CO)Si(μ-O)BPh(μ-O)}2] (2), and [{((t)BuO)(Ph3CO)Si(μ-O)B(3-HOPh)(μ-O)}2] (3) with a cyclic inorganic B2SiO3 or B2Si2O4 core, respectively. On the other hand, the reaction of phenylboronic acid with triacetoxysilylalkoxide (Ph3CO)Si(OAc)3 in 3:2 ratio resulted in the formation of a cagelike structure [{(Ph3CO)Si(μ-O)2BPh(μ-O)}2] (4) with B4Si4O10 core, while the reaction of the boronic acid with silicon tetraacetate generated an unusual 1,3-bis(acetate)-1,3-diphenyldiboraxane PhB(μ-O)(μ-O,O'-OAc)2BPh (5). Additionally, compound 1 was used to evaluate the possibility to form N→B donor-acceptor bond between the boron atom in the borosilicates and a nitrogen donor. Thus, coordination of 1 with piperazine yielded a tricyclic [{((t)BuO)(Ph3CO)Si(OBPh)2(μ-O)}2·C4H10N2] compound 6 with two borosilicate rings bridged by a piperazine molecule. Finally, the processes involved in the formation of the six- and eight-membered rings (B2SiO3 and B2Si2O4) in compounds 1 and 2 were explored using solution (1)H NMR studies and density functional theory calculations. These molecules represent to the best of our knowledge first examples of cyclic molecular borosilicates containing SiO4 units.

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

    PubMed Central

    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 ΔGbinding 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

  3. Fabrication of electrochemical interface based on boronic acid-modified pyrroloquinoline quinine/reduced graphene oxide composites for voltammetric determination of glycated hemoglobin.

    PubMed

    Zhou, Yanli; Dong, Hui; Liu, Lantao; Hao, Yuanqiang; Chang, Zhu; Xu, Maotian

    2015-02-15

    A voltammetric sensor for determination of glycated hemoglobin (HbA1c) was developed based on the composites of phenylboronic acid-modified pyrroloquinoline quinine (PBA-PQQ) and reduced graphene oxide. After the electrodeposition of reduced graphene oxide (ERGO) on the glassy carbon (GC) electrode, PQQ multilayer was decorated on the surface of the ERGO/GC electrode via potential cycling. Further modification with PBA would lead to the formation of the working electrode, namely PBA-PQQ/ERGO/GC electrode. PQQ on the electrode exhibited a quasi-reversible electrode process with 2-electron transfer and 2-proton participation, and the electron transfer efficiency was further enhanced by the introduction of ERGO layer. The complexation of PBA with HbA1c through specific boronic acid-diol recognition could cause the change of the oxidation peak current of PQQ on the electrode, which was utilized for HbA1c detection. Under the optimized conditions, the PBA-PQQ/ERGO/GC electrode provided high selectivity and high sensitivity for HbA1c detection with a linear range of 9.4-65.8 μg mL(-1) and a low detection limit of 1.25 μg mL(-1). The fabricated sensor was also successfully applied to determine the percentages of HbA1c in whole blood of healthy individuals.

  4. Cosmic abundance of boron.

    NASA Technical Reports Server (NTRS)

    Cameron, A. G. W.; Colgate, S. A.; Grossman, L.

    1973-01-01

    All abundances are expressed relative to a million atoms of Si. An average abundance of boron in ordinary chondrites is 6.2. The boron abundance in meteorites is highly variable. It has been found that the abundances in carbonaceous chondrites are very much higher than those in ordinary chondrites. The condensation of boron and beryllium from a cooling, low-pressure gas of solar composition is discussed together with the occurrence of boron in the interstellar medium, questions of element abundances in the sun, problems of boron production by cosmic rays, and boron production from supernovae.

  5. Comparative study of mono- and multi-filament MgB2 wires with different boron powders and malic acid addition

    NASA Astrophysics Data System (ADS)

    Kim, J. H.; Heo, Yoon-Uk; Matsumoto, A.; Kumakura, H.; Rindfleisch, M.; Tomsic, M.; Dou, S. X.

    2010-07-01

    We evaluated the effects of different boron (B) powders and of malic acid (C4H6O5) addition on the critical current density (Jc) of mono- and multi-filament MgB2 wires. We found that Jc of the wires made from the amorphous B showed the best performance. Low sintering processing keeps the grain size small, which leads to strong flux pinning. From transmission electron microscopy (TEM) observations, we confirmed that the crystalline B powders supplied by SMI and Tangshan had a β-rhombohedral structure as a main phase. These two powders also had numerous defects, such as twin and stacking faults inside the powder particles. However, these defects are not enough to promote the full reaction between magnesium (Mg) and B crystalline powder when sintered at low temperatures, and brings about low Jc values. Even though the morphologies of the two crystalline B powders appeared somewhat different, Jc for the two wires had similar quantitative values. For the malic acid doped wires, Jc of the wire made from the amorphous B was estimated to be above 100 000 A cm - 2 at 6 T and 4.2 K. This value is comparable to the low temperature superconductor Nb-Ti. In addition, the Jc was 25 000 A cm - 2 at 10 T and 4.2 K. This performance is the best Jc reported so far in in situ processed MgB2 wires. Interestingly, the low-field Jc performance of malic acid doped wire fabricated with crystalline B is higher than that of the pure wire fabricated with amorphous B. At 20 K, enhanced performance of Jc by malic acid doping is much higher than that of the pure MgB2 wire. The Jc at 5 T and 20 K was estimated to be 13 000 A cm - 2.

  6. On-column labeling of gram-positive bacteria with a boronic acid functionalized squarylium cyanine dye for analysis by polymer-enhanced capillary transient isotachophoresis.

    PubMed

    Saito, Shingo; Massie, Tara L; Maeda, Takeshi; Nakazumi, Hiroyuki; Colyer, Christa L

    2012-03-06

    A new asymmetric, squarylium cyanine dye functionalized by boronic acid ("SQ-BA") was designed and synthesized for on-capillary labeling of gram-positive bacteria to provide for high sensitivity detection by way of a modified form of capillary electrophoresis with laser induced fluorescence detection (CE-LIF). The CE-based separation employed a polymer-enhanced buffer with capillary transient isotachophoresis in a new hybrid method dubbed "PectI." It was found that the addition of various monosaccharides to SQ-BA in a batch aqueous solution greatly enhanced the emission of the boronic acid functionalized dye by a factor of up to 18.3 at a long wavelength (λ(ex) = 630 nm, λ(em) = 660 nm) with a high affinity constant (K = ~10(2.80) M(-1)) superior to other sugar probes. Semiempirical quantum mechanics calculations suggest that the mechanism for this high enhancement may involve the dissociation of initially nonemissive dye associates (stabilized by an intramolecular hydrogen bond) upon complex formation with sugars. The fluorescence emission of SQ-BA was also significantly enhanced in the presence of a gram-positive bacterial spore, Bacillus globigii (Bg), which serves as a simulant of B. anthracis (or anthrax) and which possesses a peptidoglycan (sugar)-rich spore coat to provide ample sites for interaction with the dye. Several peaks were observed for a pure Bg sample even with polyethyleneoxide (PEO) present in the CE separation buffer, despite the polymer's previously demonstrated ability to focus microoorganisms to a single peak during migration. Likewise, several peaks were observed for a Bg sample when capillary transient isotachophoresis (ctITP) alone was employed. However, the new combination of these techniques as "PectI" dramatically and reproducibly focused the bacteria to a single peak with no staining procedure. Using PectI, the trace detection of Bg spores (corresponding to approximately three cells per injection) along with separation efficiency

  7. Biological activity of N(4)-boronated derivatives of 2'-deoxycytidine, potential agents for boron-neutron capture therapy.

    PubMed

    Nizioł, Joanna; Uram, Łukasz; Szuster, Magdalena; Sekuła, Justyna; Ruman, Tomasz

    2015-10-01

    Boron-neutron capture therapy (BNCT) is a binary anticancer therapy that requires boron compound for nuclear reaction during which high energy alpha particles and lithium nuclei are formed. Unnatural, boron-containing nucleoside with hydrophobic pinacol moiety was investigated as a potential BNCT boron delivery agent. Biological properties of this compound are presented for the first time and prove that boron nucleoside has low cytotoxicity and that observed apoptotic effects suggest alteration of important functions of cancer cells. Mass spectrometry analysis of DNA from cancer cells proved that boron nucleoside is inserted into nucleic acids as a functional nucleotide derivative. NMR studies present very high degree of similarity of natural dG-dC base pair with dG-boron nucleoside system. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Switchable Surface Wettability by Using Boronic Ester Chemistry.

    PubMed

    Taleb, Sabri; Noyer, Elisabeth; Godeau, Guilhem; Darmanin, Thierry; Guittard, Frédéric

    2016-01-18

    Here, we report for the first time the use of a boronic ester as an efficient tool for reversible surface post-functionalization. The boronic ester bond allows surfaces to be reversibly switched from hydrophilic to hydrophobic. Based on the well-known boronic acid/glycol affinity, this strategy offers the opportunity to play with surface hydrophobic properties by adding various boronic acids onto substrates bearing glycol groups. The post-functionalization can then be reversed to regenerate the starting glycol surface. This pathway allows for the preparation of various switchable surfaces for a large range of applications in biosensors, liquid transportation, and separation membranes.

  9. Boronate-tau mediated uptake in neurons.

    PubMed

    Pérez, Mar; Cuadros, Raquel; Pallas-Bazarra, Noemi; García, Carlos; Langa, Elena; Jurado-Arjona, Jerónimo; Hernández, Félix; Avila, Jesús

    2014-01-01

    We modified tau protein with boronic acid to facilitate its delivery into non neural or neural cultured cells lacking tau protein. Our results indicate that the incorporated tau promotes the formation of cytoplasmic extensions in non-neuronal cells, as well as the appearance of neurites in cultured tau knockout hippocampal neurons. In addition, boronated tau is incorporated into hippocampal neurons of tau knockout mice after intracranial injection in vivo. These findings describe a novel method to deliver exogenous tau protein into cells.

  10. 4-Hydroxyphenylacetic acid oxidation in sulfate and real olive oil mill wastewater by electrochemical advanced processes with a boron-doped diamond anode.

    PubMed

    Flores, Nelly; Cabot, Pere Lluís; Centellas, Francesc; Garrido, José Antonio; Rodríguez, Rosa María; Brillas, Enric; Sirés, Ignasi

    2017-01-05

    The degradation of 4-hydroxyphenylacetic acid, a ubiquitous component of olive oil mill wastewater (OOMW), has been studied by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed in either a 0.050M Na2SO4 solution or a real OOMW at pH 3.0, using a cell with a boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 generation. Hydroxyl radicals formed at the BDD surface from water oxidation in all processes and/or in the bulk from Fenton's reaction between added Fe(2+) and generated H2O2 in EF and PEF were the main oxidants. In both matrices, the oxidation ability of the processes increased in the order AO-H2O2acid decay obeyed a pseudo-first-order kinetics. The PEF treatment of 1.03mM 4-hydroxyphenylacetic acid in 0.050M Na2SO4 allowed 98% mineralization at 360min even at low current density, whereas 80% mineralization and a significant enhancement of biodegradability were achieved with the real OOMW.

  11. An efficient 2D (11)B-(11)B solid-state NMR spectroscopy strategy for monitoring covalent self-assembly of boronic acid-derived compounds: the transformation and unique architecture of bortezomib molecules in the solid state.

    PubMed

    Brus, J; Czernek, J; Urbanova, M; Kobera, L; Jegorov, A

    2016-12-21

    The difficulty in the prediction of the complicated solid-state structure of boronic acid derivatives, resulting from the complex pathway of reversible covalent interactions, represents a significant obstacle to the development of a new generation of advanced supramolecular systems such as covalent organic frameworks of efficient anticancer drugs. In this contribution, various 2D (11)B-(11)B solid-state NMR correlation techniques supported by DFT calculations were explored to formulate a reliable tool for monitoring the covalent assembly of boronic acid residues in the solid state. This way, the self-condensation of bortezomib molecules was investigated, different local constitutions of boroxine motifs were unveiled, and the previously unreported boroxine structures of bortezomib polymorphs exhibiting secondary coordination were discovered and described in detail. The recorded (11)B NMR parameters responded sensitively to subtle changes in the local geometries, which were reliably interpreted and directly visualized by the DFT calculations. A uniform 2.6 Å distance in bortezomib (11)B-(11)B spin pairs was conclusively identified by the through-space (11)B-(11)B double-quantum (DQ) coherence build-up curves, whereas distinct 2D (11)B-(11)B DQ correlation patterns revealed unique boroxine structures existing in the crystalline as well as amorphous state. The boroxine rings were found to be internally stabilized through the transformation of the trigonal boron sites toward tetrahedral geometry, as the secondary five-membered rings were formed. This way, the nature of bortezomib polymorphism is disclosed, and an efficient strategy for exploring the assembly of boronic acid derivatives in the solid state, for which no crystallographic data are available, is thus demonstrated.

  12. A space network structure constructed by tetraneedlelike ZnO whiskers supporting boron nitride nanosheets to enhance comprehensive properties of poly(L-lacti acid) scaffolds

    PubMed Central

    Feng, Pei; Peng, Shuping; Wu, Ping; Gao, Chengde; Huang, Wei; Deng, Youwen; Shuai, Cijun

    2016-01-01

    In this study, the mechanical strength and modulus of poly(L-lacti acid) (PLLA) scaffolds were enhanced with the mechanical properties of boron nitride nanosheets (BNNSs) and tetraneedlelike ZnO whiskers (T-ZnOw). The adhesion and proliferation of cells were improved as well as osteogenic differentiation of stem cells was increased. Their dispersion statues in PLLA matrix were improved through a space network structure constructed by three-dimensional T-ZnOw supporting two-dimensional BNNSs. The results showed that the compressive strength, modulus and Vickers hardness of the scaffolds with incorporation of 1 wt% BNNSs and 7 wt% T-ZnOw together were about 96.15%, 32.86% and 357.19% higher than that of the PLLA scaffolds, respectively. This might be due to the effect of the pull out and bridging of BNNSs and T-ZnOw as well as the crack deflection, facilitating the formation of effective stress transfer between the reinforcement phases and the matrix. Furthermore, incorporation of BNNSs and T-ZnOw together into PLLA scaffolds was beneficial for attachment and viability of MG-63 cells. More importantly, the scaffolds significantly increased proliferation and promoted osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs). The enhanced mechanical and biological properties provide the potentials of PLLA/BNNSs/T-ZnOw scaffolds for the application into bone tissue engineering. PMID:27629058

  13. Structure analysis and spectroscopic characterization of 2-Fluoro-3-Methylpyridine-5-Boronic Acid with experimental (FT-IR, Raman, NMR and XRD) techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Alver, Özgür; Dikmen, Gökhan

    2016-03-01

    Possible stable conformers, geometrical molecular structures, vibrational properties as well as band assignments, nuclear magnetic shielding tensors of 2-Fluoro-3-Methylpyridine-5-Boronic Acid (2F3MP5BA) were studied experimentally and theoretically using FT-IR, Raman, (CP/MAS) NMR and XRD spectroscopic methods. FT-IR and Raman spectra were evaluated in the region of 3500-400 cm-1, and 3200-400 cm-1, respectively. The optimized geometric structures, vibrational wavenumbers and nuclear magnetic shielding tensors were examined using Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-311++G(d, p) basis set. 1H, 13C NMR chemical shifts were calculated using the gauge invariant atomic orbital (GIAO) method. 1H, 13C, APT and HETCOR NMR experiments of title molecule were carried out in DMSO solution. 13C CP/MAS NMR measurement was done with 4 mm zirconium rotor and glycine was used as an external standard. Single crystal of 2F3MP5BA was also prepared for XRD measurements. Assignments of vibrational wavenumbers were also strengthened by calculating the total energy distribution (TED) values using scaled quantum mechanical (SQM) method.

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

    PubMed

    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.

  15. Controlling false-positive results obtained with the Hodge and Masuda assays for detection of class a carbapenemase in species of enterobacteriaceae by incorporating boronic Acid.

    PubMed

    Pasteran, Fernando; Mendez, Tania; Rapoport, Melina; Guerriero, Leonor; Corso, Alejandra

    2010-04-01

    The modified Hodge method (MHT) has been recommended by the CLSI for confirmation of suspected class A carbapenemase production in species of Enterobacteriaceae. This test and the Masuda method (MAS) have advantages over traditional phenotypic methods in that they directly analyze carbapenemase activity. In order to identify the potential interferences of these tests, we designed a panel composed of diverse bacterial genera with distinct carbapenem susceptibility patterns (42 carbapenemase producers and 48 nonproducers). About 25% of results among carbapenemase nonproducers, mainly strains harboring CTX-M and AmpC hyperproducers, were observed to be false positive. Subsequently, we developed an optimized approach for more-accurate detection of suspicious isolates of carbapenemase by addition of boronic acid (BA) derivatives (reversible inhibitor of class A carbapenemases and AmpC cephalosporinases) and oxacillin (inhibitor of AmpCs enzymes). The use of the modified BA- and oxacillin-based MHT and MAS resulted in high sensitivity (>90%) and specificity (100%) for class A carbapenemase detection. By use of these methodologies, isolates producing KPCs and GES, Sme, IMI, and NMC-A carbapenemases were successfully distinguished from those producing other classes of ss-lactamases (extended-spectrum beta-lactamases [ESBLs], AmpC beta-lactamases, metallo-beta-lactamases [MBLs], etc.). These methods will provide the fast and useful information needed for targeting of antimicrobial therapy and appropriate infection control.

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

    PubMed

    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 H2O2 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 H2O2 biosensor can be easily achieved without any complex processing. Meanwhile, the immobilized HRP exhibited enhanced stability and remarkable catalytic activity towards H2O2 reduction. Under optimal conditions, the biosensor showed a fast response time (less than 4s) to H2O2 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 H2O2 released from living cells with satisfactory results, thus showing the potential application in the study of H2O2-involved dynamic pathological and physiological process. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. A space network structure constructed by tetraneedlelike ZnO whiskers supporting boron nitride nanosheets to enhance comprehensive properties of poly(L-lacti acid) scaffolds.

    PubMed

    Feng, Pei; Peng, Shuping; Wu, Ping; Gao, Chengde; Huang, Wei; Deng, Youwen; Shuai, Cijun

    2016-09-15

    In this study, the mechanical strength and modulus of poly(L-lacti acid) (PLLA) scaffolds were enhanced with the mechanical properties of boron nitride nanosheets (BNNSs) and tetraneedlelike ZnO whiskers (T-ZnOw). The adhesion and proliferation of cells were improved as well as osteogenic differentiation of stem cells was increased. Their dispersion statues in PLLA matrix were improved through a space network structure constructed by three-dimensional T-ZnOw supporting two-dimensional BNNSs. The results showed that the compressive strength, modulus and Vickers hardness of the scaffolds with incorporation of 1 wt% BNNSs and 7 wt% T-ZnOw together were about 96.15%, 32.86% and 357.19% higher than that of the PLLA scaffolds, respectively. This might be due to the effect of the pull out and bridging of BNNSs and T-ZnOw as well as the crack deflection, facilitating the formation of effective stress transfer between the reinforcement phases and the matrix. Furthermore, incorporation of BNNSs and T-ZnOw together into PLLA scaffolds was beneficial for attachment and viability of MG-63 cells. More importantly, the scaffolds significantly increased proliferation and promoted osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs). The enhanced mechanical and biological properties provide the potentials of PLLA/BNNSs/T-ZnOw scaffolds for the application into bone tissue engineering.

  18. Dopamine sensor based on a boron-doped diamond electrode modified with a polyaniline/Au nanocomposites in the presence of ascorbic acid.

    PubMed

    Song, Min-Jung; Lee, Seung-Koo; Kim, Jong-Hoon; Lim, Dae-Soon

    2012-01-01

    A selective dopamine (DA) sensor was developed using gold nanoparticles (Au-NPs) dispersed overoxidized-polyaniline (PANI(ox)) based on a boron-doped diamond (BDD) thin-film electrode. The concentration of the DA was determined using voltammetry as a non-enzymatic sensor. BDD thin film has a high signal-to-noise ratio, a long-term stability, a high sensitivity, and a good reproducibility. PANI nanocomposites were directly synthesized on the BDD electrode and overoxidized using 0.5 M H(2)SO(4) solution. The overoxidized PANI film enhances selectivity and sensitivity toward DA. The Au-NPs were dispersed on the PANI nanocomposite by electrochemical deposition. The nanometer-sized Au-NPs favor the sensing of DA in the presence of ascorbic acid (AA). The combination of the PANI with the Au-NPs and the BDD electrode can create synergetic effects for the performance of the biosensor, such as a fast response time, a lower detection limit, a wider linear range, enhanced selectivity, and higher sensitivity for the determination of DA.

  19. Electrochemical behavior of chlorogenic acid at a boron-doped diamond electrode and estimation of the antioxidant capacity in the coffee samples based on its oxidation peak.

    PubMed

    Yardım, Yavuz

    2012-04-01

    In this study, an electroanalytical methodology for the determination of chlorogenic acid (CGA) was achieved at a boron-doped diamond electrode under adsorptive transfer stripping voltammetric conditions. The values obtained for CGA were used to estimate the antioxidant properties of the coffee sample based on CGA oxidation. By using square-wave stripping mode, the compound yielded a well-defined voltammetric response at +0.49 V with respect to Ag/AgCl in Britton-Robinson buffer at pH 3.0 (after 120 s accumulations at a fixed potential of 0.40 V). At the optimum experimental conditions, linear calibration curve is obtained within the concentration range of 0.25 to 4.0 μg mL⁻¹ with the limit of detection 0.049 μg mL⁻¹ . The developed protocol was successfully applied for the analysis of antioxidant capacity in the coffee products such as Turkish coffee and instant coffee.

  20. Metabolic analysis revealed altered amino acid profiles in Lupinus albus organs as a result of boron deficiency.

    PubMed

    Alves, Marta; Chicau, Paula; Matias, Helena; Passarinho, José; Pinheiro, Carla; Ricardo, Cândido Pinto

    2011-07-01

    We analysed the changes in the metabolites of Lupinus albus organs (leaf-blades, petioles, apexes, hypocotyls and roots) as a consequence of B deficiency. The deficiency did not affect malate concentration and induced only minor changes in the sugar content, suggesting that the carbohydrate metabolism is little affected by the deficiency. Contrarily, marked changes in the content of free amino acids were observed, with some specific variations associated with the different organs. These changes indicate that various aspects of metabolism implicated in the amino acid accumulation were affected by B deficiency. Most of the detected changes appear to have implications with some stress responses or signalling processes. Asparagine and proline that increase in many stresses also accumulated in petioles, apexes and hypocotyls. Accumulation of γ-aminobutyric acid shunt amino acids, indicative of production of reactive oxygen species, occurs in the same three organs and also the roots. The increase in the branched-chain amino acids, observed in all organs, suggests the involvement of B with the cytoskeleton, whereas glycine decrease in leaf-blades and active growing organs (apexes and roots) could be associated with the proposed role of this amino acids in plant signalling in processes that might be associated with the decreased growth rates observed in B deficiency. Despite the admitted importance of free amino acids in plant metabolism, the available information on this matter is scarce. So our results bring new information concerning the effects of B deficiency in the metabolism of the several L. albus organs.

  1. Boron nitride converted carbon fiber

    SciTech Connect

    Rousseas, Michael; Mickelson, William; Zettl, Alexander K.

    2016-04-05

    This disclosure provides systems, methods, and apparatus related to boron nitride converted carbon fiber. In one aspect, a method may include the operations of providing boron oxide and carbon fiber, heating the boron oxide to melt the boron oxide and heating the carbon fiber, mixing a nitrogen-containing gas with boron oxide vapor from molten boron oxide, and converting at least a portion of the carbon fiber to boron nitride.

  2. Modular Attachment of Appended Boron Lewis Acids to a Ruthenium Pincer Catalyst: Metal-Ligand Cooperativity Enables Selective Alkyne Hydrogenation.

    PubMed

    Tseng, Kuei-Nin T; Kampf, Jeff W; Szymczak, Nathaniel K

    2016-08-24

    A new series of bifunctional Ru complexes with pendent Lewis acidic boranes were prepared by late-stage modification of an active hydrogen-transfer catalyst. The appended boranes modulate the reactivity of a metal hydride as well as catalytic hydrogenations. After installing acidic auxiliary groups, the complexes become multifunctional and catalyze the cis-selective hydrogenation of alkynes with higher rates, conversions, and selectivities compared with the unmodified catalyst.

  3. Synthesis of [18F]arenes via the copper-mediated [18F]fluorination of boronic acids

    DOE PAGES

    Mossine, Andrew V.; Brooks, Allen F.; Makaravage, Katarina J.; ...

    2015-11-14

    Here, a copper-mediated radiofluorination of aryl- and vinylboronic acids with K18F is described. This method exhibits high functional group tolerance and is effective for the radiofluorination of a range of electron-deficient, -neutral, and -rich aryl-, heteroaryl-, and vinylboronic acids. This method has been applied to the synthesis of [18F]FPEB, a PET radiotracer for quantifying metabotropic glutamate 5 receptors.

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

    PubMed

    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.

  5. Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets

    NASA Astrophysics Data System (ADS)

    Xue, Yafang; Liu, Qian; He, Guanjie; Xu, Kaibing; Jiang, Lin; Hu, Xianghua; Hu, Junqing

    2013-01-01

    The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.

  6. Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets.

    PubMed

    Xue, Yafang; Liu, Qian; He, Guanjie; Xu, Kaibing; Jiang, Lin; Hu, Xianghua; Hu, Junqing

    2013-01-24

    The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.

  7. Chemical disposition of boron in animals and humans.

    PubMed Central

    Moseman, R F

    1994-01-01

    Elemental boron was isolated in 1808. It typically occurs in nature as borates hydrated with varying amounts of water. Important compounds are boric acid and borax. Boron compounds are also used in the production of metals, enamels, and glasses. In trace amounts, boron is essential for the growth of many plants, and is found in animal and human tissues at low concentrations. Poisoning in humans has been reported as the result of accidental ingestion or use of large amounts in the treatment of burns. Boron as boric acid is fairly rapidly absorbed and excreted from the body via urine. The half-life of boric acid in humans is on the order of 1 day. Boron does not appear to accumulate in soft tissues of animals, but does accumulate in bone. Normal levels of boron in soft tissues, urine, and blood generally range from less than 0.05 ppm to no more than 10 ppm. In poisoning incidents, the amount of boric acid in brain and liver tissue has been reported to be as high as 2000 ppm. Recent studies at the National Institute of Environmental Health Sciences have indicated that boron may contribute to reduced fertility in male rodents fed 9000 ppm of boric acid in feed. Within a few days, boron levels in blood and most soft tissues quickly reached a plateau of about 15 ppm. Boron in bone did not appear to plateau, reaching 47 ppm after 7 days on the diet. Cessation of exposure to dietary boron resulted in a rapid drop in bone boron.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7889870

  8. Mechanism of Enhanced Electrochemical Oxidation of 2,4-dichlorophenoxyacetic Acid with in situ Microwave Activated Boron-doped Diamond and Platinum Anodes

    NASA Astrophysics Data System (ADS)

    Gao, Junxia; Zhao, Guohua; Liu, Meichuan; Li, Dongming

    2009-09-01

    Remarkable enhancement in degradation effect is achieved at in situ activated boron-doped diamond (BDD) and Pt anodes with different extent through electrochemical oxidation (EC) of 2,4-dichlorophenoxyacetic acid (2,4-D) with microwave (MW) radiation in a flow system. Results show that when EC is activated with MW radiation, the complete mineralization time of 2,4-D at the BDD is reduced quickly from 10 to 4 h while Chemical oxygen demand (COD) removal at Pt is increased from 37.7 to 58.3% at 10 h; the initial current efficiency is both improved about 1.5 times while the pseudo-first-order rate constant is increased by 153 and 119% at the BDD and Pt, respectively. To gain insight into the higher efficiency in microwave activated EC, the mechanism has therefore been systematically evaluated from the essence of electrochemical reaction and the accumulated hydroxyl radical concentration. 2,4-Dichlorophenol, catechol, benquinone, and maleic and oxalic acids are the main intermediates on the Pt anode measured by high performance liquid chromatography (HPLC), while the intermediates on the BDD electrode include 2,4-dichlorophenol, hydroquinone, and maleic and oxalic acids. The reaction pathway with microwave radiation is the same as that in a conventional electrochemical oxidation on both electrodes. While less and lower aromatic intermediates produce at the BDD with MW, which suggests the higher ring-open ratio and the faster oxidation of carboxylic acids. With microwave radiation, the ring-open ratio at the BDD is increased to 98.8% from 85.6%; the value at Pt is increased to 67.3% from 35.9%. So microwave radiation can activate the electrochemical oxidation, which leads to the higher efficiency. This promotion is mainly due to the higher accumulated hydroxyl radical concentration and the effects by microwave radiation. All the results prove that the BDD electrode presents much better mineralization performance with MW. To the best of our knowledge, it is the first

  9. Single step synthesis of nanostructured boron nitride for boron neutron capture therapy

    NASA Astrophysics Data System (ADS)

    Singh, Bikramjeet; Singh, Paviter; Kumar, Manjeet; Thakur, Anup; Kumar, Akshay

    2015-05-01

    Nanostructured Boron Nitride (BN) has been successfully synthesized by carbo-thermic reduction of Boric Acid (H3BO3). This method is a relatively low temperature synthesis route and it can be used for large scale production of nanostructured BN. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analyzer (DTA). XRD analysis confirmed the formation of single phase nanostructured Boron Nitride. SEM analysis showed that the particles are spherical in shape. DTA analysis showed that the phase is stable upto 900 °C and the material can be used for high temperature applications as well boron neutron capture therapy (BNCT).

  10. Properties of boron/boron-nitride multilayers

    SciTech Connect

    Jankowski, A.F.; Wall, M.A.; Hayes, J.P.; Alexander, K.B.

    1996-06-01

    Boron-Nitride films are of interest for their high hardness and wear resistance. Large intrinsic stresses and poor adhesion which often accompany high hardness materials can be moderated through the use of a layered structure. Alternate layers of boron (B) and boron-nitride (BN) are formed by modulating the composition of the sputter gas during deposition from a pure B target. The thin films are characterized with TEM to evaluate the microstructure and with nanoindentation to determine hardness. Layer pair spacing and continuity effects on hardness are evaluated for the B/BN films.

  11. Copper-Catalyzed Synthesis of Unsymmetrical Diorganyl Chalcogenides (Te/Se/S) from Boronic Acids under Solvent-Free Conditions.

    PubMed

    Saba, Sumbal; Botteselle, Giancarlo Vaccari; Godoi, Marcelo; Frizon, Tiago Elias Allievi; Galetto, Fábio Zazyki; Rafique, Jamal; Braga, Antonio L

    2017-08-18

    The efficient and mild copper-catalyzed synthesis of unsymmetrical diorganyl chalcogenides under ligand- and solvent-free conditions is described. The cross-coupling reaction was performed using aryl boric acids and 0.5 equiv. of diorganyl dichalcogenides (Te/Se/S) in the presence of 3 mol % of CuI and 3 equiv. of DMSO, under microwave irradiation. This new protocol allowed the preparation of several unsymmetrical diorganyl chalcogenides in good to excellent yields.

  12. C3 -Symmetric Boron Lewis Acid with a Cage-Shape for Chiral Molecular Recognition and Asymmetric Catalysis.

    PubMed

    Konishi, Akihito; Nakaoka, Koichi; Maruyama, Hikaru; Nakajima, Hideto; Eguchi, Tomohiro; Baba, Akio; Yasuda, Makoto

    2017-01-26

    Chiral Lewis acids play an important role in the precise construction of various types of chiral molecules. Here, a cage-shaped borate 2 was designed and synthesized as a chiral Lewis acid that possesses a unique C3 -symmetric structure composed of three homochiral binaphthyl moieties. The highly symmetrical structure of 2 with homochirality was clearly elucidated by X-ray crystallographic analysis. The peculiar chiral environment of 2⋅THF exhibited chiral recognition of some simple amines and a sulfoxide. Moreover, the application of 2⋅THF to hetero-Diels-Alder reactions as a chiral Lewis-acid catalyst afforded the enantioselective products, which were obtained through an entropy-controlled pathway according to the analysis of the relationship between optical yield and reaction temperature. In particular, the robust chiral reaction field of 2⋅THF allowed the first example of an asymmetric hetero-Diels-Alder reaction with a simple diene despite the requirement of high temperature.

  13. Application of palladium-catalyzed carboxyl anhydride-boronic acid cross coupling in the synthesis of novel bile acids analogs with modified side chains.

    PubMed

    Mayorquín-Torres, Martha C; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A

    2015-09-01

    Palladium-catalyzed cross coupling of 4-methoxycarbonyl phenyboronic acid with acetylated bile acids in which the carboxyl functions was activated by formation of a mixed anhydride with pivalic anhydride afforded the cross coupled compounds, which were converted in novel side chain modified bile acids by one pot carbonyl reduction/removal of the protecting acetyl groups by Wolff-Kishner reduction. Unambiguous assignments of the NMR signals and crystal characterization of the heretofore unknown compounds are provided.

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

    PubMed

    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.

  15. Effect of consumption of fatty acids, calcium, vitamin D and boron with regular physical activity on bone mechanical properties and corresponding metabolic hormones in rats.

    PubMed

    Naghii, M R; Ebrahimpour, Y; Darvishi, P; Ghanizadeh, G; Mofid, M; Torkaman, G; Asgari, A R; Hedayati, M

    2012-03-01

    The consumption of fatty acids, nutrients, and regular physical activity, individually influence bone mechanical properties in rats. To investigate their effects in combination, male rats were divided into the seven groups: G1: regular food and drinking water; G2: same as Gr.1 + physical activity (Whole body vibration; WBV); G3: same as Gr.2 + Calcium, Vit. D, Boron; G4: same as Gr.3 + canola oil; G5: same as Gr.3 + sunflower oil; G6: same as Gr.3 + mix of sunflower oil and canola oil; and G7: same as Gr.3 + coconut oil; and treated for 8 weeks. Analysis between the control with the groups 2 and 3 revealed that vibration in the G2 increased the body weight (P = 0.04), with no other major difference in plasma and bone indices. Comparison between the control with the G4-G7 (the oil groups) revealed that the rats in the G5 had a lower body weight (15 % less) and a significant increase in plasma levels of Estradiol in the G7 was noted. In addition, levels of Testosterone in the G4 and G7, and Free Testosterone in the G7 had a remarkable increase. Similar trend was observed for plasma levels of Vit. D in the G4 and G5. The stiffness and the breaking strength of the femur in the G7, and the breaking strength of the lumbar in the G7 compared to the control and the G4 and G5 was significantly higher and tended to increase in comparison to the G6. Better and stronger measurements observed for coconut oil is warranted to further study its effect on biomechanical properties of bones.

  16. Novel Insights Into The Mode of Inhibition of Class A SHV-1 Beta-Lactamases Revealed by Boronic Acid Transition State Inhibitors

    SciTech Connect

    W Ke; J Sampson; C Ori; F Prati; S Drawz; C Bethel; R Bonomo; F van den Akker

    2011-12-31

    Boronic acid transition state inhibitors (BATSIs) are potent class A and C {beta}-lactamase inactivators and are of particular interest due to their reversible nature mimicking the transition state. Here, we present structural and kinetic data describing the inhibition of the SHV-1 {beta}-lactamase, a clinically important enzyme found in Klebsiella pneumoniae, by BATSI compounds possessing the R1 side chains of ceftazidime and cefoperazone and designed variants of the latter, compounds 1 and 2. The ceftazidime and cefoperazone BATSI compounds inhibit the SHV-1 {beta}-lactamase with micromolar affinity that is considerably weaker than their inhibition of other {beta}-lactamases. The solved crystal structures of these two BATSIs in complex with SHV-1 reveal a possible reason for SHV-1's relative resistance to inhibition, as the BATSIs adopt a deacylation transition state conformation compared to the usual acylation transition state conformation when complexed to other {beta}-lactamases. Active-site comparison suggests that these conformational differences might be attributed to a subtle shift of residue A237 in SHV-1. The ceftazidime BATSI structure revealed that the carboxyl-dimethyl moiety is positioned in SHV-1's carboxyl binding pocket. In contrast, the cefoperazone BATSI has its R1 group pointing away from the active site such that its phenol moiety moves residue Y105 from the active site via end-on stacking interactions. To work toward improving the affinity of the cefoperazone BATSI, we synthesized two variants in which either one or two extra carbons were added to the phenol linker. Both variants yielded improved affinity against SHV-1, possibly as a consequence of releasing the strain of its interaction with the unusual Y105 conformation.

  17. NMR, FT-IR, Raman and UV-Vis spectroscopic investigation and DFT study of 6-Bromo-3-Pyridinyl Boronic Acid

    NASA Astrophysics Data System (ADS)

    Dikmen, Gökhan; Alver, Özgür

    2015-11-01

    Possible stable conformers and geometrical molecular structures of 6-Bromo-3-Pyridinyl Boronic acid (6B3PBA; C5H5BBrNO2) were studied experimentally and theoretically using FT-IR and Raman spectroscopic methods. FT-IR and Raman spectra were recorded in the region of 4000-400 cm-1 and 3700-400 cm-1, respectively. The structural properties were investigated further, using 1H, 13C, 1H coupled 13C, HETCOR, COSY and APT NMR techniques. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-311++G(d, p) basis set. Vibrational wavenumbers of 6B3PBA were calculated whereby B3LYP density functional methods including 6-311++G(d, p), 6-311G(d, p), 6-311G(d), 6-31G(d, p) and 6-31G(d) basis sets. The comparison of the experimentally and theoretically obtained results using mean absolute error and experimental versus calculated correlation coefficients for the vibrational wavenumbers indicates that B3LYP method with 6-311++G(d, p) gives more satisfactory results for predicting vibrational wavenumbers when compared to the 6-311G(d, p), 6-311G(d), 6-31G(d, p) and 6-31G(d) basis sets. However, this method and none of the mentioned methods here seem suitable for the calculations of OH stretching modes, most likely because increasing unharmonicity in the high wave number region and possible intra and inter molecular interactions at OH edges lead some deviations between experimental and theoretical results. Moreover, reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated using scaled quantum mechanical (SQM) method.

  18. Synthese and characterization of boronic acid functionalized macroporous uniform poly(4-chloromethylstyrene-co-divinylbenzene) particles and its use in the isolation of antioxidant compounds from plant extracts.

    PubMed

    Cetinkaya, Onur; Duru, Mehmet Emin; Ciçek, Hüseyin

    2012-11-15

    Aminophenyl boronic acid (APBA) carrying uniform-macroporous poly(chloromethylstyrene-co-divinylbenzene), poly(CMS-co-DVB) particles were synthesized for selective separation of cis-diol-containing flavonoids from plant extracts. For this purpose, 2.5 μm polystyrene seed particles were first swelled by a mixture of dibutyl phthalate (DBP), toluene and dodecanol, then by a monomer mixture including CMS and DVB. The repolymerization of the monomer phase in the swollen seed particles provided macroporous and uniform particles, approximately 7 μm in size. Chlorine atoms on the surface of these particles were derivatized with APBA to gain affinity properties for flavonoids containing vicinal hydroxyl groups. Model adsorption studies showed that these particles selectively adsorbed quercetin and rutin containing cis-diol groups, but did not adsorb apigenin similar to quercetin and not carrying cis-diol groups. These particles were also tested in adsorption/desorption studies for ethanol and ethyl acetate extracts of the Hypericum perforatum (HP) stems to obtain high antioxidant mixtures. With ethanol extract, the antioxidant activity of the desorption solution was a bit higher than that of the post-adsorption solutions. However, the DPPH radical scavenging activity of the desorption solution decreased with respect to the original extract and post-adsorption solutions. A similar result was obtained for the antioxidant activity of the desorption solution using ethyl acetate extract. An interesting result was obtained that DPPH radical scavenging activity of the post-adsorption solution was higher than that of the original ethyl acetate extract and desorption solutions. These results were attributed to selective adsorption of antioxidant characterized cis-diol-containing apolar molecules much more rather than that radical scavenger characterized polar molecules.

  19. The properties of the Lewis acid-base complexes of boron trifluoride with some carbon dioxide analogues. An ab initio study

    NASA Astrophysics Data System (ADS)

    Ford, Thomas A.

    2017-07-01

    The properties of nine binary Lewis acid-base complexes, formed between boron trifluoride, on the one hand, and the carbon dioxide analogues XCY (X, Y = O, S, Se) on the other, have been investigated by means of ab initio calculations. The properties of most interest are the structures, the interaction energies, the vibrational spectra and the natural orbital population changes. The structures of the complexes bound through either a sulphur or a selenium atom are remarkably similar, and feature a FB … XC fragment in a trans arrangement, with FB … X and B … XC angles close to 90°. The adducts bound through oxygen have quite different structures, with a B … OC angle close to 150° in the case of BF3·OCO and with linear B … OCS and B … OCSe moieties in the other two cases. The binding energies of all nine complexes span a very narrow range, and are all less than 10 kJ mol-1. The changes of the intramolecular BF, XC and CY bond lengths are small, but they vary in a systematic way with the strength of interaction. The wavenumber shifts of the modes of the BF3 and XCY fragments are also fairly insignificant, except for the symmetric bending mode of the BF3 molecule, where the shifts are found to be in the range from -20 to -40 cm-1. The similarities and differences in the properties of the three families of adducts have been rationalized by reference to the redistribution of the natural orbital populations resulting from complex formation.

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

    PubMed

    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.

  1. In vitro percutaneous absorption of boron as boric acid, borax, and disodium octaborate tetrahydrate in human skin: a summary.

    PubMed

    Wester, R C; Hartway, T; Maibach, H I; Schell, M J; Northington, D J; Culver, B D; Strong, P L

    1998-01-01

    Literature from the first half of this century reports concern for toxicity from topical use of boric acid, but assessment of percutaneous absorption has been impaired by lack of analytical sensitivity. Analytical methods in this study included inductively coupled plasma-mass spectrometry which now allows quantitation of percutaneous absorption of 10B in 10B-enriched boric acid, borax and disodium octaborate tetrahydrate (DOT) in biological matrices. In vitro human skin percent doses of boric acid absorbed were 1.2 for a 0.05% solution, 0.28 for a 0.5% solution, and 0.70 for a 5.0% solution. These absorption amounts translated into flux values of, respectively, 0.25, 0.58, and 14.58 microg/cm2/h, and permeability constants (Kp) of 5.0 x 10(-4), 1.2 x 10(-4), and 2.9 x 10(-4) cm/h for the 0.05%, 0.5%, and 5.0% solutions. The above in vitro doses were at infinite, 1000 microL/cm2 volume. At 2 microL/cm2 (the in vivo dosing volume), flux decreased some 200-fold to 0.07 microg/cm2/h and Kp of 1.4 x 10(-6) cm/h, while percent dose absorbed was 1.75%. Borax dosed at 5.0%/1000 microL/cm2 had 0.41 percent dose absorbed, flux at 8.5 microg/cm2/h, and Kp was 1.7 x 10(-4) cm/h. Disodium octaborate tetrahydrate (DOT) dosed at 10%/1000 microL/cm2 was 0.19 percent dose absorbed, flux at 7.9 microg/cm2/h, and Kp was 0.8 x 10(-4) cm/h. These in vitro results from infinite doses (1000 microL/cm2) were a 1000-fold greater than those obtained in the companion in vivo study. The results from the finite (2 microL/cm2) dosing were closer (10-fold difference) to the in vivo results. General application of infinite dose percutaneous absorption values for risk assessment is questioned by these results.

  2. A simple ratiometric fluorescent sensor for fructose based on complexation of 10-hydroxybenzo[h]quinoline with boronic acid

    NASA Astrophysics Data System (ADS)

    Li, Huihui; Yang, Cailing; Zhu, Xinyue; Zhang, Haixia

    2017-06-01

    A simple ratiometric fluorescent sensor for fructose was presented. It consisted of 10-hydroxybenzo[h]quinoline (HBQ) which showed emission at 572 nm and 3-pyridylboronic acid (PDBA) whose complex with HBQ gave emission at 500 nm. The reaction of fructose with PDBA inhibited the complexation of HBQ with PDBA, resulting in the change of dual-emission intensity ratio. The sensor well quantified fructose in the range of 0.015-2.5 mM with detection limit of 0.005 mM. Besides, this sensor exhibited excellent selectivity and was successfully applied to fructose detection in food. This work provides a simple ratiometric sensing platform for sensitive and selective detection of fructose.

  3. Fabrication of boron articles

    DOEpatents

    Benton, Samuel T.

    1976-01-01

    This invention is directed to the fabrication of boron articles by a powder metallurgical method wherein the articles are of a density close to the theoretical density of boron and are essentially crackfree. The method comprises the steps of admixing 1 to 10 weight percent carbon powder with amorphous boron powder, cold pressing the mixture and then hot pressing the cold pressed compact into the desired article. The addition of the carbon to the mixture provides a pressing aid for inhibiting the cracking of the hot pressed article and is of a concentration less than that which would cause the articles to possess significant concentrations of boron carbide.

  4. Selective recognition of protein tetraserine motifs with a cell-permeable, pro-fluorescent bis-boronic acid

    PubMed Central

    Halo, Tiffany L.; Appelbaum, Jacob; Hobert, Elissa M.; Balkin, Daniel M.; Schepartz, Alanna

    2009-01-01

    There is considerable interest in novel cell imaging tools that avoid the use of fluorescent proteins. One widely used class of such reagents are “pro-fluorescent” biarsenical dyes such as FlAsH, ReAsH, CrAsH, and Cy3As. Despite their utility, biarsenicals are plagued by high background labeling and cytotoxicity, and are challenging to apply in oxidizing cellular locale. Here we demonstrate that [(3-oxospiro[isobenzofuran-1(3H),9′-[9H]xanthene]-3′,6′-diyl)bis(iminomethylene-2,1-phenylene)]bis-(9CI), a rhodamine-derived bisboronic acid (RhoBo) described initially as a monosaccharide sensor, functions as a cell-permeable, turn-on fluorescent sensor for a tetraserine-motifs in recombinant proteins. RhoBo binds peptides or proteins containing Ser-Ser-Pro-Gly-Ser-Ser with affinities in the nanomolar concentration range, and prefers this sequence to simple monosaccharides by >10,000-fold. RhoBo fails to form fluorescent complexes with constituents of the mammalian cell surface, as judged by epifluorescent, confocal, and TIRF microscopy, but fluoresces brightly within the Ser-Ser-Pro-Gly-Ser-Ser-rich cell interior. These results suggest that current efforts to identify optimal serine-rich sequences for RhoBo will allow it to function effectively as a selective small-molecule label for appropriately tagged proteins either upon or within living cells. PMID:19105691

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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

  7. Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer† †Electronic supplementary information (ESI) available: Experimental procedures, assay details and spectra, characterization data for all compounds. See DOI: 10.1039/c6sc04014d Click here for additional data file.

    PubMed Central

    Molloy, John J.; Clohessy, Thomas A.; Irving, Craig; Anderson, Niall A.; Lloyd-Jones, Guy C.

    2017-01-01

    We report the direct chemoselective Brown-type oxidation of aryl organoboron systems containing two oxidizable boron groups. Basic biphasic reaction conditions enable selective formation and phase transfer of a boronic acid trihydroxyboronate in the presence of boronic acid pinacol (BPin) esters, while avoiding speciation equilibria. Spectroscopic investigations validate a base-promoted phase-selective discrimination of organoboron species. This phenomenon is general across a broad range of organoboron compounds and can also be used to invert conventional protecting group strategies, enabling chemoselective oxidation of BMIDA species over normally more reactive BPin substrates. We also demonstrate the selective oxidation of diboronic acid systems with chemoselectivity predictable a priori. The utility of this method is exemplified through the development of a chemoselective oxidative nucleophile coupling. PMID:28572912

  8. Dative Bonding between Group 13 Elements Using a Boron-Centered Lewis Base.

    PubMed

    Braunschweig, Holger; Dewhurst, Rian D; Pentecost, Leanne; Radacki, Krzysztof; Vargas, Alfredo; Ye, Qing

    2016-01-04

    An electron-rich monovalent boron compound is used as a Lewis base to prepare adducts with Group 13 Lewis acids using both its boron and nitrogen sites. The hard Lewis acid AlCl3 binds through a nitrogen atom of the Lewis base, while softer Lewis acids GaX3 (Cl, Br, I) bind at the boron atom. The latter are the first noncluster Lewis adducts between a boron-centered Lewis base and a main-group Lewis acid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The structure of boron in boron fibres

    NASA Technical Reports Server (NTRS)

    Bhardwaj, J.; Krawitz, A. D.

    1983-01-01

    The structure of noncrystalline, chemically vapour-deposited boron fibres was investigated by computer modelling the experimentally obtained X-ray diffraction patterns. The diffraction patterns from the models were computed using the Debye scattering equation. The modelling was done utilizing the minimum nearest-neighbour distance, the density of the model, and the broadening and relative intensity of the various peaks as boundary conditions. The results suggest that the fibres consist of a continuous network of randomly oriented regions of local atomic order, about 2 nm in diameter, containing boron atoms arranged in icosahedra. Approximately half of these regions have a tetragonal structure and the remaining half a distorted rhombohedral structure. The model also indicates the presence of many partial icosahedra and loose atoms not associated with any icosahedra. The partial icosahedra and loose atoms indicated in the present model are in agreement with the relaxing sub-units which have been suggested to explain the anelastic behavior of fibre boron and the loosely bound boron atoms which have been postulated to explain the strengthening mechanism in boron fibres during thermal treatment.

  10. Effect of combination therapy of fatty acids, calcium, vitamin D and boron with regular physical activity on cardiovascular risk factors in rat.

    PubMed

    Naghii, M R; Darvishi, P; Ebrahimpour, Y; Ghanizadeh, G; Mofid, M; Hedayati, M; Asgari, A R

    2012-01-01

    The effect of consumption of fatty acids and selected nutrients, along with regular physical activity, on cardiovascular risk factors in rats was investigated.Male rats were divided into the seven groups: Group 1: regular food and drinking water, Group 2: same as Group. 1 + physical activity (whole body vibration; WBV), Group 3: same as Group. 2 + calcium, vitamin D, boron, Group 4: same as Group. 3 + canola oil, Group 5: same as Group. 3 + sunflower oil, Group 6: same as Group. 3 + mix of sunflower oil and canola oil, Group 7: same as Group. 3 + coconut oil. Rats were treated for 8 weeks, and analysis of the frozen plasmas was performed. A- Analysis between the treatment groups and control revealed that vibration training in Group 2 increased body weight (P = 0.04), plasma creatin kinase (CK), (P = 0.02), and estradiol (E2), (P = 0.03). Rats in Group 5 consumed less food and plasma levels of cholesterol and LDL-cholesterol (LDL-C) increased significantly (P = 0.02) in Group 6 and in Group 7 (p<0.05). B- Analysis of data among Group 4 - 7 (the oil consuming groups) and Group 3 revealed significant differences in cholesterol (Chol), LDL-C, HDL-cholesterol (HDL-C), triglycerides (TG), C- reactive protein (hs-CRP), estradiol (E2), atherogenic index (AI), and risk factor (RF), (p<0.05). In addition, plasma levels of testosterone (T) and free testosterone (FT) in Group 7 had a remarkable but non-significant increase. As a result of vibration training, a similar trend was observed for vitamin D in Group 2-7. The findings show that WBV is effective in improving health status by influencing cardiovascular disease (CVD) risk factors. Moreover, canola oil and sunflower oil, separately, showed beneficial impacts on CVD risk factors; whereas their combination had negative impacts on lipid profile. Coconut oil revealed to be efficient to provide health benefits in terms of CVD treatments.

  11. Boronic Acid Transition State Inhibitors Active against KPC and Other Class A β-Lactamases: Structure-Activity Relationships as a Guide to Inhibitor Design

    PubMed Central

    Rojas, Laura J.; Taracila, Magdalena A.; Papp-Wallace, Krisztina M.; Bethel, Christopher R.; Caselli, Emilia; Romagnoli, Chiara; Winkler, Marisa L.; Spellberg, Brad; Prati, Fabio

    2016-01-01

    Boronic acid transition state inhibitors (BATSIs) are competitive, reversible β-lactamase inhibitors (BLIs). In this study, a series of BATSIs with selectively modified regions (R1, R2, and amide group) were strategically designed and tested against representative class A β-lactamases of Klebsiella pneumoniae, KPC-2 and SHV-1. Firstly, the R1 group of compounds 1a to 1c and 2a to 2e mimicked the side chain of cephalothin, whereas for compounds 3a to 3c, 4a, and 4b, the thiophene ring was replaced by a phenyl, typical of benzylpenicillin. Secondly, variations in the R2 groups which included substituted aryl side chains (compounds 1a, 1b, 1c, 3a, 3b, and 3c) and triazole groups (compounds 2a to 2e) were chosen to mimic the thiazolidine and dihydrothiazine ring of penicillins and cephalosporins, respectively. Thirdly, the amide backbone of the BATSI, which corresponds to the amide at C-6 or C-7 of β-lactams, was also changed to the following bioisosteric groups: urea (compound 3b), thiourea (compound 3c), and sulfonamide (compounds 4a and 4b). Among the compounds that inhibited KPC-2 and SHV-1 β-lactamases, nine possessed 50% inhibitory concentrations (IC50s) of ≤600 nM. The most active compounds contained the thiopheneacetyl group at R1 and for the chiral BATSIs, a carboxy- or hydroxy-substituted aryl group at R2. The most active sulfonamido derivative, compound 4b, lacked an R2 group. Compound 2b (S02030) was the most active, with acylation rates (k2/K) of 1.2 ± 0.2 × 104 M−1 s−1 for KPC-2 and 4.7 ± 0.6 × 103 M−1 s−1 for SHV-1, and demonstrated antimicrobial activity against Escherichia coli DH10B carrying blaSHV variants and blaKPC-2 or blaKPC-3 and against clinical strains of Klebsiella pneumoniae and E. coli producing different class A β-lactamase genes. At most, MICs decreased from 16 to 0.5 mg/liter. PMID:26729496

  12. Boronic Acid Transition State Inhibitors Active against KPC and Other Class A β-Lactamases: Structure-Activity Relationships as a Guide to Inhibitor Design.

    PubMed

    Rojas, Laura J; Taracila, Magdalena A; Papp-Wallace, Krisztina M; Bethel, Christopher R; Caselli, Emilia; Romagnoli, Chiara; Winkler, Marisa L; Spellberg, Brad; Prati, Fabio; Bonomo, Robert A

    2016-01-04

    Boronic acid transition state inhibitors (BATSIs) are competitive, reversible β-lactamase inhibitors (BLIs). In this study, a series of BATSIs with selectively modified regions (R1, R2, and amide group) were strategically designed and tested against representative class A β-lactamases of Klebsiella pneumoniae, KPC-2 and SHV-1. Firstly, the R1 group of compounds 1a to 1c and 2a to 2e mimicked the side chain of cephalothin, whereas for compounds 3a to 3c, 4a, and 4b, the thiophene ring was replaced by a phenyl, typical of benzylpenicillin. Secondly, variations in the R2 groups which included substituted aryl side chains (compounds 1a, 1b, 1c, 3a, 3b, and 3c) and triazole groups (compounds 2a to 2e) were chosen to mimic the thiazolidine and dihydrothiazine ring of penicillins and cephalosporins, respectively. Thirdly, the amide backbone of the BATSI, which corresponds to the amide at C-6 or C-7 of β-lactams, was also changed to the following bioisosteric groups: urea (compound 3b), thiourea (compound 3c), and sulfonamide (compounds 4a and 4b). Among the compounds that inhibited KPC-2 and SHV-1 β-lactamases, nine possessed 50% inhibitory concentrations (IC50s) of ≤ 600 nM. The most active compounds contained the thiopheneacetyl group at R1 and for the chiral BATSIs, a carboxy- or hydroxy-substituted aryl group at R2. The most active sulfonamido derivative, compound 4b, lacked an R2 group. Compound 2b (S02030) was the most active, with acylation rates (k2/K) of 1.2 ± 0.2 × 10(4) M(-1) s(-1) for KPC-2 and 4.7 ± 0.6 × 10(3) M(-1) s(-1) for SHV-1, and demonstrated antimicrobial activity against Escherichia coli DH10B carrying blaSHV variants and blaKPC-2 or blaKPC-3 and against clinical strains of Klebsiella pneumoniae and E. coli producing different class A β-lactamase genes. At most, MICs decreased from 16 to 0.5 mg/liter.

  13. Magnetron sputtered boron films

    DOEpatents

    Makowiecki, D.M.; Jankowski, A.F.

    1998-06-16

    A method is described for the production of thin boron and titanium/boron films by magnetron sputter deposition. The amorphous boron films contain no morphological growth features, unlike those found when thin films are prepared by various physical vapor deposition processes. Magnetron sputter deposition method requires the use of a high density crystalline boron sputter target which is prepared by hot isostatic pressing. Thin boron films prepared by this method are useful for producing hardened surfaces, surfacing machine tools, etc. and for ultra-thin band pass filters as well as the low Z element in low Z/high Z optical components, such as mirrors which enhance reflectivity from grazing to normal incidence. 8 figs.

  14. Magnetron sputtered boron films

    DOEpatents

    Makowiecki, Daniel M.; Jankowski, Alan F.

    1998-01-01

    A method is described for the production of thin boron and titanium/boron films by magnetron sputter deposition. The amorphous boron films contain no morphological growth features, unlike those found when thin films are prepared by various physical vapor deposition processes. Magnetron sputter deposition method requires the use of a high density crystalline boron sputter target which is prepared by hot isostatic pressing. Thin boron films prepared by this method are useful for producing hardened surfaces, surfacing machine tools, etc. and for ultra-thin band pass filters as well as the low Z element in low Z/high Z optical components, such as mirrors which enhance reflectivity from grazing to normal incidence.

  15. Preparation of boron nitride fiber by organic precursor method

    NASA Astrophysics Data System (ADS)

    Zhou, Yingying; Sun, Runjun; Zhang, Zhaohuan; Fan, Wei; Zhou, Dan; Sheng, Cuihong

    In this paper, boron nitride polymer precursor was made by boric acid, melamine, twelve sodium alkyl sulfate as raw materials and pure water as medium which is heated to 70 °C. Boron nitride precursor polymer was soluble in formic acid solution. The boron nitride precursor can be electrostatically spun at the voltage in 23 kV and the distance between the positive and negative poles is 15 cm. The formed fiber is very uniform. The properties of the precursors were analyzed through electron microscope, infrared spectrum, X-ray and ultraviolet spectrum. The aim of the job is to got the precursor of BN and spun it.

  16. Microwave sintering of boron carbide

    DOEpatents

    Blake, R.D.; Katz, J.D.; Petrovic, J.J.; Sheinberg, H.

    1988-06-10

    A method for forming boron carbide into a particular shape and densifying the green boron carbide shape. Boron carbide in powder form is pressed into a green shape and then sintered, using a microwave oven, to obtain a dense boron carbide body. Densities of greater than 95% of theoretical density have been obtained. 1 tab.

  17. Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition.

    PubMed

    Baslé, Olivier; Porcel, Susana; Ladeira, Sonia; Bouhadir, Ghenwa; Bourissou, Didier

    2012-05-11

    Phosphine-boronates R(2)P(o-C(6)H(4))B(OR')(2) have been evaluated as bifunctional organocatalysts for the Michael addition of malonate pronucleophiles to methylvinylketone. The presence of the Lewis acidic boron center adjacent to phosphorus significantly improves catalytic performance. Isolation and complete characterization of a key intermediate, namely a β-phosphonium enolate, substantiate the role of the Lewis acidic moiety in the catalytic process.

  18. Boron nitride fibers from polymer precursors

    SciTech Connect

    Wade, B.E.

    1992-12-31

    Conversion of polymer precursors to high performance boron nitride fibers as explored through a fundamental study of the mutually dependent chemical, morphological, and processing requirements in precursor polymer synthesis, formation of continuous precursor fibers, and finally thermochemical conversion to oriented boron nitride fibers. Polyborate and polyborazylene precursors were investigated. method of incorporating polyborazine in polyborate were also explored in order to stabilize the shape of polyborate fibers and to help initiate an orientable boron nitride structure. Polyborazylene, a polyborazine of fused borazine polycyclic structures was chosen for study as a precursor for boron nitride fibers because of the closeness of its structure to that of the desired turbostratic boron nitride. Both poly(ethylene oxide) and poly(methyl methacrylate) were found to be compatible with the monomer, borazine, and polyborazylenesolutions with monoglyme. They could be used to build the viscosity of solutions. However, fibers that were hand-drawn from these solutions were very sticky and quickly hydrolyzed in room atmosphere. Conversion of polyborazylene to oriented boron nitride fibers was not realized. Processable polyborates were produced by polycondensation of trimethoxyboroxine and boric acid and also by disproportionation or trimethyoxyboraxine. It was shown that the rheological characteristics of the polyborate formed could be controlled by an appropriate combination of the conversion of the monomer to polymer and the addition of a linear organic polymer as a rheological aid. Poly(methyl methacrylate) was found to be a suitable rheological aid, with a decomposition temperature that is high enough to facilitate its incorporation in the polymerizing system and low energy to be fugitive during thermochemical conversion of the polyborate to boron nitride.

  19. Characterization of a Gene Encoding Clathrin Heavy Chain in Maize Up-Regulated by Salicylic Acid, Abscisic Acid and High Boron Supply

    PubMed Central

    Zeng, Mu-Heng; Liu, Sheng-Hong; Yang, Miao-Xian; Zhang, Ya-Jun; Liang, Jia-Yong; Wan, Xiao-Rong; Liang, Hong

    2013-01-01

    Clathrin, a three-legged triskelion composed of three clathrin heavy chains (CHCs) and three light chains (CLCs), plays a critical role in clathrin-mediated endocytosis (CME) in eukaryotic cells. In this study, the genes ZmCHC1 and ZmCHC2 encoding clathrin heavy chain in maize were cloned and characterized for the first time in monocots. ZmCHC1 encodes a 1693-amino acid-protein including 29 exons and 28 introns, and ZmCHC2 encodes a 1746-amino acid-protein including 28 exons and 27 introns. The high similarities of gene structure, protein sequences and 3D models among ZmCHC1, and Arabidopsis AtCHC1 and AtCHC2 suggest their similar functions in CME. ZmCHC1 gene is predominantly expressed in maize roots instead of ubiquitous expression of ZmCHC2. Consistent with a typical predicted salicylic acid (SA)-responsive element and four predicted ABA-responsive elements (ABREs) in the promoter sequence of ZmCHC1, the expression of ZmCHC1 instead of ZmCHC2 in maize roots is significantly up-regulated by SA or ABA, suggesting that ZmCHC1 gene may be involved in the SA signaling pathway in maize defense responses. The expressions of ZmCHC1 and ZmCHC2 genes in maize are down-regulated by azide or cold treatment, further revealing the energy requirement of CME and suggesting that CME in plants is sensitive to low temperatures. PMID:23880865

  20. An alternative approach to aldol reactions: gold-catalyzed formation of boron enolates from alkynes.

    PubMed

    Körner, Cindy; Starkov, Pavel; Sheppard, Tom D

    2010-05-05

    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh(3)AuNTf(2) at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or intramolecular Chan-Lam coupling, respectively. A combined gold/boronic acid catalyzed aldol condensation reaction of an alkynyl aldehyde was also successfully achieved.

  1. Advancements in Tumor Targeting Strategies for Boron Neutron Capture Therapy.

    PubMed

    Luderer, Micah John; de la Puente, Pilar; Azab, Abdel Kareem

    2015-09-01

    Boron neutron capture therapy (BNCT) is a promising cancer therapy modality that utilizes the nuclear capture reaction of epithermal neutrons by boron-10 resulting in a localized nuclear fission reaction and subsequent cell death. Since cellular destruction is limited to approximately the diameter of a single cell, primarily only cells in the neutron field with significant boron accumulation will be damaged. However, the emergence of BNCT as a prominent therapy has in large part been hindered by a paucity of tumor selective boron containing agents. While L-boronophenylalanine and sodium borocaptate are the most commonly investigated clinical agents, new agents are desperately needed due to their suboptimal tumor selectivity. This review will highlight the various strategies to improve tumor boron delivery including: nucleoside and carbohydrate analogs, unnatural amino acids, porphyrins, antibody-dendrimer conjugates, cationic polymers, cell-membrane penetrating peptides, liposomes and nanoparticles.

  2. A computational study of carbon dioxide adsorption on solid boron.

    PubMed

    Sun, Qiao; Wang, Meng; Li, Zhen; Du, Aijun; Searles, Debra J

    2014-07-07

    Capturing and sequestering carbon dioxide (CO2) can provide a route to partial mitigation of climate change associated with anthropogenic CO2 emissions. Here we report a comprehensive theoretical study of CO2 adsorption on two phases of boron, α-B12 and γ-B28. The theoretical results demonstrate that the electron deficient boron materials, such as α-B12 and γ-B28, can bond strongly with CO2 due to Lewis acid-base interactions because the electron density is higher on their surfaces. In order to evaluate the capacity of these boron materials for CO2 capture, we also performed calculations with various degrees of CO2 coverage. The computational results indicate CO2 capture on the boron phases is a kinetically and thermodynamically feasible process, and therefore from this perspective these boron materials are predicted to be good candidates for CO2 capture.

  3. Boron and the kidney.

    PubMed

    Pahl, Madeleine V; Culver, B Dwight; Vaziri, Nosratola D

    2005-10-01

    Boron, the fifth element in the periodic table, is ubiquitous in nature. It is present in food and in surface and ocean waters, and is frequently used in industrial, cosmetic, and medical settings. Exposure to boron and related compounds has been recently implicated as a potential cause of chronic kidney disease in Southeast Asia. This observation prompted the present review of the published data on the effects of acute and chronic exposure to boron on renal function and structure in human beings and in experimental animals.

  4. Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)2 (R = H, H3C, H2N, HO, and F): A Computational Investigation

    PubMed Central

    Bhat, Krishna L.; Markham, George D.; Larkin, Joseph D.; Bock, Charles W.

    2011-01-01

    Boroxines are the 6-membered cyclotrimeric dehydration products of organoboronic acids: 3 R– B(OH)2 → R3B3O3 + 3 H2O, and in recent years have emerged as a useful class of organoboron molecules with applications in organic synthesis both as reagents and catalysts, as structural components in boronic acid derived pharmaceutical agents, as anion acceptors and electrolyte additives for battery materials [AL Korich and PM Iovine, Dalton Trans. 39 (2010) 1423–1431]. Second-order Møller-Plesset perturbation theory, in conjunction with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ basis sets, was used to investigate the structures and relative energies of the endo-exo, anti, and syn conformers of the aliphatic boronic acids R–B(OH)2 (R = H, H3C, H2N, HO, and F), as well as the thermodynamics of their boroxine formation; single-point calculations at the MP2/aug-cc-pVQZ, MP2/aug-cc-pV5Z, and CCSD(T)/aug-cc-pVTZ level using the MP2/aug-cc-pVTZ optimized geometries were also performed in selected cases. The endo-exo conformer was generally lowest in energy in vacuo, as well as in PCM and CPCM models of aqueous and carbon tetrachloride media. The values of ΔH2980 for boroxine formation via dehydration from the endo-exo conformers of these aliphatic boronic acids ranged from −2.9 for (H2N)3B3O3 to +12.2 kcal/mol for H3B3O3 at the MP2/aug-cc-pVTZ level in vacuo; for H3B3O3 the corresponding values in PCM:UFF implicit carbon tetrachloride and aqueous media were +11.2 and +9.8 kcal/mol, respectively. Based on our calculations, we recommend that ΔHf(298 K) for boroxine listed in the JANAF compilation needs to be revised from −290.0 kcal/mol to approximately −277.0 kcal/mol. PMID:21650154

  5. Boron as a tracer of aerosol from combustion of coal

    NASA Astrophysics Data System (ADS)

    Fogg, Thomas R.; Rahn, Kenneth A.

    1984-09-01

    Atmospheric boron was found to be predominantly gaseous in ambient samples and in stacks of coal-fired power plants. Typical gas/particulate ratios ranged from 20 to more than 100, with stack ratios above 100 and ambient ratios generally below 100. In the stacks, B/SO2 ratios were lower than expected from bulk U.S. coals, consistent with volatilization of 20-80 percent of the boron during combustion. Midwestern ambient B/SO2 ratios were at or above stack values, with the lowest ratios associated with highest concentrations. SO2 was always more variable than gaseous boron. These observations are consistent with coal combustion as the major source of atmospheric boron (and SO2) in the Midwest. In northern Vermont, concentrations of gaseous boron and SO2 were several times lower than in the Midwest, but the B/SO2 ratio was several times higher. Both species passed through quasiweekly in-phase cycles of concentration with the relative amplitudes being greater for SO2 than for gaseous boron. All major pulses of boron and SO2 came from the direction of the Midwest, on the backsides of high-pressure areas. Since the ocean is also a source of gaseous boron, its anthropogenic tracer potential for acid deposition studies will be most useful in the interior of continents.

  6. Direct current sputtering of boron from boron/coron mixtures

    DOEpatents

    Timberlake, John R.; Manos, Dennis; Nartowitz, Ed

    1994-01-01

    A method for coating a substrate with boron by sputtering includes lowering the electrical resistance of a boron-containing rod to allow electrical conduction in the rod; placing the boron-containing rod inside a vacuum chamber containing substrate material to be coated; applying an electrical potential between the boron target material and the vacuum chamber; countering a current avalanche that commences when the conduction heating rate exceeds the cooling rate, and until a steady equilibrium heating current is reached; and, coating the substrate material with boron by sputtering from the boron-containing rod.

  7. Nanoscaled boron-containing delivery systems and therapeutic agents for cancer treatment.

    PubMed

    Wang, Jing; Wu, Wei; Jiang, Xiqun

    2015-01-01

    Significant efforts have recently been made to develop nanoscaled boron-containing delivery systems for improving drug delivery in cancer therapy. On one hand, borate ester chemistry has shown importance in ligand-mediated tumor targeting owing to the recognition ability of boronic acid to polyol residues in cell membranes. In particular, the phenylboronic acid-functionalized nanocarriers for specific targeting to sialic acid groups which are overexpressed on tumor cells have made great achievements. On the other hand, nanoscaled boron neutron capture therapy agents show growing potential in efficiently transporting boron to tumor. The current review outlines the recent developments in the application of borate ester chemistry in tumor targeting by nanoparticles, then summarizes recent work on the development of boron-based nanomaterials as boron neutron capture therapy agents.

  8. Boron nitride composites

    DOEpatents

    Kuntz, Joshua D.; Ellsworth, German F.; Swenson, Fritz J.; Allen, Patrick G.

    2016-02-16

    According to one embodiment, a composite product includes hexagonal boron nitride (hBN), and a plurality of cubic boron nitride (cBN) particles, wherein the plurality of cBN particles are dispersed in a matrix of the hBN. According to another embodiment, a composite product includes a plurality of cBN particles, and one or more borate-containing binders.

  9. Zeolitic Boron Imidazolate Frameworks**

    PubMed Central

    Zhang, Jian; Wu, Tao; Zhou, Cong; Chen, Shumei; Feng, Pingyun; Bu, Xianhui

    2009-01-01

    From porous AlPO4 to porous BIFs Reported here are a family of crystalline materials based on boron imidazolate frameworks (BIFs). It is demonstrated that the synthetic method, which is based on the crosslinking of various pre-synthesized boron imidazolates by monovalent cations (Li+ and Cu+), is capable of generating a large variety of open frameworks ranging from the 4-connected zeolitic sodalite type to the 3-connected chiral (10,3)-a type. PMID:19241428

  10. Fluorescent chirality recognition by simple boronate ensembles with aggregation-induced emission capability.

    PubMed

    Kawai, Meiko; Hoshi, Ayaka; Nishiyabu, Ryuhei; Kubo, Yuji

    2017-09-12

    Chiral ensembles were spontaneously formed in solution through boronate esterification of structurally defined di(boronic acid)-appended tetraphenylethylene (DB-TPE) and commercially available l- or d-tartaric acid, showing enantioselective aggregation behavior for chiral diamines as well as cinchona alkaloids enabling the fluorescent recognition of their chirality.

  11. An introduction to boron: history, sources, uses, and chemistry.

    PubMed Central

    Woods, W G

    1994-01-01

    Following a brief overview of the terrestrial distribution of boron in rocks, soil, and water, the history of the discovery, early utilization, and geologic origin of borate minerals is summarized. Modern uses of borate-mineral concentrates, borax, boric acid, and other refined products include glass, fiberglass, washing products, alloys and metals, fertilizers, wood treatments, insecticides, and microbiocides. The chemistry of boron is reviewed from the point of view of its possible health effects. It is concluded that boron probably is complexed with hydroxylated species in biologic systems, and that inhibition and stimulation of enzyme and coenzymes are pivotal in its mode of action. Images Figure 1. PMID:7889881

  12. An introduction to boron: history, sources, uses, and chemistry.

    PubMed

    Woods, W G

    1994-11-01

    Following a brief overview of the terrestrial distribution of boron in rocks, soil, and water, the history of the discovery, early utilization, and geologic origin of borate minerals is summarized. Modern uses of borate-mineral concentrates, borax, boric acid, and other refined products include glass, fiberglass, washing products, alloys and metals, fertilizers, wood treatments, insecticides, and microbiocides. The chemistry of boron is reviewed from the point of view of its possible health effects. It is concluded that boron probably is complexed with hydroxylated species in biologic systems, and that inhibition and stimulation of enzyme and coenzymes are pivotal in its mode of action.

  13. Synthesis of aluminium nitride/boron nitride composite materials

    SciTech Connect

    Xiao, T.D. . Polymer Science Program and Dept. of Chemistry); Gonsalves, K.E. . Polymer Science Program and Dept. of Chemistry Univ. of Connecticut, Storrs, CT . Dept. of Chemistry); Strutt, P.R. . Dept. of Metallurgy)

    1993-04-01

    Aluminum nitride/boron nitride composite was synthesized by using boric acid, urea, and aluminum chloride (or aluminum lactate) as the starting compounds. The starting materials were dissolved in water and mixed homogeneously. Ammonolysis of this aqueous solution resulted in the formation of a precomposite gel, which converted into the aluminum nitride/boron nitride composite on further heat treatment. Characterization of both the precomposite and the composite powders included powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. Analysis of the composite revealed that the aluminum nitride phase had a hexagonal structure, and the boron nitride phase a turbostratic structure.

  14. Ambiphilic boron in 1,4,2,5-diazadiborinine

    PubMed Central

    Wang, Baolin; Li, Yongxin; Ganguly, Rakesh; Hirao, Hajime; Kinjo, Rei

    2016-01-01

    Boranes have long been known as the archetypal Lewis acids owing to an empty p-orbital on the boron centre. Meanwhile, Lewis basic tricoordinate boranes have been developed in recent years. Here we report the synthesis of an annulated 1,4,2,5-diazadiborinine derivative featuring boron atoms that exhibit both Lewis acidic and basic properties. Experimental and computational studies confirmed that two boron atoms in this molecule are spectroscopically equivalent. Nevertheless, this molecule cleaves C–O, B–H, Si–H and P–H bonds heterolytically, and readily undergoes [4+2] cycloaddition reaction with non-activated unsaturated bonds such as C=O, C=C, C≡C and C≡N bonds. The result, thus, indicates that the indistinguishable boron atoms in 1,4,2,5-diazadiborinine act as both nucleophilic and electrophilic centres, demonstrating ambiphilic nature. PMID:27279265

  15. Intermolecular Redox-Neutral Amine C-H Functionalization Induced by the Strong Boron Lewis Acid B(C6 F5 )3 in the Frustrated Lewis Pair Regime.

    PubMed

    Chen, Guo-Qiang; Kehr, Gerald; Daniliuc, Constantin G; Bursch, Markus; Grimme, Stefan; Erker, Gerhard

    2017-02-06

    N,N-Dimethylmesitylamine undergoes an intermolecular redox-neutral C-H activation/C-C coupling process upon treatment with dimethyl acetylenedicarboxylate and the strong boron Lewis acid B(C6 F5 )3 . Similarly, N,N-dimethylmesitylamine reacts with two molar equivalents of ethyl acrylate to give the respective unsaturated coupling product with H2 transfer to the acrylic ester to form the ethyl propionate/B(C6 F5 )3 adduct. N,N-Dimethylmesitylamine also undergoes a C-H activation at the benzylic ortho sp(3) -carbon atom with dihydrogen formation upon treatment with Piers' borane [HB(C6 F5 )2 ]. The last two reactions of N,N-dimethylmesitylamine were analyzed by DFT calculations.

  16. Process for making boron nitride using sodium cyanide and boron

    DOEpatents

    Bamberger, Carlos E.

    1990-02-06

    This a very simple process for making boron nitride by mixing sodium cyanide and boron phosphate and heating the mixture in an inert atmosphere until a reaction takes place. The product is a white powder of boron nitride that can be used in applications that require compounds that are stable at high temperatures and that exhibit high electrical resistance.

  17. Process for making boron nitride using sodium cyanide and boron

    DOEpatents

    Bamberger, Carlos E.

    1990-01-01

    This a very simple process for making boron nitride by mixing sodium cyanide and boron phosphate and heating the mixture in an inert atmosphere until a reaction takes place. The product is a white powder of boron nitride that can be used in applications that require compounds that are stable at high temperatures and that exhibit high electrical resistance.

  18. Boronated liposome development and evaluation

    SciTech Connect

    Hawthorne, M.F.

    1995-11-01

    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.

  19. Effects of hypochlorous acid exposure on the rejection of salt, polyethylene glycols, boron and arsenic(V) by nanofiltration and reverse osmosis membranes.

    PubMed

    Do, Van Thanh; Tang, Chuyang Y; Reinhard, Martin; Leckie, James O

    2012-10-15

    The separation layer of polyamide-based (PA) thin film composite (TFC) membranes can be modified by active chlorine species. The PA-TFC membranes, NF90, BW30 and NF270, were exposed to different concentrations of sodium hypochlorite (NaOCl) at pH 5 for 24 h. Elemental composition obtained from X-ray Photoelectron Spectroscopy (XPS) showed that the chlorine content in the PA layer increased with the chlorine concentrations. Treatment of membranes with 10 ppm Cl increased the membrane hydrophilicity. By contrast, when treated with 1000 ppm Cl or more, the membranes became less hydrophilic. Water permeability values for all 3 membrane types declined with increased chlorine concentrations. Filtration of polyethylene glycols (PEGs) with molecular weights of 200, 400 and 600 Daltons (Da) was performed to investigate the influence of chlorine treatment on membrane molecular weight cut off (MWCO) and rejection by size exclusion. Treatment with 10 and 100 ppm Cl lowered the MWCO while treatment with higher concentrations increased the MWCO. All chlorinated membranes experienced higher NaCl rejection compared to virgin ones. The performance of NF90 was tested with respect to the rejection of inorganic contaminants including boron (H(3)BO(3)) and arsenic (H(2)AsO(4)(-)). The boron rejection results paralleled PEG rejection whereas those for arsenic followed NaCl rejection patterns. The changes in membrane performance due to chlorine treatment were explained in terms of competing mechanisms: membrane tightening, bond cleavage by N-chlorination and chlorination promoted polyamide hydrolysis.

  20. Method for separating boron isotopes

    DOEpatents

    Rockwood, Stephen D.

    1978-01-01

    A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

  1. Status of Boron Combustion Research

    DTIC Science & Technology

    1984-10-01

    layer . . . . . . . . . . . . . . . . . . . . . . . . . . 10 5 Vaporization of boron oxide drops In wet and dry .-. environments. From Turns et al . ([1...19 10 SEN photographs of boron slurry agglomerates: a. Oxide layer present: b. Oxide layer absent.From Turns et al . [7...21 -- f- 11 Ignition of boron agglomerates as a function of particle and agglomerate diameters. From Shevahuk et al . [26

  2. Mineral of the month: boron

    USGS Publications Warehouse

    Lyday, Phyllis A.

    2005-01-01

    What does boron have to do with baseball, apple pie, motherhood and Chevrolet? Boron minerals and chemicals are used in the tanning of leather baseballs and gloves; in micro-fertilizer to grow apples and in the glass and enamels of bakewares to cook apple pie; in boron detergents for soaking baby clothes and diapers; and in fiberglass parts for the Chevrolet Corvette.

  3. Risk assessment of boron in glass wool insulation.

    PubMed

    Jensen, Allan Astrup

    2009-01-01

    Glass wools are man-made vitreous fibres, which consist principally of sodium, calcium and magnesium silicates, but may contain smaller amounts of other elements, including boron. The boron contents originate from the use of borates in the glass melting process as a glass former and a flux agent. During the production and application of glass wool insulation products, workers may legally be exposed to glass fibre up to the occupational limit value, commonly of 1 fibre/cm3. However, in practice, the fibre exposure will be at least ten times lower. Boron is a non-metallic element widely distributed in nature, where it occurs as boric acid, borates and borosilicates. Humans are mainly exposed to boron via vegetarian food and drinking water, mineral supplements and various consumer products. Boron is an essential element for plant growth, but the essentiality for humans is not proven, although intakes of trace amounts of the element seem to be useful for bone health and proper brain function; higher concentrations of boron, however, may be toxic. In relation to the European Union legislation on dangerous substances, an EU Expert Group has recommended classifying boric acid and borates with risk phrases for reproductive toxicity. The aim of this paper is to assess whether the new EU hazard classification of boron compounds should imply that glass wool products used for building insulation in the future should be labelled, "may impair fertility and cause harm to the unborn child", because of the low boron content. Boron intakes are estimated in a worst-case occupational situation with human exposure to glass wool fibres at the occupational limit of 1 fibre/cm3 by calculation of the mass of the amount of fibres inhaled during an 8-h work day. Fibres are supposed to be cylinders of glass with a length of 30 microm, an average diameter of 1.5-2 microm and containing either 1.5% or 3.5% boron. As a worst-case scenario, the density of the fibres is set to 2,700 kg/m3. The

  4. Single step synthesis of nanostructured boron nitride for boron neutron capture therapy

    SciTech Connect

    Singh, Bikramjeet; Singh, Paviter; Kumar, Akshay; Kumar, Manjeet; Thakur, Anup

    2015-05-15

    Nanostructured Boron Nitride (BN) has been successfully synthesized by carbo-thermic reduction of Boric Acid (H{sub 3}BO{sub 3}). This method is a relatively low temperature synthesis route and it can be used for large scale production of nanostructured BN. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analyzer (DTA). XRD analysis confirmed the formation of single phase nanostructured Boron Nitride. SEM analysis showed that the particles are spherical in shape. DTA analysis showed that the phase is stable upto 900 °C and the material can be used for high temperature applications as well boron neutron capture therapy (BNCT)

  5. A modular synthesis of functionalised phenols enabled by controlled boron speciation.

    PubMed

    Molloy, John J; Law, Robert P; Fyfe, James W B; Seath, Ciaran P; Hirst, David J; Watson, Allan J B

    2015-03-14

    A modular synthesis of functionalised biaryl phenols from two boronic acid derivatives has been developed via one-pot Suzuki-Miyaura cross-coupling, chemoselective control of boron solution speciation to generate a reactive boronic ester in situ, and oxidation. The utility of this method has been further demonstrated by application in the synthesis of drug molecules and components of organic electronics, as well as within iterative cross-coupling.

  6. In Vivo Boron Uptake Determination for Boron Neutron Capture Synovectomy

    SciTech Connect

    Binello, Emanuela; Shortkroff, Sonya; Yanch, Jacquelyn C.

    1999-06-06

    Boron neutron capture synovectomy (BNCS) has been proposed as a new application of the boron neutron capture reaction for the treatment of rheumatoid arthritis. In BNCS, a boron compound is injected into the joint space, where it is taken up by the synovium. The joint is then irradiated with neutrons of a desired energy range, inducing the boron neutron capture reaction in boron-loaded cells. Boron uptake by the synovium is an important parameter in the assessment of the potential of BNCS and in the determination of whether to proceed to animal irradiations for the testing of therapeutic efficacy. We present results from an investigation of boron uptake in vivo by the synovium.

  7. Boron isotope exchange in a heterogeneous boron-boron fluoride system

    SciTech Connect

    Begak, O.Yu.; Fedorov, V.V.

    1988-11-01

    Studies have been made on exchange between /sup 10/B and /sup 11/B in heterogeneous systems containing finely divided amorphous boron and BF/sub 3/ gas. The kinetic and thermodynamic parameters have been examined. The self-diffusion coefficient for boron in amorphous boron has been determined at 973-1273 K.

  8. A high boronate avidity monolithic capillary for the selective enrichment of trace glycoproteins.

    PubMed

    Li, Daojin; Li, Yang; Li, Xinglin; Bie, Zijun; Pan, Xianghua; Zhang, Qian; Liu, Zhen

    2015-03-06

    Boronate affinity materials, as effective sample enrichment sorbents for glycoproteomic analysis, have attracted increasing attention in recent years. However, most of boronate affinity materials suffer from an apparent limitation, limited binding strength. As a result, extraction of glycoproteins of trace concentration is rather difficult or impossible. In this study, we present a high boronate avidity monolithic capillary. Branched polyethyleneimine (PEI) was used as a scaffold to amplify the number of boronic acid moieties. While 2,4-difluoro-3-formyl-phenylboronic acid (DFFPBA), which exhibited ultrahigh affinity toward cis-diol-containing compounds, was employed as an affinity ligand. Due to the PEI-assisted synergistic multivalent binding, the monolithic column exhibited high boronate avidity toward glycoproteins, with binding constants of 10(-6)-10(-7)M. Such binding strength was the highest among already reported boronic acid-functionalized materials that can be used for glycoproteomic analysis. Besides, the boronate avidity monolithic column exhibited one additional beneficial feature, lowered binding pH (≥6.5). These features greatly favored the selective enrichment of trace glycoproteins from real samples. The feasibility for practical applications was demonstrated with the selective enrichment of trace glycoproteins in human saliva. As compared with other boronate avidity/affinity materials, the boronate avidity monolithic capillary exhibited the best performance.

  9. Boron hydride polymer coated substrates

    DOEpatents

    Pearson, Richard K.; Bystroff, Roman I.; Miller, Dale E.

    1987-01-01

    A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

  10. Boron hydride polymer coated substrates

    DOEpatents

    Pearson, R.K.; Bystroff, R.I.; Miller, D.E.

    1986-08-27

    A method is disclosed for coating a substrate with a uniformly smooth layer of a boron hydride polymer. The method comprises providing a reaction chamber which contains the substrate and the boron hydride plasma. A boron hydride feed stock is introduced into the chamber simultaneously with the generation of a plasma discharge within the chamber. A boron hydride plasma of ions, electrons and free radicals which is generated by the plasma discharge interacts to form a uniformly smooth boron hydride polymer which is deposited on the substrate.

  11. Activation of the EIF2α/ATF4 and ATF6 Pathways in DU-145 Cells by Boric Acid at the Concentration Reported in Men at the US Mean Boron Intake.

    PubMed

    Kobylewski, Sarah E; Henderson, Kimberly A; Yamada, Kristin E; Eckhert, Curtis D

    2017-04-01

    Fruits, nuts, legumes, and vegetables are rich sources of boron (B), an essential plant nutrient with chemopreventive properties. Blood boric acid (BA) levels reflect recent B intake, and men at the US mean intake have a reported non-fasting level of 10 μM. Treatment of DU-145 prostate cancer cells with physiological concentrations of BA inhibits cell proliferation without causing apoptosis and activates eukaryotic initiation factor 2 (eIF2α). EIF2α induces cell differentiation and protects cells by redirecting gene expression to manage endoplasmic reticulum stress. Our objective was to determine the temporal expression of endoplasmic reticulum (ER) stress-activated genes in DU-145 prostate cells treated with 10 μM BA. Immunoblots showed post-treatment increases in eIF2α protein at 30 min and ATF4 and ATF6 proteins at 1 h and 30 min, respectively. The increase in ATF4 was accompanied by an increase in the expression of its downstream genes growth arrest and DNA damage-induced protein 34 (GADD34) and homocysteine-induced ER protein (Herp), but a decrease in GADD153/CCAAT/enhancer-binding protein homologous protein (CHOP), a pro-apoptotic gene. The increase in ATF6 was accompanied by an increase in expression of its downstream genes GRP78/BiP, calreticulin, Grp94, and EDEM. BA did not activate IRE1 or induce cleavage of XBP1 mRNA, a target of IRE1. Low boron status has been associated with increased cancer risk, low bone mineralization, and retinal degeneration. ATF4 and BiP/GRP78 function in osteogenesis and bone remodeling, calreticulin is required for tumor suppressor p53 function and mineralization of teeth, and BiP/GRP78 and EDEM prevent the aggregation of misfolded opsins which leads to retinal degeneration. The identification of BA-activated genes that regulate its phenotypic effects provides a molecular underpinning for boron nutrition and biology.

  12. Fabrication of boron sputter targets

    DOEpatents

    Makowiecki, D.M.; McKernan, M.A.

    1995-02-28

    A process is disclosed for fabricating high density boron sputtering targets with sufficient mechanical strength to function reliably at typical magnetron sputtering power densities and at normal process parameters. The process involves the fabrication of a high density boron monolithe by hot isostatically compacting high purity (99.9%) boron powder, machining the boron monolithe into the final dimensions, and brazing the finished boron piece to a matching boron carbide (B{sub 4}C) piece, by placing aluminum foil there between and applying pressure and heat in a vacuum. An alternative is the application of aluminum metallization to the back of the boron monolithe by vacuum deposition. Also, a titanium based vacuum braze alloy can be used in place of the aluminum foil. 7 figs.

  13. Fabrication of boron sputter targets

    DOEpatents

    Makowiecki, Daniel M.; McKernan, Mark A.

    1995-01-01

    A process for fabricating high density boron sputtering targets with sufficient mechanical strength to function reliably at typical magnetron sputtering power densities and at normal process parameters. The process involves the fabrication of a high density boron monolithe by hot isostatically compacting high purity (99.9%) boron powder, machining the boron monolithe into the final dimensions, and brazing the finished boron piece to a matching boron carbide (B.sub.4 C) piece, by placing aluminum foil there between and applying pressure and heat in a vacuum. An alternative is the application of aluminum metallization to the back of the boron monolithe by vacuum deposition. Also, a titanium based vacuum braze alloy can be used in place of the aluminum foil.

  14. Determination of phase stability of elemental boron.

    PubMed

    White, Mary Anne; Cerqueira, Anthony B; Whitman, Catherine A; Johnson, Michel B; Ogitsu, Tadashi

    2015-03-16

    Boron is an important element, used in applications from superhard materials to superconductors. Boron exists in several forms (allotropes) and, surprisingly, it was not known which form (α or β) is stable at ambient conditions. Through experiment, we quantify the relative stability of α-boron and β-boron as a function of temperature. The ground-state energies of α-boron and β-boron are nearly identical. For all temperatures up to 2000 K, the complicated β-boron structure is more stable than the simpler α-boron structure at ambient pressure. Below 1000 K, β-boron is entropically stabilized with respect to α-boron owing to its partially occupied sites, whereas at higher temperatures β-boron is enthalpically stabilized with respect to α-boron. We show that α-boron only becomes stable on application of pressure.

  15. Effects assessment: boron compounds in the aquatic environment.

    PubMed

    Schoderboeck, Lucia; Mühlegger, Simone; Losert, Annemarie; Gausterer, Christian; Hornek, Romana

    2011-01-01

    In previous studies, boron compounds were considered to be of comparatively low toxicity in the aquatic environment, with predicted no effect concentration (PNEC) values ranging around 1 mg B/L (expressed as boron equivalent). In the present study, we describe an evaluation of toxicity data for boron available for the aquatic environment by different methods. For substances with rich datasets, it is often possible to perform a species sensitivity distribution (SSD). The typical outcome of an SSD is the Hazardous Concentration 5% (HC5), the concentration at which 95% of all species are protected with a probability of 95%. The data set currently available on the toxic effects of boron compounds to aquatic organisms is comprehensive, but a careful evaluation of these data revealed that chronic data for aquatic insects and plants are missing. In the present study both the standard assessment factor approach as well as the SSD approach were applied. The standard approach led to a PNEC of 0.18 mg B/L (equivalent to 1.03 mg boric acid/L), while the SSD approach resulted in a PNEC of 0.34 mg B/L (equivalent to 1.94 mg boric acid/L). These evaluations indicate that boron compounds could be hazardous to aquatic organisms at concentrations close to the natural environmental background in some European regions. This suggests a possible high sensitivity of some ecosystems for anthropogenic input of boron compounds. Another concern is that the anthropogenic input of boron could lead to toxic effects in organisms adapted to low boron concentration.

  16. Methods of producing continuous boron carbide fibers

    SciTech Connect

    Garnier, John E.; Griffith, George W.

    2015-12-01

    Methods of producing continuous boron carbide fibers. The method comprises reacting a continuous carbon fiber material and a boron oxide gas within a temperature range of from approximately 1400.degree. C. to approximately 2200.degree. C. Continuous boron carbide fibers, continuous fibers comprising boron carbide, and articles including at least a boron carbide coating are also disclosed.

  17. Boron and Compounds

    Integrated Risk Information System (IRIS)

    EPA 635 / 04 / 052 www.epa.gov / iris TOXICOLOGICAL REVIEW OF BORON AND COMPOUNDS ( CAS No . 7440 - 42 - 8 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2004 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been reviewed

  18. Boronate affinity materials for separation and molecular recognition: structure, properties and applications.

    PubMed

    Li, Daojin; Chen, Yang; Liu, Zhen

    2015-11-21

    Boronate affinity materials, as unique sorbents, have emerged as important media for the selective separation and molecular recognition of cis-diol-containing compounds. With the introduction of boronic acid functionality, boronate affinity materials exhibit several significant advantages, including broad-spectrum selectivity, reversible covalent binding, pH-controlled capture/release, fast association/desorption kinetics, and good compatibility with mass spectrometry. Because cis-diol-containing biomolecules, including nucleosides, saccharides, glycans, glycoproteins and so on, are the important targets in current research frontiers such as metabolomics, glycomics and proteomics, boronate affinity materials have gained rapid development and found increasing applications in the last decade. In this review, we critically survey recent advances in boronate affinity materials. We focus on fundamental considerations as well as important progress and new boronate affinity materials reported in the last decade. We particularly discuss on the effects of the structure of boronate ligands and supporting materials on the properties of boronate affinity materials, such as binding pH, affinity, selectivity, binding capacity, tolerance for interference and so on. A variety of promising applications, including affinity separation, proteomics, metabolomics, disease diagnostics and aptamer selection, are introduced with main emphasis on how boronate affinity materials can solve the issues in the applications and what merits boronate affinity materials can provide.

  19. Accumulation and loss of arsenic and boron, alone and in combination, in mallard ducks

    SciTech Connect

    Pendleton, G.W.; Whitworth, M.R.; Olsen, G.H.

    1995-08-01

    Arsenic and boron are common in the environment, and wildlife can be exposed to toxic concentrations through both natural and human-influenced processes. The authors exposed adult male mallard ducks to dietary concentrations of 300 ppm arsenic as sodium arsenate, 1,600 ppm boron as boric acid, or both and estimated the tissue accumulation and loss rates when the ducks were returned to uncontaminated food. Both elements were accumulated rapidly; equilibrium levels were reached for arsenic in 10 to 30 d and for boron in 2 to 15 d. Accumulation of each element was slowed by the presence of the other in the diet. Boron was eliminated by mallards very rapidly, with few detectable residues {ge}1 d after removal of boron from the diet; arsenic was also rapidly lost with half-lives of 1 to 3 d (half-lives were not constant throughout the loss period). Arsenic loss rate was not affected by the presence of boron. Arsenic accumulated to the highest level in liver tissue, with blood and brain levels lower; concentrations in the liver and blood were proportional but affected by the presence of boron. Boron concentrations were highest in the blood, followed by the brain and liver; concentrations in the liver and blood were proportional but affected by the presence of boron. Boron concentrations were highest in the blood, followed by the brain and liver; concentrations in the blood and liver were proportional.

  20. Chemical Vapor Deposition of Phosphorous- and Boron-Doped Graphene Using Phenyl-Containing Molecules.

    PubMed

    Mekan Ovezmyradov; Magedov, Igor V; Frolova, Liliya V; Chandler, Gary; Garcia, Jill; Bethke, Donald; Shaner, Eric A; Kalugin, Nikolai G

    2015-07-01

    Simultaneous chemical vapor deposition (CVD) of graphene and "in-situ" phosphorous or boron doping of graphene was accomplished using Triphenylphosphine (TPP) and 4-Methoxyphenylboronic acid (4-MPBA). The TPP and 4-MPBA molecules were sublimated and supplied along with CH4 molecules during graphene growth at atmospheric pressure. The grown graphene samples were characterized using Raman spectroscopy. Phosphorous and boron presence in phosphorous and boron doped graphene was confirmed with Auger electron spectroscopy. The possibility of obtaining phosphorous and boron doped graphene using solid-source molecule precursors via CVD can lead to an easy and rapid production of modified large area graphene.

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

    PubMed

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

    2012-06-01

    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.

  2. Nothing Boring About Boron.

    PubMed

    Pizzorno, Lara

    2015-08-01

    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; osteoarthritis (OA

  3. Azomethine H colorimetric method for determining dissolved boron in water

    USGS Publications Warehouse

    Spencer, R.R.; Erdmann, D.E.

    1979-01-01

    An automated colorimetric method for determining dissolved boron in water is described. The boron is complexed with azomethine H, which is readily available as the condensation product of H acid (8-amino-1-naphthol-3,6-disulfonic acid) and salicylaldehyde. The absorbance of the yellow complex formed is then measured colorimetrically at 410 nm. Interference effects from other dissolved species are minimized by the addition of diethylenetriaminepentaacetic acid (DTPA); however, iron, zinc, and bicarbonate interfere at concentrations above 400 ??g/L, 2000 ??g/L, and 200 mg/L, respectively. The bicarbonate interference can be eliminated by careful acidification of the sample with concentrated HCl to a pH between 5 and 6. Thirty samples per hour can be routinely analyzed over the range of from 10 to 400 ??g/L, boron.

  4. Cp*-Substituted Boron Cations: The Effect of NHC, NHO, and CAAC Ligands.

    PubMed

    Huang, Jih-Sheng; Lee, Wan-Hua; Shen, Chao-Tang; Lin, Ya-Fan; Liu, Yi-Hung; Peng, Shie-Ming; Chiu, Ching-Wen

    2016-12-05

    The effect of a ligand on the electron deficiency and Lewis acidity of the Cp*-substituted boron dication has been investigated experimentally and theoretically. In addition to the reported IMes- and N-heterocyclic olefin (NHO)-stabilized boron dications, the related cyclic alkylamino carbene (CAAC)-coordinated boron mono- and dications have also been synthesized and structurally characterized. An electrochemical study of dications [3a-3c](2+) confirms the higher electron deficiency of the dicationic system than the related boron monocations. Moreover, the presence of a π-acidic CAAC ligand is critical for realizing stable radical species generated from the chemical reduction of boron cations. The nature of the axial ligand also significantly affects the selectivity of the hydride addition reaction of boron dications. While bulky superhydride reacts with [3a-3c](2+) in the same manner to give the cyclic boreniums, [BH4](-) attacks three different electrophilic sites of boron dications: the sp(2) carbon of Cp* of the IMes-coordinated system ([3a](2+)), the central boron atom of the NHO-stabilized analogue ([3b](2+)), and the ylidene carbon of the CAAC-containing boron dication ([3c](2+)).

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

    PubMed

    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.

  6. Boron impregnation treatment of Eucalyptus grandis wood.

    PubMed

    Dhamodaran, T K; Gnanaharan, R

    2007-08-01

    Eucalyptus grandis is suitable for small timber purposes, but its wood is reported to be non-durable and difficult to treat. Boron compounds being diffusible, and the vacuum-pressure impregnation (VPI) method being more suitable for industrial-scale treatment, the possibility of boron impregnation of partially dry to green timber was investigated using a 6% boric acid equivalent (BAE) solution of boric acid and borax in the ratio 1:1.5 under different treatment schedules. It was found that E. grandis wood, even in green condition, could be pressure treated to desired chemical dry salt retention (DSR) and penetration levels using 6% BAE solution. Up to a thickness of 50mm, in order to achieve a DSR of 5 kg/m(3) boron compounds, the desired DSR level as per the Indian Standard for perishable timbers for indoor use, it was found that neither the moisture content of wood nor the treatment schedule posed any problem as far as the treatability of E. grandis wood was concerned.

  7. Impact of boron dilution accidents on low boron PWR safety

    SciTech Connect

    Papukchiev, A.; Liu, Y.; Schaefer, A.

    2006-07-01

    In conventional pressurized water reactor (PWR) designs, soluble boron is used for reactivity control over core fuel cycle. As an inadvertent reduction of the boron concentration during a boron dilution accident could introduce positive reactivity and have a negative impact on PWR safety, design changes to reduce boron concentration in the reactor coolant are of general interest. In the framework of an investigation into the feasibility of low boron design, a PWR core configuration based on fuel with higher gadolinium (Gd) load has been developed which permits to reduce the natural boron concentration at begin of cycle (BOC) to 518 ppm. For the assessment of the potential safety advantages, a boron dilution accident due to small break loss-of-coolant-accident (SBLOCA) has been simulated with the system code ATHLET for two PWR core designs: a low boron design and a standard core design. The results from the comparative analyses showed that the impact of the boron dilution accident on the new PWR design safety is significantly lower in comparison with the standard design. The new reactor design provided at least 4, 4% higher reactivity margin to recriticality during the whole accident which is equivalent to the negative reactivity worth of additional 63% of all control rods fully inserted in to the core. (authors)

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Dynamic-covalent macromolecular stars with boronic ester linkages.

    PubMed

    Bapat, Abhijeet P; Roy, Debashish; Ray, Jacob G; Savin, Daniel A; Sumerlin, Brent S

    2011-12-14

    Macromolecular stars containing reversible boronic ester linkages were prepared by an arm-first approach by reacting well-defined boronic acid-containing block copolymers with multifunctional 1,2/1,3-diols. Homopolymers of 3-acrylamidophenylboronic acid (APBA) formed macroscopic dynamic-covalent networks when cross-linked with multifunctional diols. On the other hand, adding the diol cross-linkers to block copolymers of poly(N,N-dimethylacrylamide (PDMA))-b-poly(APBA) led to nanosized multiarm stars with boronic ester cores and PDMA coronas. The assembly of the stars under a variety of conditions was considered. The dynamic-covalent nature of the boronic ester cross-links allowed the stars to reconfigure their covalent structure in the presence of monofunctional diols that competed for bonding with the boronic acid component. Therefore, the stars could be induced to dissociate via competitive exchange reactions. The star formation-dissociation process was shown to be repeatable over multiple cycles. © 2011 American Chemical Society

  10. Microstructure Analysis of Boron Nanotubes

    DTIC Science & Technology

    2012-05-01

    figure 1 2 3 High resolution TEM showing very small elongated BNT filaments 3 4 SAED from an area in figure 3 showing exactly the same kind of...scattered large numbers of BNT 4 7 EDAX analyses of boron nitride nano powder showing boron and oxygen 5 8 Low magnification SEM picture of folded 600...Picatinny Arsenal, New Jersey. INTRODUCTION Boron nanotubes ( BNT ) have never been produced in a reliable manner, yet they remain a promising

  11. Structures, stability, mechanical and electronic properties of α-boron and α∗-boron

    NASA Astrophysics Data System (ADS)

    He, Chaoyu; Zhong, J. X.

    2013-04-01

    The structures, stability, mechanical and electronic properties of α-boron and a promising metastable boron phase (α*-boron) have been studied by first-principles calculations. α-boron and α*-boron consist of equivalent icosahedra B12 clusters in different connecting configurations of "3S-6D-3S" and "2S-6D-4S", respectively. The total energy calculations show that α*-boron is less stable than α-boron but more favorable than the well-known β-boron and γ-boron at zero pressure. Both α-boron and α*-boron are confirmed dynamically and mechanically stable. The mechanical and electronic properties of α-boron and α*-boron indicate that they are potential superhard semiconducting phases of element boron.

  12. Boron nitride nanotubes.

    PubMed

    Chopra, N G; Luyken, R J; Cherrey, K; Crespi, V H; Cohen, M L; Louie, S G; Zettl, A

    1995-08-18

    The successful synthesis of pure boron nitride (BN) nanotubes is reported here. Multi-walled tubes with inner diameters on the order of 1 to 3 nanometers and with lengths up to 200 nanometers were produced in a carbon-free plasma discharge between a BN-packed tungsten rod and a cooled copper electrode. Electron energy-loss spectroscopy on individual tubes yielded B:N ratios of approximately 1, which is consistent with theoretical predictions of stable BN tube structures.

  13. Spectrophotometric determination of traces of boron in high purity silicon

    SciTech Connect

    Parashar, D.C.; Sarkar, A.K.; Singh, N. )

    1989-07-01

    A reddish brown complex is formed between boron and curcumin in concentrated sulfuric acid and glacial acetic acid mixture (1:1). The colored complex is highly selective and stable for about 3 hours and has the maximum absorbance at 545 nm. The sensitivity of the method is extremely high and the detection limit is 3 parts per billion based on 0.004 absorbance value. The interference of some of the important cations and anions relevant to silicon were studied and it is found that 100 fold excess of most of these cations and anions do not interfere in the determination of boron. The method is successfully employed for the determination of boron in silicon used in semiconductor devices. The results have been verified by standard addition method.

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

    PubMed

    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.

  15. Method of fabricating boron containing coatings

    DOEpatents

    Makowiecki, Daniel M.; Jankowski, Alan F.

    1999-01-01

    Hard coatings are fabricated from boron nitride, cubic boron nitride, and multilayer boron/cubic boron nitride, and the fabrication thereof involves magnetron sputtering in a selected atmosphere. These hard coatings may be applied to tools and engine and other parts, as well to reduce wear on tribological surfaces and electronic devices. These boron coatings contain no morphological growth features. For example, the boron is formed in an inert (e.g. argon) atmosphere, while the cubic boron nitride is formed in a reactive (e.g. nitrogen) atmosphere. The multilayer boron/cubic boron nitride, is produced by depositing alternate layers of boron and cubic boron nitride, with the alternate layers having a thickness of 1 nanometer to 1 micrometer, and at least the interfaces of the layers may be discrete or of a blended or graded composition.

  16. Method of fabricating boron containing coatings

    DOEpatents

    Makowiecki, D.M.; Jankowski, A.F.

    1999-04-27

    Hard coatings are fabricated from boron nitride, cubic boron nitride, and multilayer boron/cubic boron nitride, and the fabrication thereof involves magnetron sputtering in a selected atmosphere. These hard coatings may be applied to tools and engine and other parts, as well to reduce wear on tribological surfaces and electronic devices. These boron coatings contain no morphological growth features. For example, the boron is formed in an inert (e.g. argon) atmosphere, while the cubic boron nitride is formed in a reactive (e.g. nitrogen) atmosphere. The multilayer boron/cubic boron nitride, is produced by depositing alternate layers of boron and cubic boron nitride, with the alternate layers having a thickness of 1 nanometer to 1 micrometer, and at least the interfaces of the layers may be discrete or of a blended or graded composition. 3 figs.

  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.

    PubMed

    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.

  18. A facile and high-yield formation of dipyrrin-boronic acid dyads and triads: a light-harvesting system in the visible region based on the efficient energy transfer.

    PubMed

    Yamamura, Masaki; Yazaki, Shinya; Seki, Motofumi; Matsui, Yasunori; Ikeda, Hiroshi; Nabeshima, Tatsuya

    2015-03-07

    Artificial light-harvesting systems, Ar,O-BODIPY dyads and triads conjugated with a light harvester, were synthesized in high yield by the reaction of an N2O2-type dipyrrin with boronic acids. Dyad 2 having a pyrene unit underwent quantitative Förster resonance energy transfer (FRET) from the antenna unit, pyrene, to the fluorophore unit, Ar,O-BODIPY. Triads 3·5 and 4·5 were quantitatively prepared by mixing pyridine-appended compounds 3 and 4 with saloph·Zn complex 5, respectively. Triad 4·5 underwent efficient FRET from the saloph·Zn complex unit to the fluorophore unit at the rate of 2.0 × 10(11) s(-1). Interestingly, the fluorescence quenching process in the excited state of the triad 3·5 took place following the energy transfer event. Thus, appropriate positioning of the energy donor and acceptor is necessary to construct a highly efficient FRET system.

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

    NASA Astrophysics Data System (ADS)

    Zhiani, Rahele

    2017-07-01

    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. Hypergolic Ionic Liquids to Mill, Suspend and Ignite Boron Nanoparticles

    DTIC Science & Technology

    2012-01-01

    by milling micron-sized B with a ligand to create ligand-protected B nanoparticles. For example, oleic acid was utilized as a ligand to create...Boron (2 g) was added to the ball milling apparatus and dry milled, followed by additional milling with either no ligand, a combination of oleic acid ...milled in the oleic acid /olelyl amine surfactant mixture led to a complex flame behavior reproducibly exhibiting two flames which lengthened the

  1. Atomically controlled substitutional boron-doping of graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Kawai, Shigeki; Saito, Shohei; Osumi, Shinichiro; Yamaguchi, Shigehiro; Foster, Adam S.; Spijker, Peter; Meyer, Ernst

    2015-08-01

    Boron is a unique element in terms of electron deficiency and Lewis acidity. Incorporation of boron atoms into an aromatic carbon framework offers a wide variety of functionality. However, the intrinsic instability of organoboron compounds against moisture and oxygen has delayed the development. Here, we present boron-doped graphene nanoribbons (B-GNRs) of widths of N=7, 14 and 21 by on-surface chemical reactions with an employed organoboron precursor. The location of the boron dopant is well defined in the centre of the B-GNR, corresponding to 4.8 atom%, as programmed. The chemical reactivity of B-GNRs is probed by the adsorption of nitric oxide (NO), which is most effectively trapped by the boron sites, demonstrating the Lewis acid character. Structural properties and the chemical nature of the NO-reacted B-GNR are determined by a combination of scanning tunnelling microscopy, high-resolution atomic force microscopy with a CO tip, and density functional and classical computations.

  2. 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

    PubMed Central

    2009-01-01

    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. PMID:20596476

  3. 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.

    PubMed

    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.

  4. 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

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

    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 10B 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.

  5. Boron isotopic compositions of some boron minerals

    SciTech Connect

    Oi, Takao; Musashi, Masaaki; Ossaka, Tomoko; Kakihana, Hidetake ); Nomura, Masao; Okamoto, Makoto )

    1989-12-01

    Boron minerals that have different structural formulae but are supposed to have the same geologic origin have been collected and analyzed for the {sup 11}B/{sup 10}B isotopic ratio. It has been reconfirmed that minerals of marine origin have higher {sup 11}B/{sup 10}B ratios than those of nonmarine origin. It has been found that the sequence of decreasing {sup 11}B/{sup 10}B values among the minerals with the same geologic origin is; borax, tincal, kernite (Na borates) > ulexite (Na/Ca borate) > colemanite, iyoite, meyerhofferite (Ca borates). This sequence is explainable on the basis of the difference in crystal structure among the minerals. That is, minerals with high BO{sub 3}/BO{sub 4} ratios, (the ratio of the number of the BO{sub 3} triangle units to the number of the BO{sub 4} tetrahedron units in the structural formula of a mineral) have higher {sup 11}B/{sup 10}B ratios.

  6. Boron containing multilayer coatings and method of fabrication

    DOEpatents

    Makowiecki, Daniel M.; Jankowski, Alan F.

    1997-01-01

    Hard coatings are fabricated from multilayer boron/boron carbide, boron carbide/cubic boron nitride, and boron/boron nitride/boron carbide, and the fabrication thereof involves magnetron sputtering in a selected atmosphere. These hard coatings may be applied to tools and engine and other parts, as well to reduce wear on tribological surfaces and electronic devices. These boron coatings contain no morphological growth features. For example, the boron and boron carbide used in forming the multilayers are formed in an inert (e.g. argon) atmosphere, while the cubic boron nitride is formed in a reactive (e.g. nitrogen) atmosphere. The multilayer boron/boron carbide, and boron carbide/cubic boron nitride is produced by depositing alternate layers of boron, cubic boron nitride or boron carbide, with the alternate layers having a thickness of 1 nanometer to 1 micrometer, and at least the interfaces of the layers may be of a discrete or a blended or graded composition.

  7. Boron Clusters Come of Age

    ERIC Educational Resources Information Center

    Grimes, Russell N.

    2004-01-01

    Boron is the only element other than carbon that can build molecules of unlimited size by covalently boding to itself, a property known as catenation. In contrast to the chains and rings favored by carbon, boron arguably adopts a cluster motif that is reflected in the various forms of the pure element and in the huge area of polyhedral borane…

  8. Boron Clusters Come of Age

    ERIC Educational Resources Information Center

    Grimes, Russell N.

    2004-01-01

    Boron is the only element other than carbon that can build molecules of unlimited size by covalently boding to itself, a property known as catenation. In contrast to the chains and rings favored by carbon, boron arguably adopts a cluster motif that is reflected in the various forms of the pure element and in the huge area of polyhedral borane…

  9. Release and recovery of guest molecules during the reversible borate gel formation of guest-included macrocyclic boronic esters.

    PubMed

    Ito, Suguru; Takata, Hisatsugu; Ono, Kosuke; Iwasawa, Nobuharu

    2013-10-11

    Borate gel formation from guest-encapsulated macrocyclic boronic esters was realized by the addition of a diamine to the suspension of the boronic esters in various organic solvents, which triggered the release of the guest compounds. The guest molecules could be recovered from the borate gel by addition of an acid to remove the diamine, which facilitated the reconstruction of the initial guest-encapsulated macrocyclic boronic esters.

  10. Boron-containing aptamers to ATP

    PubMed Central

    Lato, Susan M.; Ozerova, Nicole D. S.; He, Kaizhang; Sergueeva, Zinaida; Shaw, Barbara Ramsay; Burke, Donald H.

    2002-01-01

    Boron neutron capture therapy (BNCT), an experimental treatment for certain cancers, destroys only cells near the boron; however, there is a need to develop highly specific delivery agents. As nucleic acid aptamers recognize specific molecular targets, we investigated the influence of boronated nucleotide analogs on RNA function and on the systematic evolution of ligands by exponential enrichment (SELEX) process. Substitution of guanosine 5′-(α-P-borano) triphosphate (bG) for GTP or uridine 5′-(α-P-borano) triphosphate (bU) for UTP in several known aptamers diminished or eliminated target recognition by those RNAs. Specifically, ATP-binding aptamers containing the ζ-fold, which appears in several selections for adenosine aptamers, became inactive upon bG substitution but were only moderately affected by bU substitution. Selections were carried out using the bG or bU analogs with C8-linked ATP agarose as the binding target. The selections with bU and normal NTP yielded some ζ-fold aptamers, while the bG selection yielded none of this type. Non-ζ aptamers from bU and bG populations tolerated the borano substitution and many required it. The borano nucleotide requirement is specific; bU could not be used in bG-dependent aptamers nor vice versa. The borano group plays an essential role, as yet undefined, in target recognition or RNA structure. We conclude that the bG and bU nucleotides are fully compatible with SELEX, and that these analogs could be used to make boronated aptamers as therapeutics for BNCT. PMID:11884639

  11. Method and apparatus for the preparation of liquid samples for determination of boron

    DOEpatents

    Siemer, Darryl D.

    1986-03-04

    A method and apparatus for the preparation of a liquid sample for the quantitative determination of boron by flame photometry. The sample is combined in a vessel with sulfuric acid, and an excess of methanol is added thereto. The methanol reacts with any boron present in the sample to form trimethyl borate which is volatilized by the heat of reaction between the excess methanol and sulfuric acid. The volatilized trimethyl borate is withdrawn from the vessel by either a partial vacuum or a positive pressure and is rapidly transferred to a standard flame photometer. The method is free of interference from typical boron concomitants.

  12. Method and apparatus for the preparation of liquid samples for determination of boron

    DOEpatents

    Siemer, D.D.

    A method and apparatus are described for the preparation of a liquid sample for the quantitative determination of boron by flame photometry. The sample is combined in a vessel with sulfuric acid, and an excess of methanol is added thereto. The methanol reacts with any boron present in the sample to form trimethyl borate which is volatilized by the heat of reaction between the excess methanol and sulfuric acid. The volatilized trimethyl borate is withdrawn from the vessel by either a partial vacuum or a positive pressure and is rapidly transferred to a standard flame photometer. The method is free of interference from typical boron concomitants.

  13. Method and apparatus for the preparation of liquid samples for determination of boron

    DOEpatents

    Siemer, Darryl D.

    1986-01-01

    A method and apparatus for the preparation of a liquid sample for the quantitative determination of boron by flame photometry. The sample is combined in a vessel with sulfuric acid, and an excess of methanol is added thereto. The methanol reacts with any boron present in the sample to form trimethyl borate which is volatilized by the heat of reaction between the excess methanol and sulfuric acid. The volatilized trimethyl borate is withdrawn from the vessel by either a partial vacuum or a positive pressure and is rapidly transferred to a standard flame photometer. The method is free of interference from typical boron concomitants.

  14. The role of boron in flame-retardant treatments

    Treesearch

    S. L. LeVan; H. C. Tran

    1990-01-01

    Flame retardants for wood alter the combustion properties of wood to reduce surface flame spread. Flame retardant chemicals cause acid catalyzed dehydration reactions in wood to facilitate the formation of char and reduce the effective heat of combustion, resulting in lower heat release and flame spread. Boron compounds can also form glassy fiis that may inhibit mass...

  15. Boron deprivation decreases liver S-adenosylmethionine and spermidine and increases plasma homocysteine and cysteine in rats.

    PubMed

    Nielsen, Forrest Harold

    2009-01-01

    Two experiments were conducted with weanling Sprague-Dawley rats to determine whether changes in S-adenosylmethionine utilization or metabolism contribute to the diverse responses to boron deprivation. In both experiments, four treatment groups of 15 male rats were fed ground corn-casein based diets that contained an average of 0.05 mg (experiment 1) or 0.15 mg (experiment 2) boron/kg. In experiment 2, some ground corn was replaced by sucrose and fructose to increase oxidative stress. The dietary variables were supplemental 0 (boron-deprived) or 3 (boron-adequate) mg boron/kg and different fat sources (can affect the response to boron) of 75 g corn oil/kg or 65 g fish (menhaden) oil/kg plus 10 linoleic acid/kg. When euthanized at age 20 (experiment 1) and 18 (experiment 2) weeks, rats fed the low-boron diet were considered boron-deprived because they had decreased boron concentrations in femur and kidney. Boron deprivation regardless of dietary oil increased plasma cysteine and homocysteine and decreased liver S-adenosylmethionine, S-adenosylhomocysteine, and spermidine. Plasma concentration of 8-iso-prostaglandin F2alpha (indicator of oxidative stress) was not affected by boron, but was decreased by feeding fish oil instead of corn oil. Fish oil instead of corn oil decreased S-adenosylmethionine, increased spermidine, and did not affect S-adenosylhomocysteine concentrations in liver. Additionally, fish oil versus corn oil did not affect plasma homocysteine in experiment 1, and slightly increased it in experiment 2. The findings suggest that boron is bioactive through affecting the formation or utilization of S-adenosylmethionine. Dietary fatty acid composition also affects S-adenosylmethionine formation or utilization, but apparently through a mechanism different from that of boron.

  16. Boron and silicon: Effects on growth, plasma lipids, urinary cyclic AMP and bone and brain mineral composition of male rats

    SciTech Connect

    Seaborn, C.D.; Nielsen, F.H. . Grand Forks Human Nutrition Research Center)

    1994-06-01

    Because boron resembles silicon in its chemical properties, an experiment was performed to determine if excessive dietary boron would affect the response to silicon deprivation and, conversely, if silicon would influence the effects of an excessive intake of boron. Male weanling Sprague-Dawley rats were assigned to groups of 6 or 12 in a two-by-two factorially arranged experiment. Supplemented to a ground corn/casein diet containing 1.2 [mu]g silicon and 3 [mu]g boron per gram were silicon as sodium metasilicate at 0 or 50 [mu]g/g and boron as orthoboric acid at 0 or 500 [mu]g/g diet. At nine weeks, animals fed high dietary boron had significantly decreased final body weights, liver-weight-to-body-weight ratios, urinary cAMP concentrations, plasma triglyceride, cholesterol, glycine, valine, leucine, and lysine concentrations and skull copper, sodium, and manganese concentrations. High dietary boron also significantly increased brain-weight-to-body-weight ratios, magnesium concentrations of femur, brain, and plasma, zinc concentration of femur, and iron concentration of skull. The bone mineral findings suggest that excess dietary boron exerts subtle effects on bone composition. Dietary silicon affected blood urea nitrogen, hematocrit, hemoglobin, and the concentrations of plasma threonine and aspartic acid in animals fed excess boron. Depression of the testes-weight-to-body-weight ratio of animals fed 500 [mu]g boron per gram diet was most marked in animals not fed silicon. Although excessive dietary boron did not markedly enhanced the response of rats to silicon deprivation, dietary silicon affected their response to high dietary boron. Thus, dietary silicon apparently can influence boron toxicity.

  17. Functionalized boron nitride nanotubes

    DOEpatents

    Sainsbury, Toby; Ikuno, Takashi; Zettl, Alexander K

    2014-04-22

    A plasma treatment has been used to modify the surface of BNNTs. In one example, the surface of the BNNT has been modified using ammonia plasma to include amine functional groups. Amine functionalization allows BNNTs to be soluble in chloroform, which had not been possible previously. Further functionalization of amine-functionalized BNNTs with thiol-terminated organic molecules has also been demonstrated. Gold nanoparticles have been self-assembled at the surface of both amine- and thiol-functionalized boron nitride Nanotubes (BNNTs) in solution. This approach constitutes a basis for the preparation of highly functionalized BNNTs and for their utilization as nanoscale templates for assembly and integration with other nanoscale materials.

  18. Is Boron a Prebiotic Element? A Mini-review of the Essentiality of Boron for the Appearance of Life on Earth

    NASA Astrophysics Data System (ADS)

    Scorei, Romulus

    2012-02-01

    Boron is probably a prebiotic element with special importance in the so-called "sugars world". Boron is not present on Earth in its elemental form. It is found only in compounds, e.g., borax, boric acid, kernite, ulexite, colemanite and other borates. Volcanic spring waters sometimes contain boron-based acids (e.g., boric, metaboric, tetraboric and pyroboric acid). Borates influence the formation of ribofuranose from formaldehyde that feeds the "prebiotic metabolic cycle". The importance of boron in the living world is strongly related to its implications in the prebiotic origins of genetic material; consequently, we believe that throughout the evolution of life, the primary role of boron has been to provide thermal and chemical stability in hostile environments. The complexation of boric acid and borates with organic cis-diols remains the most probable chemical mechanism for the role of this element in the evolution of the living world. Because borates can stabilize ribose and form borate ester nucleotides, boron may have provided an essential contribution to the "pre-RNA world".

  19. Is boron a prebiotic element? A mini-review of the essentiality of boron for the appearance of life on earth.

    PubMed

    Scorei, Romulus

    2012-02-01

    Boron is probably a prebiotic element with special importance in the so-called "sugars world". Boron is not present on Earth in its elemental form. It is found only in compounds, e.g., borax, boric acid, kernite, ulexite, colemanite and other borates. Volcanic spring waters sometimes contain boron-based acids (e.g., boric, metaboric, tetraboric and pyroboric acid). Borates influence the formation of ribofuranose from formaldehyde that feeds the "prebiotic metabolic cycle". The importance of boron in the living world is strongly related to its implications in the prebiotic origins of genetic material; consequently, we believe that throughout the evolution of life, the primary role of boron has been to provide thermal and chemical stability in hostile environments. The complexation of boric acid and borates with organic cis-diols remains the most probable chemical mechanism for the role of this element in the evolution of the living world. Because borates can stabilize ribose and form borate ester nucleotides, boron may have provided an essential contribution to the "pre-RNA world".

  20. The levels of boron-uptake proteins in roots are correlated with tolerance to boron stress in barley

    USDA-ARS?s Scientific Manuscript database

    Boron (B) is an essential micronutrient required for plant growth and development. Recently, two major B-uptake proteins, BOR1 and NIP5;1 have been identified and partially characterized. BOR1 is a high-affinity B transporter involved in xylem loading in roots, and NIP5;1 acts is a major boric-acid ...

  1. Merging visible-light photocatalysis and transition-metal catalysis in the copper-catalyzed trifluoromethylation of boronic acids with CF3I.

    PubMed

    Ye, Yingda; Sanford, Melanie S

    2012-06-06

    This communication describes the development of a mild method for the cross-coupling of arylboronic acids with CF(3)I via the merger of photoredox and Cu catalysis. This method has been applied to the trifluoromethylation of electronically diverse aromatic and heteroaromatic substrates and tolerates many common functional groups.

  2. METHOD OF COATING SURFACES WITH BORON

    DOEpatents

    Martin, G.R.

    1949-10-11

    A method of forming a thin coating of boron on metallic, glass, or other surfaces is described. The method comprises heating the article to be coated to a temperature of about 550 d C in an evacuated chamber and passing trimethyl boron, triethyl boron, or tripropyl boron in the vapor phase and under reduced pressure into contact with the heated surface causing boron to be deposited in a thin film.

  3. Biocompatibility of functionalized boron phosphate (BPO4) nanoparticles for boron neutron capture therapy (BNCT) application.

    PubMed

    Achilli, Cesare; Grandi, Stefania; Ciana, Annarita; Guidetti, Gianni F; Malara, Alessandro; Abbonante, Vittorio; Cansolino, Laura; Tomasi, Corrado; Balduini, Alessandra; Fagnoni, Maurizio; Merli, Daniele; Mustarelli, Piercarlo; Canobbio, Ilaria; Balduini, Cesare; Minetti, Giampaolo

    2014-04-01

    Boron neutron capture therapy (BNCT) is a radiotherapy treatment based on the accumulation in the tumor of a (10)B-containing drug and subsequent irradiation with low energy neutrons, which bring about the decay of (10)B to (7)Li and an α particle, causing the death of the neoplastic cell. The effectiveness of BNCT is limited by the low delivery and accumulation of the used boron-containing compounds. Here we report the development and the characterization of BPO4 nanoparticles (NPs) as a novel possible alternative drug for BNCT. An extensive analysis of BPO4 NP biocompatibility was performed using both mature blood cells (erythrocytes, neutrophils and platelets) and a model of hematopoietic progenitor cells. A time- and concentration-dependent cytotoxicity study was performed on neoplastic coloncarcinoma and osteosarcoma cell lines. BPO4 functionalization with folic acid, introduced to improve the uptake by tumor cells, appeared to effectively limit the unwanted effects of NPs on the analyzed blood components. Boron neutron capture therapy (BNCT) is a radiotherapy treatment modality based on the accumulation of a (10)B-containing drug and subsequent irradiation with low energy neutrons, inducing the decay of (10)B to (7)Li and an α particle, causing neoplastic cell death. This team of authors reports on a folic acid functionalized BPO4 nanoparticle with improved characteristics compared with conventional BNCT approaches, as demonstrated in tumor cell lines, and hopefully to be followed by translational human studies. © 2014.

  4. Boron implanted strontium titanate

    NASA Astrophysics Data System (ADS)

    Cooper, C. J. M.

    Single crystals of strontium titanate implanted with boron were found to have highly conductive surface layers. The effects of varying dose from 10 to the 16th power to 10 to the 17th power ions/sq cm, implantation voltage from 50 to 175 keV and annealing conditions on the room temperature surface resistance and Hall mobility are presented. Variation of the implantation voltage did not have a major effect on the sheet resistances obtained by boron implantation of strontium titanate, while dose and annealing conditions have major effects. Doses of 5 x 10 to the 16th power ions/sq cm required annealing on the order of one hour at 500 K for maximum reduction of the room temperature resistance in the implanted layer. Samples implanted with a dose of 1 x 10 to the 17th power ions/sq cm required slightly higher temperatures (approximately 575 K) to obtain a minimum resistance at room temperature. Long term (several weeks) room temperature annealing was found to occur in high dose samples. After one to two months at room temperature followed by an anneal to 575 K, the surface resistances were found to be lower than those produced by the annealing of a freshly implanted sample to 575 K.

  5. Transition metals as Lewis bases: "Z-type" boron ligands and metal-to-boron dative bonding.

    PubMed

    Braunschweig, Holger; Dewhurst, Rian D

    2011-01-21

    While the vast majority of inorganic chemistry involves electron donation from main-group atoms to metals, an intriguing yet flip-side exists: where Lewis-basic metals donate electron density to Lewis-acidic main-group atoms (most often boron). These so-called "Z-type" ligands, along with other less clear-cut complexes, are examples of this metal-ligand role reversal. This perspective article offers an introduction to metal-to-boron dative bonding, and attempts to correlate spectroscopic and structural data from the complexes.

  6. On-plate-selective enrichment of glycopeptides using boronic acid-modified gold nanoparticles for direct MALDI-QIT-TOF MS analysis.

    PubMed

    Tang, Jia; Liu, Yingchao; Qi, Dawei; Yao, Guoping; Deng, Chunhui; Zhang, Xiangmin

    2009-11-01

    In this study, an on-plate-selective enrichment method is developed for fast and efficient glycopeptide investigation. Gold nanoparticles were first spotted and sintered on a stainless-steel plate, then modified with 4-mercaptophenylboronic acid to provide porous substrate with large specific surface and dual functions. These spots were used to selectively capture glycopeptides from peptide mixtures and the captured target peptides could be analyzed by MALDI-MS simply by deposition of 2,5-dihydroxybenzoic acid matrix. Horseradish peroxidase was employed as a standard glycoprotein to investigate the enrichment efficiency. In this way, the enrichment, washing and detection steps can all be fulfilled on a single MALDI target plate. The relatively small sample amount needed, low detection limit and rapid selective enrichment have made this on-plate strategy promising for online enrichment of glycopeptides, which could be applied in high-throughput proteome research.

  7. Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite.

    PubMed

    Shavnya, Andre; Hesp, Kevin D; Mascitti, Vincent; Smith, Aaron C

    2015-11-09

    A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis.

  8. Entropy of gaseous boron monobromide

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Feng; Peng, Xiao-Long; Zhang, Lie-Hui; Wang, Chao-Wen; Jia, Chun-Sheng

    2017-10-01

    We present an explicit representation of molar entropy for gaseous boron monobromide in terms of experimental values of only three molecular constants. Fortunately, through comparison of theoretically calculated results and experimental data, we find that the molar entropy of gaseous boron monobromide can be well predicted by employing the improved Manning-Rosen oscillator to describe the internal vibration of boron monobromide molecule. The present approach provides also opportunities for theoretical predictions of molar entropy for other gases with no use of large amounts of experimental spectroscopy data.

  9. NHC Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes.

    PubMed

    Zhou, Jing; Berthel, Johannes H J; Kuntze-Fechner, Maximilian W; Friedrich, Alexandra; Marder, Todd B; Radius, Udo

    2016-07-01

    An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with aryl boronate esters using NHC nickel complexes as catalysts is described. The efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin, p-tolyl-Bcat) and the corresponding boronic acid (p-tolyl-B(OH)2) in this type of cross-coupling reaction were evaluated (eg, ethyleneglycolato; neop, neopentylglycolato; pin, pinacolato; cat, catecholato). Aryl-Beg was shown to be the most reactive boronate ester among those studied. The use of CsF as an additive is essential for an efficient reaction of hexafluorobenzene with aryl neopentylglycolboronates.

  10. A new and effective approach to boron removal by using novel boron-specific fungi isolated from boron mining wastewater.

    PubMed

    Taştan, Burcu Ertit; Çakir, Dilara Nur; Dönmez, Gönül

    2016-01-01

    Boron-resistant fungi were isolated from the wastewater of a boron mine in Turkey. Boron removal efficiencies of Penicillium crustosum and Rhodotorula mucilaginosa were detected in different media compositions. Minimal Salt Medium (MSM) and two different waste media containing molasses (WM-1) or whey + molasses (WM-2) were tested to make this process cost effective when scaled up. Both isolates achieved high boron removal yields at the highest boron concentrations tested in MSM and WM-1. The maximum boron removal yield by P. crustosum was 45.68% at 33.95 mg l(-1) initial boron concentration in MSM, and was 38.97% at 42.76 mg l(-1) boron for R. mucilaginosa, which seemed to offer an economically feasible method of removing boron from the effluents.

  11. Interactions between dietary boron and thiamine affect lipid metabolism

    SciTech Connect

    Herbel, J.L.; Hunt, C.D. )

    1991-03-15

    An experiment was designed to test the hypothesis that dietary boron impacts upon the function of various coenzymes involved in energy metabolism. In a 2 {times} 7 factorially-arranged experiment, weanling, vitamin D{sub 3}-deprived rats were fed a ground corn-casein-corn oil based diet supplemented with 0 or 2 mg boron/kg and 50% of the requirement for thiamine (TM), riboflavin (RF), pantothenic acid (PA) or pyridoxine (PX); 0% for folic acid (FA) or nicotinic acid (NA). All vitamins were supplemented in adequate amounts in the control diet. At 8 weeks of age, the TM dietary treatment was the one most affected by supplemental dietary boron (SDB). In rats that were fed 50% TM, SDB increased plasma concentrations of triglyceride (TG) and activity of alanine transaminase (ALT), and the liver to body weight (L/B) ratio. However, in the SDB animals, adequate amounts of TM decreased the means of those variables to near that observed in non-SDB rats fed 50% TM. The findings suggest that an interaction between dietary boron and TM affects lipid metabolism.

  12. Boron compounds reduce vanadium tetraoxide genotoxicity in human lymphocytes.

    PubMed

    Geyikoglu, Fatime; Turkez, Hasan

    2008-11-01

    Vanadium has potential medical and pharmacological uses although it may also show genotoxic effects. Biological effects of boron are defined, but its interaction with vanadium is not known for therapeutic uses. The objective of present study was especially to determine whether boron compounds (boric acid and borax) conferred the protection against vanadium(IV) tetraoxide genotoxicity. After the application of vanadium (5, 10 and 20mg/l) and boron compounds (5 and 10mg/l), blood cultures were assessed by genetic endpoints and total antioxidant capacity (TAC). According to our results, vanadium(IV) tetraoxide induced a reduction in proliferation index (PI). Besides, the frequencies of sister-chromatid exchanges (SCEs), micronuclei (MN) rates and chromosomal aberrations (CAs) in peripheral lymphocytes were significantly increased by vanadium(IV) tetraoxide (10 and 20mg/l) compared to controls. On the other hand, boric acid and borax did not show cytotoxic and genotoxic effects at the concentrations tested. Moreover, these compounds elevated TAC in erythrocytes. The order of anti-genotoxicity efficacy against vanadium was boric acid and borax, respectively. In conclusion, boron compounds have been shown to protect vanadium-induced DNA damage in vitro for the first time. Copyright © 2008 Elsevier B.V. All rights reserved.

  13. Boron and Boron-Rich Solids at High Pressures

    NASA Astrophysics Data System (ADS)

    Polian, Alain; Ovsyannikov, Sergey V.; Gauthier, Michel; Munsch, Pascal; Chervin, Jean-Claude; Lemarchand, Gilles

    Boron seems to be the indispensable ingredient to obtain materials with high hardness. It exists under many different structures. The simplest member of the family, α-boron is based on an arrangement of slightly distorted B12 icosahedra in a rhombohedral unit cell. B12X2 compounds, with X = O, P, As, are based on the α-boron structure, with the X atoms in the inter-icosahedra space. The stability of α-boron has been studied by x-ray diffraction and Raman scattering up to 100 GPa, showing no sign of phase transformation, and by Raman scattering for B12P2 and B12As2 with the observation of phase transformation in the 80 GPa range.

  14. The effect of boron oxide on the composition, structure, and adsorptivity of glass surfaces

    NASA Astrophysics Data System (ADS)

    Schaut, Robert A.

    Boron oxide has been added to commercial silicate glasses for many years to aid in lowering melting temperatures, lowering thermal expansion, and controlling chemical durability. The fact that simple borate glasses have rather high thermal expansion and low chemical durability attests to the unique influence of boron oxide additions upon the properties of silicate glasses. However, the impact of boron oxide additions upon surface properties of multicomponent borosilicates such as adsorption and reactivity is not yet well understood. In particular, the presence of multiple coordination states for boron is expected to introduce adsorption sites with different acidic or basic behavior, but their existence is yet unproven. To investigate these effects, multicomponent sodium aluminosilicate glasses have been prepared with varying sodium and boron concentrations and drawn into moderately high-surface-area continuous filament fibers. A relatively new technique, boron K-edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is applied to study the local boron coordination at fracture and melt-derived fiber surfaces of these glasses. This structural information is combined with surface compositional information by X-ray Photoelectron Spectroscopy (XPS) to characterize the local atomic structure of boron at the as-formed glass surface. Finally, this information is used to interpret the adsorptivity of these as-formed and leached surfaces toward short-chain alcohol molecules through a new Inverse Gas Chromatography---Temperature Programmed Desorption (IGC-TPD) experiment. The results clearly show that boron additions to alkali-free glass surfaces introduce a unique adsorption site which is not present on boron-free glass surfaces and is easily removed by leaching in acidic solutions.

  15. Combined 3D-QSAR, Molecular Docking and Molecular Dynamics Study on Derivatives of Peptide Epoxyketone and Tyropeptin-Boronic Acid as Inhibitors Against the β5 Subunit of Human 20S Proteasome

    PubMed Central

    Liu, Jianling; Zhang, Hong; Xiao, Zhengtao; Wang, Fangfang; Wang, Xia; Wang, Yonghua

    2011-01-01

    An abnormal ubiquitin-proteasome is found in many human diseases, especially in cancer, and has received extensive attention as a promising therapeutic target in recent years. In this work, several in silico models have been built with two classes of proteasome inhibitors (PIs) by using 3D-QSAR, homology modeling, molecular docking and molecular dynamics (MD) simulations. The study resulted in two types of satisfactory 3D-QSAR models, i.e., the CoMFA model (Q2 = 0.462, R2pred = 0.820) for epoxyketone inhibitors (EPK) and the CoMSIA model (Q2 = 0.622, R2pred = 0.821) for tyropeptin-boronic acid derivatives (TBA). From the contour maps, some key structural factors responsible for the activity of these two series of PIs are revealed. For EPK inhibitors, the N-cap part should have higher electropositivity; a large substituent such as a benzene ring is favored at the C6-position. In terms of TBA inhibitors, hydrophobic substituents with a larger size anisole group are preferential at the C8-position; higher electropositive substituents like a naphthalene group at the C3-position can enhance the activity of the drug by providing hydrogen bond interaction with the protein target. Molecular docking disclosed that residues Thr60, Thr80, Gly106 and Ser189 play a pivotal role in maintaining the drug-target interactions, which are consistent with the contour maps. MD simulations further indicated that the binding modes of each conformation derived from docking is stable and in accord with the corresponding structure extracted from MD simulation overall. These results can offer useful theoretical references for designing more potent PIs. PMID:21673924

  16. An experimental and theoretical investigation of Acenaphthene-5-boronic acid: conformational study, NBO and NLO analysis, molecular structure and FT-IR, FT-Raman, NMR and UV spectra.

    PubMed

    Karabacak, Mehmet; Sinha, Leena; Prasad, Onkar; Asiri, Abdullah M; Cinar, Mehmet

    2013-11-01

    The solid state Fourier transform infrared (FT-IR) and FT-Raman spectra of Acenaphthene-5-boronic acid (AN-5-BA), have been recorded in the range 4000-400cm(-1) and 4000-10cm(-1), respectively. Density functional theory (DFT), with the B3LYP functional was used for the optimization of the ground state geometry and simulation of the infrared and Raman spectra of the molecule. The vibrational wave numbers and their assignments were examined theoretically using the Gaussian 09 set of quantum chemistry codes and the normal modes were assigned by a scaled quantum mechanical (SQM) force field approach. Hydrogen-bonded dimer of AN-5-BA, optimized by counterpoise correction, has also been studied by B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge-Including Atomic Orbital (GIAO) method. Natural bond orbital (NBO) analysis has been applied to study stability of the molecule arising from charge delocalization. UV spectrum of the title compound was also recorded and the electronic properties, such as frontier orbitals, and band gap energies were measured by TD-DFT approach. The first order hyperpolarizability 〈β〉, its components and associated properties such as average polarizability and anisotropy of the polarizability (α and Δα) of AN-5-BA was calculated using the finite-field approach.

  17. The boron efflux transporter ROTTEN EAR is required for maize inflorescence development and fertility.

    PubMed

    Chatterjee, Mithu; Tabi, Zara; Galli, Mary; Malcomber, Simon; Buck, Amy; Muszynski, Michael; Gallavotti, Andrea

    2014-07-01

    Although boron has a relatively low natural abundance, it is an essential plant micronutrient. Boron deficiencies cause major crop losses in several areas of the world, affecting reproduction and yield in diverse plant species. Despite the importance of boron in crop productivity, surprisingly little is known about its effects on developing reproductive organs. We isolated a maize (Zea mays) mutant, called rotten ear (rte), that shows distinct defects in vegetative and reproductive development, eventually causing widespread sterility in its inflorescences, the tassel and the ear. Positional cloning revealed that rte encodes a membrane-localized boron efflux transporter, co-orthologous to the Arabidopsis thaliana BOR1 protein. Depending on the availability of boron in the soil, rte plants show a wide range of phenotypic defects that can be fully rescued by supplementing the soil with exogenous boric acid, indicating that rte is crucial for boron transport into aerial tissues. rte is expressed in cells surrounding the xylem in both vegetative and reproductive tissues and is required for meristem activity and organ development. We show that low boron supply to the inflorescences results in widespread defects in cell and cell wall integrity, highlighting the structural importance of boron in the formation of fully fertile reproductive organs. © 2014 American Society of Plant Biologists. All rights reserved.

  18. Evaluation of ecological and in vitro effects of boron on prostate cancer risk (United States).

    PubMed

    Barranco, Wade T; Hudak, Paul F; Eckhert, Curtis D

    2007-02-01

    To determine: (1) the correlation of prostate cancer incidence and mortality with groundwater boron and selenium concentrations; and (2) the impact of boron on prostate cancer cell proliferation during co-treatment with alternative chemo-preventative agents, along with boron pre-treatment effects on cell sensitivity to ionizing radiation. For regression analysis, data on prostate cancer incidence and mortality were obtained from the Texas Cancer Registry, while groundwater boron and selenium concentrations were derived from the Texas Water Development Board. Cultured DU-145 prostate cancer cells were used to assess the impact of boric acid on cell proliferation when applied in combination with selenomethionine and genistein, or preceding radiation exposure. Groundwater boron levels correlated with a decrease in prostate cancer incidence (R = 0.6) and mortality (R = 0.6) in state planning regions, whereas selenium did not (R = 0.1; R = 0.2). Growth inhibition was greater during combined treatments of boric acid and selenomethionine, or boric acid and genistein, versus singular treatments. 8-day boric acid pre-exposure enhanced the toxicity of ionizing radiation treatment, while dose-dependently decreasing the expression of anti-apoptotic protein Bcl-2. Increased groundwater boron concentrations, across the state of Texas, correlate with reduced risk of prostate cancer incidence and mortality. Also, boric acid improves the anti-proliferative effectiveness of chemo-preventative agents, selenomethionine and genistein, while enhancing ionizing radiation cell kill.

  19. A surprising substituent effect provides a superior boronic acid catalyst for mild and metal-free direct Friedel-Crafts alkylations and prenylations of neutral arenes.

    PubMed

    Ricardo, Carolynne L; Mo, Xiaobin; McCubbin, J Adam; Hall, Dennis G

    2015-03-09

    The development of more general and efficient catalytic processes for Friedel-Crafts alkylations is an important objective of interest toward the production of pharmaceuticals and commodity chemicals. Herein, 2,3,4,5-tetrafluorophenylboronic acid was identified as a potent air- and moisture-tolerant metal-free catalyst that significantly improves the scope of direct Friedel-Crafts alkylations of a variety of slightly activated and neutral arenes, including polyarenes, with allylic and benzylic alcohols. This method also provides a simple alternative for the direct installation of prenyl units commonly found in naturally occurring arenes. Alkylations with benzylic alcohols occur under exceptionally mild conditions.

  20. Copper passivation of boron in silicon and boron reactivation kinetics

    NASA Astrophysics Data System (ADS)

    Aboelfotoh, M. O.; Svensson, B. G.

    1991-12-01

    Copper passivation of substitutional boron in single-crystal silicon and the reactivation kinetics of the passivated boron have been investigated with the use of Schottky-barrier structures formed by the deposition of copper on boron-doped silicon at room temperature. It is found that passivation of the boron acceptors occurs after copper deposition. The results suggest that the fast-diffusing interstitial Cu+ passivates the boron acceptors by forming neutral B-Cu complexes, rather than by direct compensation. No compensating donor levels associated with Cu are observed. These results are consistent with recent theoretical predictions. The reactivation kinetics are first order with an activation energy of 0.89 eV, and the annealing process is found to be controlled by long-range diffusion, rather than by pure dissociation. The thermal dissociation of the B-Cu complexes is driven by the formation of the copper silicide η'-Cu3Si, indicating the importance of silicide formation in the reactivation of the boron acceptors.

  1. Nothing Boring About Boron

    PubMed Central

    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

  2. Tris(tert-butoxy)siloxy derivatives of boron, including the boronous acid HOB[OSi(O(t)Bu)(3)](2) and the metal (siloxy)boryloxide complex Cp(2)Zr(Me)OB[OSi(O(t)Bu)(3)](2): a remarkable crystal structure with 18 independent molecules in its asymmetric unit.

    PubMed

    Fujdala, Kyle L; Oliver, Allen G; Hollander, Frederick J; Tilley, T Don

    2003-02-24

    Silanolysis of B(O(t)Bu)(3) with 2 and 3 equiv of HOSi(O(t)Bu)(3) led to the formation of (t)BuOB[OSi(O(t)Bu)(3)](2) (1) and B[OSi(O(t)Bu)(3)](3) (2), respectively. Compounds 1 and 2 are efficient single-source molecular precursors to B/Si/O materials via thermolytic routes in nonpolar media, as demonstrated by the generation of BO(1.5).2SiO(2) (BOSi2(xg)) and BO(1.5).3SiO(2) (BOSi3(xg)) xerogels, respectively. Use of a block copolymer template provided B/Si/O materials (BOSi2(epe) and BOSi3(epe)) with a broad distribution of mesopores (by N(2) porosimetry) and smaller, more uniform particle sizes (by TEM) as compared to the nontemplated materials. Hydrolyses of 1 and 2 with excess H(2)O resulted in formation of the expected amounts of (t)BuOH and HOSi(O(t)Bu)(3); however, reaction of 1 with 1 equiv of H(2)O led to isolation of the new boronous acid HOB[OSi(O(t)Bu)(3)](2) (3). This ligand precursor is well suited for the synthesis of new metal (siloxy)boryloxide complexes via proton-transfer reactions involving the BOH group. The reaction of 3 with Cp(2)ZrMe(2) resulted in formation of Cp(2)Zr(Me)OB[OSi(O(t)Bu)(3)](2) (4) in high yield. This rare example of a transition metal boryloxide complex crystallizes in the triclinic space group Ponemacr; and exhibits a crystal structure with an unprecedented number of independent molecules in its asymmetric unit (i.e., Z' = 18 and Z = 36). This unusual crystal structure presented an opportunity to perform statistical analyses of the metric parameters for the 18 crystallographically independent molecules. Complex 4 readily converts to Cp(2)Zr[OSi(O(t)Bu)(3)](2) (5) upon thermolysis or upon dissolution in Et(2)O at room temperature.

  3. Reducing Boron Toxicity by Microbial Sequestration

    SciTech Connect

    Hazen, T.; Phelps, T.J.

    2002-01-01

    While electricity is a clean source of energy, methods of electricity-production, such as the use of coal-fired power plants, often result in significant environmental damage. Coal-fired electrical power plants produce air pollution, while contaminating ground water and soils by build-up of boron, which enters surrounding areas through leachate. Increasingly high levels of boron in soils eventually overcome boron tolerance levels in plants and trees, resulting in toxicity. Formation of insoluble boron precipitates, mediated by mineral-precipitating bacteria, may sequester boron into more stable forms that are less available and toxic to vegetation. Results have provided evidence of microbially-facilitated sequestration of boron into insoluble mineral precipitates. Analyses of water samples taken from ponds with high boron concentrations showed that algae present contained 3-5 times more boron than contained in the water in the samples. Boron sequestration may also be facilitated by the incorporation of boron within algal cells. Experiments examining boron sequestration by algae are in progress. In bacterial experiments with added ferric citrate, the reduction of iron by the bacteria resulted in an ironcarbonate precipitate containing boron. An apparent color change showing the reduction of amorphous iron, as well as the precipitation of boron with iron, was more favorable at higher pH. Analysis of precipitates by X-ray diffraction, scanning electron microscopy, and inductively coupled plasma mass spectroscopy revealed mineralogical composition and biologicallymediated accumulation of boron precipitates in test-tube experiments.

  4. Nano boron nitride flatland.

    PubMed

    Pakdel, Amir; Bando, Yoshio; Golberg, Dmitri

    2014-02-07

    Recent years have witnessed many breakthroughs in research on two-dimensional (2D) nanomaterials, among which is hexagonal boron nitride (h-BN), a layered material with a regular network of BN hexagons. This review provides an insight into the marvellous nano BN flatland, beginning with a concise introduction to BN and its low-dimensional nanostructures, followed by an overview of the past and current state of research on 2D BN nanostructures. A comprehensive review of the structural characteristics and synthetic routes of BN monolayers, multilayers, nanomeshes, nanowaves, nanoflakes, nanosheets and nanoribbons is presented. In addition, electronic, optical, thermal, mechanical, magnetic, piezoelectric, catalytic, ecological, biological and wetting properties, applications and research perspectives for these novel 2D nanomaterials are discussed.

  5. Boron diffusion in silicon devices

    DOEpatents

    Rohatgi, Ajeet; Kim, Dong Seop; Nakayashiki, Kenta; Rounsaville, Brian

    2010-09-07

    Disclosed are various embodiments that include a process, an arrangement, and an apparatus for boron diffusion in a wafer. In one representative embodiment, a process is provided in which a boric oxide solution is applied to a surface of the wafer. Thereafter, the wafer is subjected to a fast heat ramp-up associated with a first heating cycle that results in a release of an amount of boron for diffusion into the wafer.

  6. Neutron detectors comprising boron powder

    DOEpatents

    Wang, Zhehui; Morris, Christopher; Bacon, Jeffrey Darnell; Makela, Mark F; Spaulding, Randy Jay

    2013-05-21

    High-efficiency neutron detector substrate assemblies comprising a first conductive substrate, wherein a first side of the substrate is in direct contact with a first layer of a powder material comprising .sup.10boron, .sup.10boron carbide or combinations thereof, and wherein a conductive material is in proximity to the first layer of powder material; and processes of making said neutron detector substrate assemblies.

  7. In situ product removal of ketoses by immobilized 3-amino phenyl boronic acid: effect of immobilization method on pH profile.

    PubMed

    Dukler, A; Freeman, A

    2001-10-05

    The use of polymeric derivatives of phenylboronic acid (PBA) as an effective means for specific in situ product removal of ketoses from aldose-containing reaction mixtures, strongly depends on the retention of selective binding of ketoses exhibited by soluble PBA and 3-amino PBA, by their polymeric, water insoluble analogs. In this communication we demonstrate that immobilization chemistry has a strong effect on ketose preferred binding by polymeric PBA derivatives. Our results indicate that for the preparation of an effective and more specific adsorbent, 3-amino PBA should be coupled to the polymeric carrier via alkylamino chemistry and not via the commonly employed amido derivative. Immobilized alkylamino-PBA exhibited selective fructose and xylulose binding throughout glucose and xylose isomerization processes at the pH range of 7.0-8.0.

  8. New evidences on efficacy of boronic acid-based derivatization method to identify sugars in plant material by gas chromatography-mass spectrometry.

    PubMed

    Faraco, Marianna; Fico, Daniela; Pennetta, Antonio; De Benedetto, Giuseppe E

    2016-10-01

    This work presents an analytical procedure based on gas chromatography-mass spectrometry which allows the determination of aldoses (glucose, mannose, galactose, arabinose, xylose, fucose, rhamnose) and chetoses (fructose) in plant material. One peak for each target carbohydrate was obtained by using an efficient derivatization employing methylboronic acid and acetic anhydride sequentially, whereas the baseline separation of the analytes was accomplished using an ionic liquid capillary column. First, the proposed method was optimized and validated. Successively, it was applied to identify the carbohydrates present in plant material. Finally, the procedure was successfully applied to samples from a XVII century painting, thus highlighting the occurrence of starch glue and fruit tree gum as polysaccharide materials.

  9. Controlling the Morphology and Oxidation Resistance of Boron Carbide Synthesized Via Carbothermic Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Ahmed, Yasser M. Z.; El-Sheikh, Said M.; Ewais, Emad M. M.; Abd-Allah, Asmaa A.; Sayed, Said A.

    2017-02-01

    Boron carbide powder was synthesized from boric acid and lactose mixtures via easy procedure. Boric acid and lactose solution mixtures were roasted in stainless steel pot at 280 °C for 24 h. Boron carbide was obtained by heating the roasted samples under flowing of industrial argon gas at 1500 °C for 3 h. The amount of borate ester compound in the roasted samples was highly influenced by the boron/carbon ratio in the starting mixtures and plays a versatile role in the produced boron carbide. The high-purity boron carbide powder was produced with a sample composed of lowest boron/carbon ratio of 1:1 without calcination step. Particle morphology was changed from nano-needles like structure of 8-10 nm size with highest carbon ratio mixture to spherical shape of >150 nm size with lowest one. The oxidation resistance performance of boron carbide is highly dependent on the morphology and grain size of the synthesized powder.

  10. Controlling the Morphology and Oxidation Resistance of Boron Carbide Synthesized Via Carbothermic Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Ahmed, Yasser M. Z.; El-Sheikh, Said M.; Ewais, Emad M. M.; Abd-Allah, Asmaa A.; Sayed, Said A.

    2017-03-01

    Boron carbide powder was synthesized from boric acid and lactose mixtures via easy procedure. Boric acid and lactose solution mixtures were roasted in stainless steel pot at 280 °C for 24 h. Boron carbide was obtained by heating the roasted samples under flowing of industrial argon gas at 1500 °C for 3 h. The amount of borate ester compound in the roasted samples was highly influenced by the boron/carbon ratio in the starting mixtures and plays a versatile role in the produced boron carbide. The high-purity boron carbide powder was produced with a sample composed of lowest boron/carbon ratio of 1:1 without calcination step. Particle morphology was changed from nano-needles like structure of 8-10 nm size with highest carbon ratio mixture to spherical shape of >150 nm size with lowest one. The oxidation resistance performance of boron carbide is highly dependent on the morphology and grain size of the synthesized powder.

  11. Relationships of anion-exchange sorption of boron from natural thermal-spring water

    SciTech Connect

    Meichik, N.R.; Leikin, Yu.A.; Antipov, M.A.; Goryacheva, N.V.; Klimenko, I.S.; Medvedev, S.A.; Galitskaya, N.B.

    1988-02-20

    Boric acid is one of the characteristic components of Kamchatka waters. Extraction of boron from thermal waters for production of potable water is closely linked with current problems of multiproduct utilization of resources and protection of the environment. The authors have investigated the possibilities of using ion exchange for extraction of boron from natural waters, and studied the sorption relationships by a dynamic method. They synthesized a macroporous anion-exchanger based on a copolymer of styrene with divinylbenzene, containing N-methylglucamine groups (ANB-11 resin). ANB-11 resin had high sorption capacity for boron anions during sorption from thermal-spring water. The experimental data were described by Elkins equation.

  12. Non-crystalline composite tissue engineering scaffolds using boron-containing bioactive glass and poly(D,L-lactic acid) coatings.

    PubMed

    Mantsos, T; Chatzistavrou, X; Roether, J A; Hupa, L; Arstila, H; Boccaccini, A R

    2009-10-01

    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 degrees 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. In vitro determination of uptake, retention, distribution, biological efficacy, and toxicity of boronated compounds for neutron capture therapy: a comparison of porphyrins with sulfhydryl boron hydrides.

    PubMed

    Fairchild, R G; Kahl, S B; Laster, B H; Kalef-Ezra, J; Popenoe, E A

    1990-08-15

    A major problem remaining in the evaluation of boronated compounds for neutron capture therapy (NCT) is the need to know the intra- or extracellular microdistribution of boron. This is a consequence of the short range of the 10B(n,alpha)7Li reaction products (approximately 10 microns), such that biological efficacy is dependent upon intracellular distribution. In particular, if boron location is predominantly extracellular, a significant reduction in efficacy would be expected. The in vitro procedure described here was developed mainly to provide information regarding the intra- and extracellular location and concentration of boron. However, use of the technique also allows the measurement of compound uptake and retention (binding) and the determination of biological efficacy by the evaluation of survival curves obtained following irradiation with thermal neutrons. Comparison is made to results obtained with boric acid (H3(10)BO3) and to results calculated for various boron distributions. Concomitantly, an indication of compound toxicity can be obtained from the plating efficiency of unirradiated control cells. Currently, most investigators utilize in vivo systems for testing and evaluating boron uptake from various carrier molecules. Given the large number of boron compounds being synthesized and needing evaluation as to their usefulness for NCT, the in vitro technique described here is simple and advantageous for initial compound screening. In addition to sparing animal lives, it is both time and cost effective and utilizes much smaller quantities of test compound than are required for an in vivo assay. A boronated porphyrin (BOPP) evaluated by the above procedure shows an uptake and retention approximately 20 times that of sulfhydryl boron hydride monomer (BSH); the latter compound is currently being used clinically for NCT in Japan and is anticipated for use in clinical trials in the United States. If the advantages demonstrated by BOPP in these in vitro

  14. Inexpensive Method for Coating the Interior of Silica Growth Ampoules with Pyrolytic Boron Nitride

    NASA Technical Reports Server (NTRS)

    Wang, Jianbin; Regel, Liya L.; Wilcox, William R.

    2003-01-01

    An inexpensive method was developed for coating the interior of silica ampoules with hexagonal boron nitride. An aqueous solution of boric acid was used to coat the ampoule prior to drying in a vacuum at 200 C. This coating was converted to transparent boron nitride by heating in ammonia at 1000 C. Coated ampoules were used to achieve detached solidification of indium antimonide on earth.

  15. Trivalent boron nucleophile as a new tool in organic synthesis: reactivity and asymmetric induction.

    PubMed

    Cid, Jessica; Gulyás, Henrik; Carbó, Jorge J; Fernández, Elena

    2012-05-07

    Boron compounds have been traditionally regarded as "Lewis acids" preferring to accept electrons rather than donate them in the course of their reactions but current examples of unusual reactivity between tricoordinated boranes and electrophilic sites suggest a new conceptual context for the boryl moieties, based on their nucleophilic character which can be enhanced depending on the substituents on boron. This journal is © The Royal Society of Chemistry 2012

  16. Boronated porhyrins and methods for their use

    DOEpatents

    Miura, Michiko; Shelnutt, John A.; Slatkin, Daniel N.

    1999-03-02

    The present invention covers boronated porphyrins containing multiple carborane cages which selectively accumulate in neoplastic tissue within the irradiation volume and thus can be used in cancer therapies such as boron neutron capture therapy and photodynamic therapy.

  17. Boronated porhyrins and methods for their use

    DOEpatents

    Miura, M.; Shelnutt, J.A.; Slatkin, D.N.

    1999-03-02

    The present invention covers boronated porphyrins containing multiple carborane cages which selectively accumulate in neoplastic tissue within the irradiation volume and thus can be used in cancer therapies such as boron neutron capture therapy and photodynamic therapy. 3 figs.

  18. Synthesis and Utility of Dihydropyridine Boronic Esters**

    PubMed Central

    Panda, Santanu; Coffin, Aaron; Nguyen, Q. Nhu; Tantillo, Dean; Ready, Joseph M.

    2016-01-01

    When activated by an acylating agent, pyridine boronic esters react with organometallic reagents to form a dihydropyridine boronic ester. This intermediate allows access to a number of valuable substituted pyridine, dihydropyridine and piperidine products. PMID:26694785

  19. Synthesis and Utility of Dihydropyridine Boronic Esters.

    PubMed

    Panda, Santanu; Coffin, Aaron; Nguyen, Q Nhu; Tantillo, Dean J; Ready, Joseph M

    2016-02-05

    When activated by an acylating agent, pyridine boronic esters react with organometallic reagents to form a dihydropyridine boronic ester. This intermediate allows access to a number of valuable substituted pyridine, dihydropyridine, and piperidine products.

  20. Processing of boron carbide

    NASA Astrophysics Data System (ADS)

    Cho, Namtae

    The processing of boron carbide powder including sintering optimization, green body optimization and sintering behavior of nano-sized boron carbide was investigated for the development of complex shaped body armor. Pressureless sintered B4C relative densities as high as 96.7% were obtained by optimizing the soak temperature, and holding at that temperature for the minimum time required to reach terminal density. Although the relative densities of pressureless sintered specimens were lower than that of commercially produced hot-pressed B4C, their (Vickers) hardness values were comparable. For 4.45 cm dia. 1.35 cm height disk-shaped specimens, pressureless sintered to at least 93.0% relative density, post-hot isostatic pressing resulted in vast increases in relative densities (e.g. 100.0%) and hardness values significantly greater than that of commercially produced hot-pressed B 4C. The densification behavior of 20-40nm graphite-coated B4C nano-particles was studied using dilatometry, x-ray diffraction and electron microscopy. The higher than expected sintering onset from a nano-scale powder (˜1500°C) was caused by remnant B2O3 not removed by methanol washing, keeping particles separated until volatilization, and the carbon coatings, which imposed particle to particle contact of a substance more refractory than B4C. Solid state sintering (1500-1850°C) was followed by an arrest in contraction attributed to formation of eutectic liquid droplets of size more than 10X the original nano-particles. These droplets, induced to form well below known B4C-graphite eutectic temperatures by the high surface energy of nanoparticles, are interpreted to have quickly solidified to form a vast number of voids in particle packing, which in turn, impeded continued solid state sintering. Starting at 2200°C, a permanent liquid phase formed which facilitated a rapid measured contraction by liquid phase sintering and/or compact slumping.

  1. Heats of Formation for the Boronic Acids R–B(OH)2 and Boroxines R3B3O3 (R=H, Li, HBe, H2B, H3C, H2N, HO, F, and Cl) Calculated at the G2, G3, and G4 Levels of Theory

    PubMed Central

    Bock, Charles W.; Larkin, Joseph D.

    2014-01-01

    Boronic acids (R–B(OH)2) and their boroxine (R3B3O3) dehydration products have emerged as important classes of compounds with a multitude of diverse applications. However, the available heats of formation for these compounds are not always as accurate as would be required for further use. In this study the heats of formation at 298.15 K of R–B(OH)2 and R3B3O3 (R = H, Li, HBe, H2B, H3C, H2N, HO, F, and Cl) have been calculated at the G2, G3[G3B3], and G4 levels of theory and used to determine the enthalpy changes for the dehydration reactions: 3 R–B(OH)2 → R3B3O3 + 3 H2O; comparisons are made with other rigorous levels of theory, e.g. CBS-Q[CBS-QB3] and W1U, as well as with experimental values wherever possible. Enthalpy changes for the dehydration reactions have also been calculated using second-order Møller-Plesset perturbation theory (MP2) with the Dunning-Woon correlation-consistent aug-cc-pVDZ and aug-cc-pVTZ basis sets, and B3LYP density functional theory with the 6-311++G(2df,2pd) basis set. With the exception of H2N-B(OH)2, the dehydration reactions are consistently predicted to be exothermic. Our results provide a cautionary note for the use of the B3LYP functional in the calculation of structures and energies of boronic acids and boroxines. Where comparisons could be made, the G4 and W1U predictions for the heats of formation of these boron compounds differ significantly. PMID:24653975

  2. Improving the efficiency of boron application on the vineyards during NPK fertilization

    NASA Astrophysics Data System (ADS)

    Magomadov, Andy; Batukaev, Abdulmalik; Kalinitchenko, Valeriy; Minkina, Tatiana; Sushkova, Svetlana

    2017-04-01

    The effect of different doses and time of boron fertilization on growth and development of grape plants were studied on the soils of Terek-Kumskiy sands of Chechen Republic, Russian Federation. The studies have shown that sandy soils of pilot area have a low content of main macronutrients except of potassium. The boron content in the sandy soils varies within wide limits and characterizes this soil as lack of boron content especially in water-soluble boron distribution through the soil profile. It was developed a technique for roots feeding of grapes for the first time, that allows to control chemical processes the NPK uptake by plant roots. The studied process realized by implementation of optimum amount of boron in plant-available form, introduced in a certain phase of plants growth. It helps to improve the efficiency of nitrogen, phosphate, potassium using. It was found that boron improves the movement of growth substances and ascorbic acid from the leaves to the fertile parts and cannot be replaced by other nutrients. The plants need of boron throughout the growing season. Boron plays an important role in cell division and protein synthesis is an essential component of cell membranes. The use of boric acid as a fertilizer to increase the number of ovaries on grape plants, stimulating the formation of new points of stems and root growth, increased the number of shoots, improved growth, increased the sugar content of the grapes and taste of the fruit, which is a result of more active uptake of boron by grapes. The optimal dose of boron fertilization on the sandy soil and the comparative agroecological and economic evaluation of its application presented in the research. The use of boron fertilizers allowed to increase the sugar content, acidity, tasting score grapes up to 12-38%. The greatest effect of boron fertilization achieved by application to the phase start of sap flow in a dose of 3 kg/ha in the background N90P90K90. The developed technique for sandy

  3. Methods for boron delivery to mammalian tissue

    DOEpatents

    Hawthorne, M. Frederick; Feaks, Debra A.; Shelly, Kenneth J.

    2003-01-01

    Boron neutron capture therapy can be used to destroy tumors. This treatment modality is enhanced by delivering compounds to the tumor site where the compounds have high concentrations of boron, the boron compounds being encapsulated in the bilayer of a liposome or in the bilayer as well as the internal space of the liposomes. Preferred compounds, include carborane units with multiple boron atoms within the carborane cage structure. Liposomes with increased tumor specificity may also be used.

  4. Methods and compositions for boronizing metallic surfaces

    SciTech Connect

    Reid, D. K.

    1985-11-26

    The present disclosure is directed to methods and compositions for boronizing metal and in particular ferrous surfaces. It has been discovered that if hydrocarbons are processed in metallic equipment which have been previously boronized, that coke formation and deposition which is commonly experienced at high temperatures can be minimized if not totally eliminated. The compositions utilized for this purpose are comprised of boron or boron compounds contained in an organic solvent or carrier together with specific activating materials.

  5. On the applicability of [(18)F]FBPA to predict L-BPA concentration after amino acid preloading in HuH-7 liver tumor model and the implication for liver boron neutron capture therapy.

    PubMed

    Grunewald, Catrin; Sauberer, Michael; Filip, Thomas; Wanek, Thomas; Stanek, Johann; Mairinger, Severin; Rollet, Sofia; Kudejova, Petra; Langer, Oliver; Schütz, Christian; Blaickner, Matthias; Kuntner, Claudia

    2017-01-01

    In recent years extra-corporal application of boron neutron capture therapy (BNCT) was evaluated for liver primary tumors or liver metastases. A prerequisite for such a high-risk procedure is proof of preferential delivery and high uptake of a (10)B-pharmaceutical in liver malignancies. In this work we evaluated in a preclinical tumor model if [(18)F]FBPA tissue distribution measured with PET is able to predict the tissue distribution of [(10)B]L-BPA. Tumor bearing mice (hepatocellular carcinoma cell line, HuH-7) were either subject of a [(18)F]FBPA-PET scan with subsequent measurement of radioactivity content in extracted organs using a gamma counter or injected with [(10)B]L-BPA with tissue samples analyzed by prompt gamma activation analysis (PGAA) or quantitative neutron capture radiography (QNCR). The impact of L-tyrosine, L-DOPA and L-BPA preloading on the tissue distribution of [(18)F]FBPA and [(10)B]L-BPA was evaluated and the pharmacokinetics of [(18)F]FBPA investigated by compartment modeling. We found a significant correlation between [(18)F]FBPA and [(10)B]L-BPA uptake in tumors and various organs as well as high accumulation levels in pancreas and kidneys as reported in previous studies. Tumor-to-liver ratios of [(18)F]FBPA ranged from 1.2 to 1.5. Preloading did not increase the uptake of [(18)F]FBPA or [(10)B]L-BPA in any organ and compartment modeling showed no statistically significant differences in [(18)F]FBPA tumor kinetics. [(18)F]FBPA-PET predicts [(10)B]L-BPA concentration after amino acid preloading in HuH-7 hepatocellular carcinoma models. Preloading had no effect on tumor uptake of [(18)F]FBPA. Despite differences in chemical structure and administered dose [(18)F]FBPA and [(10)B]L-BPA demonstrate an equivalent biodistribution in a preclinical tumor model. IMPLICATIONS FOR PATIENT CARE: [(18)F]FBPA-PET is suitable for treatment planning and dose calculations in BNCT applications for liver malignancies. However, alternative tracers with more

  6. Diffusion of boron in alloys

    SciTech Connect

    Wang, W.; Zhang, S; He, X.

    1995-04-01

    By means of particle tracking autoradiography (PTA), the diffusion coefficients of boron between 900 and 1,200 C were measured in 04MnNbB steel, 25MnTiB steel, Ni-B, Fe-30%Ni-B and Fe-3%Si-B alloys, and the frequency factor D{sub 0} and activation energy Q were obtained respectively. The experiment results indicated that there was an obvious difference between the present result and the result obtained by Busby (in 1953). It was found that the boron diffusivity in {gamma}-Fe increased as Ni was added. The diffusivity of boron in Fe-3%Si-B alloy with b.c.c. structure was much slower than one obtained by Busby in {alpha}-Fe (1954), which, however, was much faster than the results obtained in {gamma}-Fe (with f.c.c. structure). Based on the present data of boron diffusion coefficients, the mechanism of segregation of boron to grain boundaries is discussed.

  7. Wettability of boron carbide

    SciTech Connect

    Torvund, T.; Akselsen, O.M.; Ulvensoeen, J.H.; Grong, O.

    1994-12-31

    The wettability of boron carbide has been examined by means of the sessile drop method, using the following candidate alloys: (96wt%AG-4wt%Ti), (Ag-26.5wt%Cu-3wt%Ti), (Sn-10wt%Ag-4wt%Ti), Sn(99.95wt%) and Al(99.99wt%). The results show that B{sub 4}C is completely wetted by the Ag-based alloys. Sn-10wt%Ag-4wt%Ti alloy and pure Al partly wet the B{sub 4}C surface, while pure Sn does not wet B{sub 4}C at all. For all the alloys used, except pure Sn, a reaction layer was observed at the interface between the ceramic part and the metal drop. Although the spreading kinetics of the Al-drop was much slower compared with the Ti-containing alloys, the reaction rate was considerably higher in the former case. This suggests that aluminium is an attractive candidate material for brazing of B{sub 4}C. Formation of the low melting B{sub 2}O{sub 3} at the B{sub 4}C surface may cause oxidation of the filler metal during joining, which, in turn, leads to a low bond strength.

  8. Boron intake and prostate cancer risk.

    PubMed

    Gonzalez, Alejandro; Peters, Ulrike; Lampe, Johanna W; White, Emily

    2007-12-01

    Experimental studies suggest that boron may prevent prostate cancer. Only one small epidemiological study has been conducted of boron, which found that those in the highest quartile of boron intake had less than half the risk of prostate cancer versus those in the lowest quartile. We evaluated the association between boron intake and prostate cancer within the VITamins And Lifestyle (VITAL) cohort. A total of 35,244 men completed the baseline supplement and food frequency questionnaire (FFQ) in 2000-2002. A boron database was constructed from published sources to estimate boron intake from the FFQ and from multivitamins. A total of 832 men developed prostate cancer from baseline to 31 December 2004. Dietary boron intake and total boron intake from diet plus multivitamins were not associated with prostate cancer risk. The hazard ratio of prostate cancer for those in the highest versus lowest quartile of total boron intake was 1.17 (95% CI 0.85, 1.61). This risk did not vary by prostate cancer stage or Gleason score. Furthermore, none of the foods high in boron content was associated with a decreased risk of prostate cancer. This cohort study provides no evidence for a preventive role of boron intake on prostate cancer. Since few studies exist on this topic, future research is needed to better elucidate any role that boron may play in the prevention of prostate cancer.

  9. Mineral resource of the month: boron

    USGS Publications Warehouse

    Lyday, Phyllis A.

    2005-01-01

    What does boron have to do with baseball, apple pie, motherhood and Chevrolet? Boron minerals and chemicals are used in the tanning of leather baseballs and gloves; in micro-fertilizer to grow apples and in the glass and enamels of bakewares to cook apple pie; in boron detergents for soaking baby clothes and diapers; and in fiberglass parts for the Chevrolet Corvette.

  10. Graphene on hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    Yankowitz, Matthew; Xue, Jiamin; LeRoy, B. J.

    2014-07-01

    The field of graphene research has developed rapidly since its first isolation by mechanical exfoliation in 2004. Due to the relativistic Dirac nature of its charge carriers, graphene is both a promising material for next-generation electronic devices and a convenient low-energy testbed for intrinsically high-energy physical phenomena. Both of these research branches require the facile fabrication of clean graphene devices so as not to obscure its intrinsic physical properties. Hexagonal boron nitride has emerged as a promising substrate for graphene devices as it is insulating, atomically flat and provides a clean charge environment for the graphene. Additionally, the interaction between graphene and boron nitride provides a path for the study of new physical phenomena not present in bare graphene devices. This review focuses on recent advancements in the study of graphene on hexagonal boron nitride devices from the perspective of scanning tunneling microscopy with highlights of some important results from electrical transport measurements.

  11. Silica - Boronate affinity material for quick enrichment of intracellular nucleosides.

    PubMed

    Wang, Shuxia; Li, Huihui; Guan, Xiujuan; Cheng, Ting; Zhang, Haixia

    2017-05-01

    Boronic acid modified materials have been widely used to adsorb nucleosides, but their adsorption capacities require further improvement. Most cis-diol containing biomolecules are in very low abundance along with interfering components in real samples, and need to be enriched specially. In this study, we synthesize a kind of silica absorbent modified with boronic acid derivative, using amorphous silica as raw material and obtaining high adsorption capacity for adenosine. In addition, the adsorption equilibrium can be completed within 10s and 1min for the desorption. Finally, the material was successfully applied to enrich nucleosides from cells and the spiked recoveries were found between 82.21% and 118.9%. The results showed that the prepared adsorbent has potential to effectively enrich cis-diol substances from cell samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Experimental measurement of boron isotope fractionation in seawater

    NASA Astrophysics Data System (ADS)

    Klochko, Kateryna; Kaufman, Alan J.; Yao, Wengsheng; Byrne, Robert H.; Tossell, John A.

    2006-08-01

    The boron isotopic composition of marine carbonates is considered to be a tracer of seawater pH. Use of this proxy benefits from an intimate understanding of chemical kinetics and thermodynamic isotope exchange reactions between the two dominant boron-bearing species in seawater: boric acid B(OH) 3 and borate ion B(OH) 4-. However, because of our inability to quantitatively separate these species in solution, the degree of boron isotope exchange has only been known through theoretical estimates. In this study, we present results of a spectrophotometric procedure wherein the boron isotope equilibrium constant ( 11-10KB) is determined empirically from the difference in the dissociation constants of 11B(OH) 3 and 10B(OH) 3 in pure water, 0.6 mol kg - 1 H 2O KCl and artificial seawater. Within experimental uncertainty, our results show no dependence of 11-10KB on temperature, but 11-10KB at 25 °C in pure water was statistically different than results obtained in solutions at high ionic strength. 11-10KB of the seawater ( S = 35, B T = 0.01 mol kg - 1 H 2O) at 25 °C is 1.0272 ± 0.0006. This result is significantly larger than the theoretical value used in numerous paleo-pH studies ( 11-10KB = 1.0194).

  13. Boron oxygen complexes in Si

    NASA Astrophysics Data System (ADS)

    Sanati, M.; Estreicher, S. K.

    2006-04-01

    The carrier lifetime in boron-doped Czochralski Si is strongly reduced by irradiation (space-based solar cells) or illumination (terrestrial cells). The culprits are believed to be boron-oxygen complexes. We use first-principles theory to predict the structure, electrical activity, and stability of complexes involving substitutional or interstitial B and interstitial O or oxygen dimers. Four complexes with comparable binding energies and thermodynamic gap levels are identified and their local vibrational modes predicted. Replacing B with Ga yields complexes with much smaller binding energies.

  14. Boron Derivatives of 3-Methylpyrazole.

    DTIC Science & Technology

    1984-12-01

    AD-A14$ 988 BORON DERIVRTIYES OF 3 -IETHYLPYRRZOLECU) KENTUCKY UNIV i/i LEXINGTON DEPT OF CHEMISTRY K NIEDENZU ET AL. DEC 84 UK/DC/TR- 5 N8@814-83-K...REPORT DOCUMENTATION PAGE BEFORE CO.!?OVE~r;G FORM UK/DC/TR- 5 I - -_ E. ’and Subtitle) OF 21-P R & PZRIOD COVER=~ BORON DERIVATIVES OF 3 -METHYLPYRAZOLE...pathways for the latter process. In addition, the compounds 4 ,4 ,8,8-tetrabromo- and 4 ,4 ,8 ,8-tetrakis( 3 -methylpyrazole-l-yl)-l, 5 (7)-dimethyl

  15. Analytical boron diffusivity model in silicon for thermal diffusion from boron silicate glass film

    NASA Astrophysics Data System (ADS)

    Kurachi, Ikuo; Yoshioka, Kentaro

    2015-09-01

    An analytical boron diffusivity model in silicon for thermal diffusion from a boron silicate glass (BSG) film has been proposed in terms of enhanced diffusion due to boron-silicon interstitial pair formation. The silicon interstitial generation is considered to be a result of the silicon kick-out mechanism by the diffused boron at the surface. The additional silicon interstitial generation in the bulk silicon is considered to be the dissociation of the diffused pairs. The former one causes the surface boron concentration dependent diffusion. The latter one causes the local boron concentration dependent diffusion. The calculated boron profiles based on the diffusivity model are confirmed to agree with the actual diffusion profiles measured by secondary ion mass spectroscopy (SIMS) for a wide range of the BSG boron concentration. This analytical diffusivity model is a helpful tool for p+ boron diffusion process optimization of n-type solar cell manufacturing.

  16. Boron Nitride Nanoribbons from Exfoliation of Boron Nitride Nanotubes

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh; Hurst, Janet; Santiago, Diana

    2017-01-01

    Two types of boron nitride nanotubes (BNNTs) were exfoliated into boron nitride nanoribbons (BNNR), which were identified using transmission electron microscopy: (1) commercial BNNTs with thin tube walls and small diameters. Tube unzipping was indicated by a large decrease of the sample's surface area and volume for pores less than 2 nm in diameter. (2) BNNTs with large diameters and thick walls synthesized at NASA Glenn Research Center. Here, tube unraveling was indicated by a large increase in external surface area and pore volume. For both, the exfoliation process was similar to the previous reported method to exfoliate commercial hexagonal boron nitride (hBN): Mixtures of BNNT, FeCl3, and NaF (or KF) were sequentially treated in 250 to 350 C nitrogen for intercalation, 500 to 750 C air for exfoliation, and finally HCl for purification. Property changes of the nanosized boron nitride throughout this process were also similar to the previously observed changes of commercial hBN during the exfoliation process: Both crystal structure (x-ray diffraction data) and chemical properties (Fourier-transform infrared spectroscopy data) of the original reactant changed after intercalation and exfoliation, but most (not all) of these changes revert back to those of the reactant once the final, purified products are obtained.

  17. Computational Studies of Nanostructures of Boron

    NASA Astrophysics Data System (ADS)

    Tandy, P.; Yu, M.; Leahy, C.; Tian, W. Q.; Wu, S. Y.; Jayanthi, C. S.

    2009-03-01

    The goal of this work is to develop a reliable semi-empirical Hamiltonian for boron that may be used to predict nanostructures of boron. It is well known that bonding in boron is complicated as it may form three-center, two-electron bonds. The semi-empirical Hamiltonian used here was recently developed by Leahy et al. in the framework of linear combination of atomic orbitals[1]. The salient feature of this Hamiltonian is that it treats environment dependency and charge redistributions on equal footing. It will be shown that such a parameterized Hamiltonian can predict the B80 cage structure with C1 symmetry as found in a recent first-principles study [2]. Having validated our semi-empirical Hamiltonian for boron with small boron clusters and the B80 cage, we have performed a systematic study of other boron nanostructures: (i) larger cage structures (e.g., B215), (ii) boron clusters cut from the bulk alpha boron, and (iii) boron sheets (triangular sheets with and without holes). We will discuss the ground state structures of these boron nanostructures as well as the energetics and HOMO-LUMO gaps of different families of boron clusters as a function their diameters. 1. C. Leahy et al. Phys. Rev. B74, 155408 (2006). 2. N. G. Szwacki et al. PRL 100, 159901 (2008).

  18. Thermionic properties of the molybdenum boron system

    SciTech Connect

    Storms, E.K.

    1980-01-01

    The thermionic work function has been measured as a function of composition within the various two phase regions between Mo and MoB/sub 2/. Values at the low boron and high boron phase boundaries for the various compounds were obtained by extrapolation. The following effective work functions were obtained: Mo/sub 2/B (low boron) = 3.08 eV; Mo/sub 2/B (high boron) = 3.63 eV; ..cap alpha..-MoB (low boron) = 3.38 eV; ..cap alpha..-MoB (high boron) = 4.30 eV; ..beta..-MoB (low boron) = 2.83 eV; ..beta..-MoB (high boron) = 3.92; Mo/sub 2/B/sub 3/ (low boron) = 4.65 eV; Mo/sub 2/B/sub 3/ (high boron) = 3.85 eV; and MoB/sub 2/ (low boron) = 3.52 eV. Because the composition range of these compounds is very narrow, the work function is very sensitive to the composition within the single phase regions.

  19. Graphite-boron composite heater in a Kawai-type apparatus: the inhibitory effect of boron oxide and countermeasures

    NASA Astrophysics Data System (ADS)

    Xie, Longjian; Yoneda, Akira; Yoshino, Takashi; Fei, Hongzhan; Ito, Eiji

    2016-04-01

    We have investigated the performance of a graphite-boron composite (GBC) with 3 wt % boron as a precursor for a boron-doped diamond heater in a Kawai-type apparatus at 15 GPa. We first tested a machinable cylinder of GBC sintered at 1000°C in Ar/H2 gas (99:1 molar ratio). Boron oxide (B2O3) formed during sintering frequently hindered the GBC heater from stable operation at temperatures higher than 1400°C by producing melt throughout the heater together with oxide and/or silicates. We then rinsed the GBC heater in hydrochloric acid to remove B2O3. After rinsing, we succeeded in stably generating temperatures higher than 2000°C. We also improved a molding process of different-sized GBC tubes for convenient use and tested the molded GBC heater. It was free from the B2O3 problem. The electromotive force of the W/Re thermocouple was successfully monitored up to 2400°C.

  20. Boron analysis and boron imaging in biological materials for Boron Neutron Capture Therapy (BNCT).

    PubMed

    Wittig, Andrea; Michel, Jean; Moss, Raymond L; Stecher-Rasmussen, Finn; Arlinghaus, Heinrich F; Bendel, Peter; Mauri, Pier Luigi; Altieri, Saverio; Hilger, Ralf; Salvadori, Piero A; Menichetti, Luca; Zamenhof, Robert; Sauerwein, Wolfgang A G

    2008-10-01

    Boron Neutron Capture Therapy (BNCT) is based on the ability of the stable isotope 10B to capture neutrons, which leads to a nuclear reaction producing an alpha- and a 7Li-particle, both having a high biological effectiveness and a very short range in tissue, being limited to approximately one cell diameter. This opens the possibility for a highly selective cancer therapy. BNCT strongly depends on the selective uptake of 10B in tumor cells and on its distribution inside the cells. The chemical properties of boron and the need to discriminate different isotopes make the investigation of the concentration and distribution of 10B a challenging task. The most advanced techniques to measure and image boron are described, both invasive and non-invasive. The most promising approach for further investigation will be the complementary use of the different techniques to obtain the information that is mandatory for the future of this innovative treatment modality.

  1. Boron-enhanced diffusion of boron from ultralow-energy boron implantation

    SciTech Connect

    Agarwal, A.; Eaglesham, D.J.; Gossmann, H.J.; Pelaz, L.; Herner, S.B.; Jacobson, D.C.; Haynes, T.E.; Erokhin, Y.E.

    1998-05-03

    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{sup +}, the threshold implantation dose which leads to BED lies between 3 {times} 10{sup 14} and of 1 {times} 10{sup 15}/cm{sup {minus}2}. Formation of the shallowest possible junctions by 0.5 keV B{sup +} requires that the implant dose be kept lower than this threshold.

  2. High fluence boron implantation into polyimide

    NASA Astrophysics Data System (ADS)

    Vacík, J.; Hnatowicz, V.; Červená, J.; Peřina, V.; Popok, V.; Odzhaev, V.; Fink, D.

    1999-01-01

    100 keV B + ions are implanted at high fluences into polyimide and the boron depth distributions are measured by the neutron depth profiling technique. Subsequently the implanted samples are annealed isochronally to determine the diffusional, trapping and detrapping behaviour of the boron atoms. The boron depth profiles of as-implanted samples differ significantly from those predicted by TRIM code. Pronounced inward and outward profile tails point at increased mobility and redistribution of boron atoms after implantation. Thermal annealing to the temperatures below 150°C does not change the total boron content in 1 μm thick surface layer and the boron depth profiles as well. For higher annealing temperatures a continuous desorption and significant redistribution of boron atoms is observed.

  3. Boron neutron capture therapy of ocular melanoma and intracranial glioma using p-boronophenylalanine

    SciTech Connect

    Coderre, J.A.; Greenberg, D.; Micca, P.L.; Joel, D.D.; Saraf, S. ); Packer, S. . Div. of Ophthalmology)

    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 {sup 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.

  4. The Arabidopsis-related halophyte Thellungiella halophila: boron tolerance via boron complexation with metabolites?

    PubMed

    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.

  5. Drinking water health advisory for boron

    SciTech Connect

    Cantilli, R.

    1991-04-01

    The Health Advisory Program, sponsored by the Environmental Protection Agency's Office of Water, has issued its report on the element boron: included are the compounds boric acid and borax(sodium tetraborate). It provides information on the health effects, analytical methodology, and treatment technology that would be useful in dealing with the contamination of drinking water. Health Advisories (HAs) describe nonregulatory concentrations of drinking water contaminants at which adverse health effects would not be anticipated to occur over specific exposure durations. HAs serve as informal technical guidance to assist Federal, State, and local officials responsible for protecting public health when emergency spills or contamination situations occur. They are not legally enforceable Federal Standards and are subject to change as new information becomes available.

  6. BP: synthesis and properties of boron phosphide

    NASA Astrophysics Data System (ADS)

    Woo, Katherine; Lee, Kathleen; Kovnir, Kirill

    2016-07-01

    Cubic boron phosphide, BP, is notorious for its difficult synthesis, thus preventing it from being a widely used material in spite of having numerous favorable technological properties. In the current work, three different methods of synthesis are developed and compared: from the high temperature reaction of elements, Sn flux assisted synthesis, and a solid state metathesis reaction. Structural and optical properties of the products synthesized from the three methods were thoroughly characterized. Solid state metathesis is shown to be the cleanest and most efficient method in terms of reaction temperature and time. Synthesis by Sn flux resulted in a novel Sn-doped BP compound. Undoped BP samples exhibit an optical bandgap of ∼2.2 eV while Sn-doped BP exhibits a significantly smaller bandgap of 1.74 eV. All synthesized samples show high stability in concentrated hydrochloric acid, saturated sodium hydroxide solutions, and fresh aqua regia.

  7. Boron and Coumaphos Residues in Hive Materials Following Treatments for the Control of Aethina tumida Murray

    PubMed Central

    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

  8. Boron and Coumaphos Residues in Hive Materials Following Treatments for the Control of Aethina tumida Murray.

    PubMed

    Valdovinos-Flores, Cesar; Gaspar-Ramírez, Octavio; Heras-Ramírez, María Elena; Lara-Álvarez, Carlos; 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).

  9. Structure of boron nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Buranova, Yu. S.; Kulnitskiy, B. A.; Perezhogin, I. A.; Blank, V. D.

    2015-01-01

    The crystallographic structure of boron nitride nanotubes has been investigated. Various defects that may arise during nanotube synthesis are revealed by electron microscopy. Nanotubes with different numbers of walls and different diameters are modeled by molecular dynamics methods. Structural features of single-wall nanotubes are demonstrated. The causes of certain defects in multiwall nanotubes are indicated.

  10. Boron trifluoride coatings for plastics

    NASA Technical Reports Server (NTRS)

    Kubacki, R. M.

    1978-01-01

    Tough, durable coatings of boron triflouride can be deposited on plastic optical components to protect them from destructive effects of abrasion, scratching, and environment. Coating material can be applied simultaneously with organic polymers, using plasma glow-discharge methods, or it can be used as base material for other coatings to increase adhesion.

  11. Method of separating boron isotopes

    DOEpatents

    Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

    1981-01-23

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

  12. Method of separating boron isotopes

    DOEpatents

    Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

    1984-01-01

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

  13. Structure of boron nitride nanotubes

    SciTech Connect

    Buranova, Yu. S. Kulnitskiy, B. A.; Perezhogin, I. A.; Blank, V. D.

    2015-01-15

    The crystallographic structure of boron nitride nanotubes has been investigated. Various defects that may arise during nanotube synthesis are revealed by electron microscopy. Nanotubes with different numbers of walls and different diameters are modeled by molecular dynamics methods. Structural features of single-wall nanotubes are demonstrated. The causes of certain defects in multiwall nanotubes are indicated.

  14. Method of separating boron isotopes

    SciTech Connect

    Jensen, R.J.; Cluff, C.L.; Hayes, J.K.; Thorne, J.M.

    1984-05-08

    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

  15. Electrochemical mineralization pathway of quinoline by boron-doped diamond anodes.

    PubMed

    Wang, Chunrong; Ma, Keke; Wu, Tingting; Ye, Min; Tan, Peng; Yan, Kecheng

    2016-04-01

    Boron-doped diamond anodes were selected for quinoline mineralization, and the resulting intermediates, phenylpropyl aldehyde, phenylpropionic acid, and nonanal were identified and followed during quinoline oxidation by gas chromatography-mass spectrometry and high-performance liquid chromatography. The evolutions of formic acid, acetic acid, oxalic acid, NO2(-), NO3(-), and NH4(+) were quantified. A new reaction pathway for quinoline mineralization by boron-doped diamond anodes has been proposed, where the pyridine ring in quinoline is cleaved by a hydroxyl radical giving phenylpropyl aldehyde and NH4(+). Phenylpropyl aldehyde is quickly oxidized into phenylpropionic acid, and the benzene ring is cleaved giving nonanal. This is further oxidized to formic acid, acetic acid, and oxalic acid. Finally, these organic intermediates are mineralized to CO2 and H2O. NH4(+) is also oxidized to NO2(-) and on to NO3(-). The results will help to gain basic reference for clearing intermediates and their toxicity.

  16. Cyclic Boronates Inhibit All Classes of β-Lactamases

    PubMed Central

    Cain, Ricky; Wang, David Y.; Lohans, Christopher T.; Wareham, David W.; Oswin, Henry P.; Mohammed, Jabril; Spencer, James; Fishwick, Colin W. G.; McDonough, Michael A.

    2017-01-01

    ABSTRACT β-Lactamase-mediated resistance is a growing threat to the continued use of β-lactam antibiotics. The use of the β-lactam-based serine-β-lactamase (SBL) inhibitors clavulanic acid, sulbactam, and tazobactam and, more recently, the non-β-lactam inhibitor avibactam has extended the utility of β-lactams against bacterial infections demonstrating resistance via these enzymes. These molecules are, however, ineffective against the metallo-β-lactamases (MBLs), which catalyze their hydrolysis. To date, there are no clinically available metallo-β-lactamase inhibitors. Coproduction of MBLs and SBLs in resistant infections is thus of major clinical concern. The development of “dual-action” inhibitors, targeting both SBLs and MBLs, is of interest, but this is considered difficult to achieve due to the structural and mechanistic differences between the two enzyme classes. We recently reported evidence that cyclic boronates can inhibit both serine- and metallo-β-lactamases. Here we report that cyclic boronates are able to inhibit all four classes of β-lactamase, including the class A extended spectrum β-lactamase CTX-M-15, the class C enzyme AmpC from Pseudomonas aeruginosa, and class D OXA enzymes with carbapenem-hydrolyzing capabilities. We demonstrate that cyclic boronates can potentiate the use of β-lactams against Gram-negative clinical isolates expressing a variety of β-lactamases. Comparison of a crystal structure of a CTX-M-15:cyclic boronate complex with structures of cyclic boronates complexed with other β-lactamases reveals remarkable conservation of the small-molecule binding mode, supporting our proposal that these molecules work by mimicking the common tetrahedral anionic intermediate present in both serine- and metallo-β-lactamase catalysis. PMID:28115348

  17. Properties and electrochemical characteristics of boron-doped multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Tsierkezos, Nikos G.; Ritter, Uwe; Nugraha Thaha, Yudi; Krischok, Stefan; Himmerlich, Marcel; Downing, Clive

    2015-10-01

    Boron-doped multi-walled carbon nanotubes were synthesized upon decomposition of ethyl alcohol and boric acid via chemical vapor deposition. The boron-doped nanotubes were treated with hydrochloric acid and were characterized by means of scanning electron and transmission electron microscopy in conjunction with energy-dispersive X-ray spectrometry and X-ray photoelectron spectroscopy. The electrochemistry of ferrocyanide/ferricyanide on boron-doped nanotubes was studied in temperature range of 283.15-303.15 K. The findings exhibit an improvement of films' current response and kinetics of electron transfer with the rise in temperature. The kinetics for electron transfer enhances and the redox process occurs slightly more spontaneously upon acid treatment.

  18. The Boron Efflux Transporter ROTTEN EAR Is Required for Maize Inflorescence Development and Fertility[C][W][OPEN

    PubMed Central

    Chatterjee, Mithu; Tabi, Zara; Galli, Mary; Malcomber, Simon; Buck, Amy; Muszynski, Michael; Gallavotti, Andrea

    2014-01-01

    Although boron has a relatively low natural abundance, it is an essential plant micronutrient. Boron deficiencies cause major crop losses in several areas of the world, affecting reproduction and yield in diverse plant species. Despite the importance of boron in crop productivity, surprisingly little is known about its effects on developing reproductive organs. We isolated a maize (Zea mays) mutant, called rotten ear (rte), that shows distinct defects in vegetative and reproductive development, eventually causing widespread sterility in its inflorescences, the tassel and the ear. Positional cloning revealed that rte encodes a membrane-localized boron efflux transporter, co-orthologous to the Arabidopsis thaliana BOR1 protein. Depending on the availability of boron in the soil, rte plants show a wide range of phenotypic defects that can be fully rescued by supplementing the soil with exogenous boric acid, indicating that rte is crucial for boron transport into aerial tissues. rte is expressed in cells surrounding the xylem in both vegetative and reproductive tissues and is required for meristem activity and organ development. We show that low boron supply to the inflorescences results in widespread defects in cell and cell wall integrity, highlighting the structural importance of boron in the formation of fully fertile reproductive organs. PMID:25035400

  19. Boron neutron capture therapy for cancer

    SciTech Connect

    Barth, R.E.; Soloway, A.H. ); Fairchild, R.G. State Univ. of New York, Stony Brook )

    1990-10-01

    Boron neutron capture therapy (BNCT) bring together two components that when kept separate have only minor effects on normal cells. The first component is a stable isotope of boron (boron 10) that can be concentrated in tumor cells. The second is a beam of low-energy neutrons that produces short-range radiation when absorbed, or captured, by the boron. The combination of these two conditions at the site of a tumor releases intense radiation that can destroy malignant tissues. BNCT is based on the nuclear reaction that occurs when boron 10 is irradiated with an absorbs neutrons. The neutrons that it takes up are called thermal, or slow, neutrons. They are of such low energy that they cause little tissue damage as compared with other forms of radiation such as protons, gamma rays and fast neutrons. When an atom of boron 10 captures a neutron, an unstable isotope, boron 11, forms. The boron 11 instantly fissions, yielding lithium 7 nuclei and energetic alpha particles. These heavy particles, which carry 2.79 million electron volts of energy, are a highly lethal form of radiation. If the treatment proceeds as intended, the destructive effects of the capture reaction would occur primarily in those cancer cells that have accumulated boron 10. Normal cells with low concentrations of boron would be spared.

  20. Serum and urinary boron levels in rats after single administration of sodium tetraborate.

    PubMed

    Usuda, K; Kono, K; Orita, Y; Dote, T; Iguchi, K; Nishiura, H; Tominaga, M; Tagawa, T; Goto, E; Shirai, Y

    1998-01-01

    The pharmacokinetics of boron was studied in rats by administering a 1 ml oral dose of sodium tetraborate solution to several groups of rats (n=20) at eleven different dose levels ranging from 0 to 0.4 mg/100 g body weight as boron. Twenty-four-hour urine samples were collected after boron administration. After 24 h the average urinary recovery rate for this element was 99.6+/-7.9. The relationship between boron dose and excretion was linear (r=0.999) with a regression coefficient of 0.954. This result suggests that the oral bioavailability (F) of boron was complete. Another group of rats (n=10) was given a single oral injection of 2 ml of sodium tetraborate solution containing 0.4 mg of boron/100 g body wt. The serum decay of boron was followed and found to be monophasic. The data were interpreted according to a one-compartment open model. The appropriate pharmacokinetic parameters were estimated as follows: absorption half-life, t1/2a=0.608+/-0.432 h; elimination half-life, t1/2=4.64+/-1.19 h; volume of distribution, Vd = 142.0+/-30.2 ml/100 g body wt.; total clearance, Ctot=0.359+/-0.0285 ml/min per 100 g body wt. The maximum boron concentration in serum after administration (Cmax) was 2.13+/-0.270 mg/l, and the time needed to reach this maximum concentration (Tmax) was 1.76+/-0.887 h. Our results suggest that orally administered boric acid is rapidly and completely absorbed from the gastrointestinal tract into the blood stream. Boric acid in the intravascular space does not have a strong affinity to serum proteins, and rapidly diffuses to the extravascular space in proportion to blood flow without massive accumulation or binding in tissues. The main route of boron excretion from the body is via glomerular filtration. It may be inferred that there is partial tubular resorption at low plasma levels. The animal model is proposed as a useful tool to approach the problem of environmental or industrial exposure to boron or in cases of accidental acute boron