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PubMed2005

[Feasibility study on a noninvasive measurement system for boron concentration.].

The kinematics of boron compounds in vivo is crucial to fully and safely utilize boron neutron capture therapy. In this paper, we proposed a prompt gamma-ray Compton scatter camera (PG-CSC), which can evaluate the 3-D kinematics of boron compounds without invasion. This PG-CSC combines a Compton camera with prompt gamma-ray analysis. The results of its design optimization and tests using simulations showed that one-hour-measurement was sufficient to evaluate a 3-D boron concentration distribution in a rat's brain with the resolution of 1 mm in FWHM.

Animals↗
PubMed1998

Positron emission tomography-based boron neutron capture therapy using boronophenylalanine for high-grade gliomas: part I.

Determination of tumor boron-10 (10B) levels is required for accurate neutron dosimetry during boron neutron capture therapy. We assessed a new method for quantitative measurement of boronated drug uptake in high-grade gliomas. This method uses positron emission tomography (PET) with fluorine-18-labeled L-fluoroborono-phenylalanine (L-18F-10B-FBPA), which was synthesized as an analogue of L-boronophenylalanine. We studied the accumulation of L-18F-10B-FBPA by PET in patients with high-grade gliomas. Dynamic PET studies of brain tumors revealed that L-18F-10B-FBPA accumulated gradually after bolus injection, and the value of PET activity divided by the integrated plasma activity reached a constant level 42 min after injection, which was defined as the incorporation constant (Ic*). This constant reflected the appropriate L-18F-10B-FBPA accumulation in tumor tissue. Based on the Ic* constant, the methods for estimating tumor 10B concentration were devised. With this method, the estimated values of 10B concentration in gliomas were very close to the 10B levels in surgical specimens. This method was based solely on PET and can potentially provide data that would assist in the selection of patients for future treatment with boron neutron capture therapy after surgical resection of their brain tumors.

Boron↗
PubMed2007

Comprehensive analysis of chemical bonding in boron clusters.

We present a comprehensive analysis of chemical bonding in pure boron clusters. It is now established in joint experimental and theoretical studies that pure boron clusters are planar or quasi-planar at least up to twenty atoms. Their planarity or quasi-planarity was usually discussed in terms of pi-delocalization or pi-aromaticity. In the current article, we demonstrated that one cannot ignore sigma-electrons and that the presence of two-center two-electron (2c--2e) peripheral B--B bonds together with the globally delocalized sigma-electrons must be taken into consideration when the shape of pure boron cluster is discussed. The global aromaticity (or global antiaromaticity) can be assigned on the basis of the 4n+2 (or 4n) electron counting rule for either pi- or sigma-electrons in the planar structures. We showed that pure boron clusters could have double (sigma- and pi-) aromaticity (B3-, B4, B5+, B6(2+), B7+, B7-, B8, B(8)2-, B9-, B10, B11+, B12, and B13+), double (sigma- and pi-) antiaromaticity (B6(2-), B15), or conflicting aromaticity (B5-,sigma-antiaromatic and pi-aromatic and B14, sigma-aromatic and pi-antiaromatic). Appropriate geometric fit is also an essential factor, which determines the shape of the most stable structures. In all the boron clusters considered here, the peripheral atoms form planar cycles. Peripheral 2c--2e B--B bonds are built up from s to p hybrid atomic orbitals and this enforces the planarity of the cycle. If the given number of central atoms (1, 2, 3, or 4) can perfectly fit the central cavity then the overall structure is planar. Otherwise, central atoms come out of the plane of the cycle and the overall structure is quasi-planar.

Journal Article↗
PubMed2000

Small-Angle X-Ray Scattering Studies on Nucleation Formation of Dextran Precipitation in the Presence of Boron.

In the present study, the nucleation formation process of dextran precipitation in the presence of boron was investigated by small-angle X-ray scattering (SAXS) techniques. The formation mechanism of aggregates or nuclei is very important in the initial step of crystallization. SAXS measurement is an excellent technique for observing these processes. The results of SAXS measurement suggest that boron, as a trace impurity, induces the aggregating of dextran molecules intermolecularly as a process in the nucleation formation of dextran precipitate nuclei and causes precipitation of dextran through an elongation process. These reactions occur readily at low boron concentrations. In fact, boron, which was detected at low levels in dextran solutions, was concentrated in the precipitates. Therefore, an aqueous solution of boron-free dextran should be resistant to precipitation. Copyright 2000 Academic Press.

Journal Article↗
PubMed2005

Removal of boron from aqueous solution by clays and modified clays.

In order to increase the adsorption capacities of bentonite, sepiolite, and illite for the removal of boron form aqueous solution, the clay samples were modified by nonylammonium chloride. Specific surface areas of the samples were determined as a result of N2 adsorption-desorption at 77 K using the BET method. X-ray powder diffraction analysis of the clays and modified clays was used to determine the effects of modifying agents on the layer structure of the clays. The surface characterization of clays and modified clay samples was conducted using the FTIR technique before and after the boron adsorption. For the optimization of the adsorption of boron on clays and modified clays, the effect of pH and ionic strength was examined. The results indicate that adsorption of boron can be achieved by regulating pH values in the range of 8-10 and high ionic strength. In order to find the adsorption characteristics, Langmuir, Freundlich, and Dubinin-Radushkevich adsorption isotherms were applied to the adsorption data. The data were well described by Freundlich and Dubinin-Radushkevich adsorption isotherms while the fit of Langmuir equation to adsorption data was poor. It was reached that modification of bentonite and illite with nonylammonium chloride increased the adsorption capacity for boron sorption from aqueous solution.

Journal Article↗
PubMed2000

Standard electrochemical behavior of high-quality, boron-doped polycrystalline diamond thin-film electrodes

Standard electrochemical data for high-quality, boron-doped diamond thin-film electrodes are presented. Films from two different sources were compared (NRL and USU) and both were highly conductive, hydrogen-terminated, and polycrystalline. The films are acid washed and hydrogen plasma treated prior to use to remove nondiamond carbon impurity phases and to hydrogen terminate the surface. The boron-doping level of the NRL film was estimated to be in the mid 1019 B/cm3 range, and the boron-doping level of the USU films was approximately 5 x 10(20) B/cm(-3) based on boron nuclear reaction analysis. The electrochemical response was evaluated using Fe-(CN)6(3-/4-), Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, dopamine, ascorbic acid, Fe(3+/2+), and chlorpromazine. Comparisons are made between the apparent heterogeneous electron-transfer rate constants, k0(app), observed at these high-quality diamond films and the rate constants reported in the literature for freshly activated glassy carbon. Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, and chlorpromazine all involve electron transfer that is insensitive to the diamond surface microstructure and chemistry with k0(app) in the 10(-2)-10(-1) cm/s range. The rate constants are mainly influenced by the electronic properites of the films. Fe(CN)6(3-/4-) undergoes electron transfer that is extremely sensitive to the surface chemistry with k0(app) in the range of 10(-2)-10(-1) cm/s at the hydrogen-terminated surface. An oxygen surface termination severely inhibits the rate of electron transfer. Fe(3+/2+) undergoes slow electron transfer at the hydrogen-terminated surface with k0(app) near 10(-5) cm/s. The rate of electron transfer at sp2 carbon electrodes is known to be mediated by surface carbonyl functionalities; however, this inner-sphere, catalytic pathway is absent on diamond due to the hydrogen termination. Dopamine, like other catechol and catecholamines, undergoes sluggish electron transfer with k0(app) between 10(-4) and 10(-5) cm/s. Converting the surface to an oxygen termination has little effect on k0(app). The slow kinetics may be related to weak adsorption of these analytes on the diamond surface. Ascorbic acid oxidation is very sensitive to the surface termination with the most negative Ep(ox) observed at the hydrogen-terminated surface. An oxygen surface termination shifts Ep(ox) positive by some 250 mV or more. An interfacial energy diagram is proposed to explain the electron transfer whereby the midgap density of states results primarily from the boron doping level and the lattice hydrogen. The films were additionally characterized by scanning electron microscopy and micro-Raman imaging spectroscopy. The cyclic voltammetric and kinetic data presented can serve as a benchmark for research groups evaluating the electrochemical properties of semimetallic (i.e., conductive), hydrogen-terminated, polycrystalline diamond.

Journal Article↗
PubMed2001

Three-coordinated boron-11 chemical shifts in borates.

Despite the importance of (11)B nuclear magnetic resonance (NMR) in structural studies of borate glasses, no clear means of correlating NMR parameters with the number of nonbridging oxygens on three-coordinate boron has been demonstrated. In this work, a series of anhydrous, polycrystalline, binary borates has been examined by (11)B magic-angle spinning (MAS) NMR to obtain precise measurements of their three-coordinate boron isotropic chemical shifts. The shifts generally increase with the replacement of bridging oxygens by nonbridging oxygens, ranging from 14.6 ppm in crystalline B(2)O(3) to 22.5 ppm in magnesium orthoborate. The underlying physical basis for this trend is satisfactorily accounted for by considering second neighbor effects using bond valence sums. These data are supportive of a structural model for B(2)O(3) glass in which 72% of the boron atoms are in rings. High-field MAS NMR experiments (B(0) = 18.8 T) indicate that the boron shielding is anisotropic, with greater anisotropy measured for three-coordinate borons possessing one or two nonbridging oxygens, than for those with zero or three nonbridging oxygens.

Journal Article↗
PubMed2006

Mononuclear Schiff base boron halides: synthesis, characterization, and dealkylation of trimethyl phosphate.

A series of mononuclear boron halides of the type LBX(2) [LH = N-phenyl-3,5-di-tert-butylsalicylaldimine, X = Cl (2), Br (3)] and LBX [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (7), Br (8); LH2 = N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (9), Br (10); and LH2 = N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (11), Br (12)] were synthesized from their borate precursors LB(OMe)2 (1) (LH = N-phenyl-3,5-di-tert-butylsalicylaldimine) and LB(OMe) [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine (4), N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine (5), N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine (6)]. The boron halide compounds were air and moisture sensitive, and upon hydrolysis, compound 7 resulted in the oxo-bridged compound 13 that contained two seven-membered boron heterocycles. The boron halide compounds dealkylated trimethyl phosphate in stoichiometric reactions to produce methyl halide and unidentified phosphate materials. Compounds 8 and 12 were found to be the most effective dealkylating agents. On reaction with tert-butyl diphenyl phosphinate, compound 8 produced a unique boron phosphinate compound LB(O)OPPh2 (14) containing a terminal phosphinate group. Compounds 1-14 were characterized by 1H, 13C, 11B, 31P NMR, IR, MS, EA, and MP. Compounds 5, 6, and 11-14 also were characterized by single-crystal X-ray diffraction.

Journal Article↗
PubMed2006

Hydrogen adsorption on carbon-doped boron nitride nanotube.

The adsorption of atomic and molecular hydrogen on carbon-doped boron nitride nanotubes is investigated within the ab initio density functional theory. The binding energy of adsorbed hydrogen on carbon-doped boron nitride nanotube is substantially increased when compared with hydrogen on nondoped nanotube. These results are in agreement with experimental results for boron nitride nanotubes (BNNT) where dangling bonds are present. The atomic hydrogen makes a chemical covalent bond with carbon substitution, while a physisorption occurs for the molecular hydrogen. For the H(2) molecule adsorbed on the top of a carbon atom in a boron site (BNNT + C(B)-H(2)), a donor defect level is present, while for the H(2) molecule adsorbed on the top of a carbon atom in a nitrogen site (BNNT + C(N)-H(2)), an acceptor defect level is present. The binding energies of H(2) molecules absorbed on carbon-doped boron nitride nanotubes are in the optimal range to work as a hydrogen storage medium.

Journal Article↗
PubMed2006

Substitutional boron in nanodiamond, bucky-diamond, and nanocrystalline diamond grain boundaries.

Although boron has been known for many years to be a successful dopant in bulk diamond, efficient doping of nanocrystalline diamond with boron is still being developed. In general, the location, configuration, and bonding structure of boron in nanodiamond is still unknown, including the fundamental question of whether it is located within grains or grain boundaries of thin films and whether it is within the core or at the surface of nanoparticles. Presented here are density functional tight-binding simulations examining the configuration, potential energy surface, and electronic charge of substitutional boron in various types of nanocrystalline diamond. The results predict that boron is likely to be positioned at the surface of isolated particles and at the grain boundary of thin-film samples.

Journal Article↗
PubMed1999

Purification of catechol siderophores by boronate affinity chromatography: identification of chrysobactin from Erwinia carotovora subsp. carotovora.

Catechols are co-planar cis-diols known to form stable, isolable complexes with borate under weakly basic conditions. We exploited this chemistry and developed a boronate affinity chromatography for isolating catechol siderophores. The method was applied to the isolation of chrysobactin, enterobactin, and an unknown catechol siderophore produce by Erwinia carotovora subsp. carotovora W3C105. Yields of chrysobactin and enterobactin purified by boronate affinity chromatography were at least two-fold greater than those achieved through alternate methods. The unknown catechol produced by E. carotovora subsp. carotovora W3C105 was isolated by boronate affinity chromatography and shown to be identical to chrysobactin. Boronate affinity chromatography enabled separation of catechol from its rust-colored decomposition products, and simultaneous isolation of catechol and hydroxamate siderophores. Boronate affinity chromatography is a rapid and efficient method for purifying catechol siderophores from bacterial culture supernatants.

Borates↗
PubMed2001

1-(2-hydroxy-3-methoxybenzylideneamino)-8-hydroxynaphthalene-3,6-disulfonic acid as a reagent for the spectrophotometric determination of boron in ceramic materials.

A sensitive and selective spectrophotometric method for the determination of boron is described. The method is based on the colour reaction between boron and the reagent 1-(2-hydroxy-3-methoxybenzylideneamino)-8-hydroxynaphthalene-3,6-disulfonic acid (HMOA). In a HOAc-NH4OAc buffer of pH 5.5, HMOA reacts with boron to form a 1:2 yellow complex with a maximum absorption at 423 nm. The absorbance (lambdamax = 423 nm) is linear up to 1.2 microg ml(-1) boron in aqueous solution with a repeatability (RSD) of 1.12%. The molar absorptivity and Sandell's sensitivity are 7.19 x 10(3) l mol(-1) cm(-1) and 0.0015 microg cm(-2), respectively. The limit of quantification and limit of detection were found to be 17.1 and 5.2 ng ml(-1), respectively. The interference of various ions was examined in detail. All the metal ions studied can be tolerated in considerable amounts; in particular, the tolerance limits of Fe, Al, Zn, Ca and Mg are superior to those of other reagents such as Azomethine-H and Azomethine-HR. The proposed method was applied to the determination of boron in ceramic materials with satisfactory results.

Journal Article↗
PubMedDate not supplied

Boron supplementation inhibits the growth and local expression of IGF-1 in human prostate adenocarcinoma (LNCaP) tumors in nude mice.

Prostate-specific antigen (PSA) is a serine protease and one of the most abundant proteins secreted by the human prostate epithelium. PSA is used as a well-established marker of prostate cancer. The involvement of PSA in several early events leading to the development of malignant prostate tumors has made it a target for prevention and intervention. It is thought that PSA cleaves insulin-like growth factor binding protein-3 (IGFBP-3), providing increased local levels of IGF-1, leading to tumor growth. Separately, there are data that suggest an enzymatic regulatory role for dietary boron, which is a serine protease inhibitor. In this study we have addressed the use of boric acid as a PSA inhibitor in an animal study. We have previously reported that low concentrations (6 ug/mL) of boric acid can partially inhibit the proteolytic activity of purified PSA towards a synthetic fluorogenic substrate. Also, by Western blot we have followed the degradation of fibronectin by enzymatically active PSA and have found significant inhibition in the presence of boric acid. We proposed that dietary supplementation with boric acid would inhibit PSA and reduce the development and proliferation of prostate carcinomas in an animal model. We tested this hypothesis using nude mice implanted subcutaneously with LNCaP cells in Matrigel. Two groups (10 animals/group) were dosed with boric acid solutions (1.7, 9.0 mgB/kg/day) by gavage. Control group received only water. Tumor sizes were measured weekly for 8 weeks. Serum PSA and IGF-1 levels were determined at terminal sacrifice. The size of tumors was decreased in mice exposed to the low and high dose of boric acid by 38% and 25%, respectively. Serum PSA levels decreased by 88.6% and 86.4%, respectively, as compared to the control group. There were morphological differences between the tumors in control and boron-dosed animals, including a significantly lower incidence of mitotic figures in the boron-supplemented groups. Circulating IGF-1 levels were not different among groups, though expression of IGF-1 in the tumors was markedly reduced by boron treatment, which we have shown by immunohistochemistry. These data indicate that low-level dietary boron supplementation reduced tumor size and content of a tumor trophic factor, IGF-1. This promising model is being evaluated in further studies.

Adenocarcinoma↗
PubMed1988

Boron fertilization and carbohydrate relations in mycorrhizal and nonmycorrhizal shortleaf pine.

Eight-week-old shortleaf pine seedlings (Pinus echinata Mill.) with and without ectomycorrhizae formed by Pisolithus tinctorius were treated for two to eight weeks with 25 microg borate ml(-1) solution applied either to the soil, or as a foliar spray, or in both ways. Control seedlings were fertilized only with modified Hoagland's solution containing 0.03 microg ml(-1) borate. Five sugars (pinitol, fructose, glucose, myoinositol and sucrose) were quantitated in both mycorrhizal and nonmycorrhizal roots by gas-liquid chromatography. Fertilization with boron increased the total carbohydrate content of mycorrhizal roots except in seedlings receiving foliar applications of boron. Foliar + soil fertilization yielded a 24% increase in total carbohydrates in mycorrhizal roots, whereas foliar fertilization alone decreased the total carbohydrate content. Carbohydrate content of nonmycorrhizal roots was significantly increased only by soil fertilization with boron. Individual sugars were affected less by boron fertilization in nonmycorrhizal roots than in ectomycorrhizal roots. However, significant increases in sugars in response to boron fertilization were observed in both ectomycorrhizal and nonmycorrhizal plants.

Journal Article↗
PubMed1994

Essentiality of Boron for Symbiotic Dinitrogen Fixation in Pea (Pisum sativum) Rhizobium Nodules.

The effect of boron deficiency on symbiotic nitrogen fixation in pea (Pisum sativum) was examined. The absence of boron in the culture medium resulted in a decrease of the number of nodules and an alteration of nodule development leading to an inhibition of nitrogenase activity. Examination of boron-deficient nodules showed dramatic changes in cell walls and in both peribacteroid and infection thread membranes, suggesting a role for boron in the stability of these structures. These results indicate that boron is a requirement for normal nodule development and functionality.

Journal Article↗
PubMed1977

Early effects of boron deficiency on indoleacetic Acid oxidase levels of squash root tips.

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.

Journal Article↗
PubMed1988

Boron Protection for O(2) Diffusion in Heterocysts of Anabaena sp. PCC 7119.

The effect of boron on nitrogenase activity has been studied. When cells were dependent on N(2) fixation, the lack of boron inhibited nitrogenase activity. However, under anaerobic conditions or in the presence of Na-dithionite this effect was not observed. Nitrogenase synthesis was not affected by boron deficiency. Similarly, the heterocyst number was not altered. Examination of boron-deficient cultures showed, however, some dramatic changes in heterocyst morphology. The increased activity of those enzymes related to the maintaining of the low intracellular level of toxic oxygen species (superoxide dismutase, catalase, and peroxidase) support our hypothesis of the role of boron in heterocyst envelope stabilization.

Journal Article↗
PubMed1990

Effect of Boron Deficiency on Photosynthesis and Reductant Sources and Their Relationship with Nitrogenase Activity in Anabaena PCC 7119.

Nitrogenase activity of Anabaena PCC 7119 is inhibited under conditions of boron deficiency. To elucidate the mechanisms of this inhibition, this study examined how the deficiency of boron affected photosynthesis, photosynthetic pigments, the enzymes of the oxidative pentose phosphate pathway, and respiration of Anabaena PCC 7119 cultures. After 24 to 48 hours of boron deficiency, reductions in photosynthetic O(2) evolution and in CO(2) fixation were observed. At the same time, the activities of oxidative pentose phosphate pathway enzymes and respiration increased significantly with boron deficiency. No change was observed in these processes when assays were performed after 4 to 6 hours of deficiency, a time at which nitrogenase activity was severely inhibited. These results suggest that the requirement for boron in N(2) fixation is independent of its effects on photosynthesis and reductant supply.

Journal Article↗