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A novel glycoasparagine isolated from an ovalbumin glycopeptide fraction (GP-IV). Anion-exchange borate chromatography and structural analysis of GP-IV glycoasparagines.

The fraction GP-IV obtained from hen ovalbumin has been further fractionated on DEAE-Sephadex A-25 in borate buffer, a new system for the separation and isolation of glycoasparagines on columns. The structures of one major and two minor glycoasparagines thus obtained were determined by enzymatic (endo-beta-N-acetylglucosaminidase D and H digestion), chemical (modified Smith degradation, acetolysis, and methylation analysis), and instrumental (270 MHz 1H nuclear magnetic resonance spectroscopy) analyses. The following structure is novel for carbohydrate moieties in ovalbumin glycoasparagines: (formula; see text) The present anion exchange chromatography in borate solution is well suited for separating and preparing oligosaccharides having similar molecular size but differing in content of vicinal cis-diol group.

Animals↗

Requirement of borate cross-linking of cell wall rhamnogalacturonan II for Arabidopsis growth.

Turgor-driven plant cell growth depends on wall structure. Two allelic l-fucose-deficient Arabidopsis thaliana mutants (mur1-1 and 1-2) are dwarfed and their rosette leaves do not grow normally. mur1 leaf cell walls contain normal amounts of the cell wall pectic polysaccharide rhamnogalacturonan II (RG-II), but only half exists as a borate cross-linked dimer. The altered structure of mur1 RG-II reduces the rate of formation and stability of this cross-link. Exogenous aqueous borate rescues the defect. The reduced cross-linking of RG-II in dwarf mur1 plants indicates that plant growth depends on wall pectic polysaccharide organization.

Alleles↗

Assessment of fertility and infertility in boron-exposed Turkish subpopulations: 3. Evaluation of fertility among sibs and in "borate families".

As a part of a work to reveal the health effects of boron and its compounds, fertility and infertility states of sibs of probands, contacted and interviewed in the field, and of their spouses were given. The purposes were to prevent duplications seemingly inevitable in a relatively small community with prevailing consanguinity while analyzing marriages over respective generations and to reveal if there occurred an aggregation of infertile couples. Any family without offspring after about the second year of marriage was considered primary infertile as adopted throughout the study and such families were ascertained through the individual pedigree charts set up according to the instructions of the proband, he (she) himself (herself) being excluded. The rates of childless families of this type were 0.0-3.4% among male and 0.9-3.8% among female sibs of the participant, and 2.3-10.0% among male and 0.0-5.6% among female sibs of his (her) spouse with averages of 2.3% of 1589, 2.6% of 1589, 4.0% of 1314, and 3.3% of 1436 instances, respectively. The differences were insignificant and the rates were not different from those concerning probands themselves and that of a comparable segment of the Turkish population. "Borate families/kindreds" with two or more members engaged in the borate industry were also assessed in order to detect if there was a significant clustering of infertiles within the kindred. Although it was difficult to compare with a matched group, few couples were examples of familial concentration of infertility. These results provided further support that boron exposure does not affect human reproduction primarily and most probably secondarily.

Adult↗

Borate G-banding technique applicable to in situ deoxyribonucleic acid/deoxyribonucleic acid hybridized chicken chromosomes.

The borate G-banding technique produced excellent longitudinal bands similar to trypsin G-bands on chicken chromosomes prepared from embryo material. Aged chromosome preparations on slides were pretreated in borate buffer (pH 9.2) for 10 to 30 s at 37 C, then stained in Giemsa solution. This simple G-banding procedure gave high-resolution chromosome banding and permitted the visualization of silver grains that localized cloned gene sequences or cloned DNA fragments to specific regions by in situ hybridization.

Animals↗

Improved borate method for the rapid distinction of glucosamine and galactosamine in an exopolysaccharide produced by Citrobacter sp.

An improved borate method for the quantitative distinction of glucosamine (GlcN) and galactosamine (GalN) in a mixture is presented which is based on the Elson-Morgan method with addition of sodium borate to differentiate colour formation by the two hexosamines. The r2 value and maximum deviation of the method based on calculations derived in this study were 0.9979 and 5.1 %, respectively. Using this method, the GlcN/GalN ratio in an exopolysaccharide (EPS) produced by Citrobacter sp. was found to change with time during the production process, with a maximum value at 9.8:1.

Borates↗

[Spectral study of some polyoxovanadium borates].

Four novel polyoxovanadium borates with [(VO)12O6B18O42], namely (enH2)6 H3 [(VO)12O6B18O42].13H2O(1), [Ni (en)2]6 H3 [(VO)12 O6B18O42].8H2O(2), [Cu(en)2]5 H3 [(VO)12 O6B18 O42] [B(OH)3]2. 16H20(3) and(enH2)4 Na4H3 [(VO)12 O6B18O42].8H2O(4), were synthesized. The relationship between their properties and structures were studied by using FTIR, UV-Vis DRS and fluorescence etc. Among these compounds, compound (1) possesses isolated [(VO)12O6B18O42] cage, there is a ring of B18O42 sandwiched between two vanadium-oxygen clusters V6O18 by eighteen B--(micro3--O)--V bonds, while compound (2) is rather six [Ni(en)2], each connected with the B18O42 ring by two Ni--(micro3--O)--B. In compounds (3) and (4), the anion clusters [(VO)12 O6B18O42]13- are connected with [Cu(en)2]2+ and Na+ , respectively. Thus, the compounds (3) and (4) are extended to an infinite two-dimensional network structure, respectively. These characteristic vibrational frequencies of polyoxovanadium borates are related to the structures of these compounds. In UV/Vis DRS spectra, there are two characteristic peaks of polyoxometalates at 205 and 260 nm, respectively. The fluorescence spectra of these four compounds have been studied, and they have emission peaks at 415 nm excited by 310 nm which are caused by Omicro-->Mo. The fluorescence lifetimes of these compounds have been studied.

Borates↗

[Two-dimensional electrophoresis of the products of limited hydrolysis of human serum albumin using isoelectric focusing in a borate-polyol system].

A procedure developed involved isoelectrofocusing in borate-polyol system and thin-layer electrophoresis in polyacrylamide gel gradient containing sodium dodecylsulfate of the products of human blood serum albumin obtained after partial hydrolysis. The first dimension isoelectrofocusing in borate-polyol system allowed to separate peptides with close values of pI and to increase the procedure sensitivity. The procedure may be recommended for identification of proteins, for estimation of the protein degradation in hydrolysis as well as for studies of peptide maps of albumin under normal and pathological states.

Borates↗

[A method of isoelectric focusing in a borate-polyol system with pH gradient of 4.0 to 5.6 in a thin layer of polyacrylamide gel].

A procedure is described for thin-layer polyacrylamide gel isoelectric focusing involving borate-polyol system with gradient pH 4.0-5.6, where 0.5 M H3BO3-Tris was used as an electrode buffer. Riboflavin, TEMED, Tris-borate buffer and glycerol were used in preparation of gradient pH, which was stable and did not alter during the electrophoresis. Blood serum proteins, particularly blood serum albumin, from patients with diabetes were studied using the isoelectric focusing procedure. After isoelectrofocusing of blood serum albumin from patients with diabetes additional minor acid fractions of the protein were detected at pH 4.3-4.6. The procedure of electrophoresis in gradient pH 4.0-5.6 was highly effective and might be used in biochemical laboratories.

Blood Proteins↗

[Practical use of lithium borate in thermoluminescent dosimetry (author's transl)].

The authors recall the functional principles of thermoluminescent dosimeters: heating, apparatus for measuring the emitted light, circulation of nitrogen, reference source. They take this opportunity to stress the essential role played by the circulation of nitrogen over the dosimeters which equilibrates the temperature of the photo multiplier, reduces the emission of unwanted light, prevents the combustion of dust or other possible impurities and finally improves the reproductibility of the measurements even for high dosod for finding the optimum working conditions for the heating apparatus of the planchette in the most simple T.L.D. readers and in those where the heating apparatus of the planchette has a pre-heating phase. They then study the dosimetric properties of lithium borate incorporated in thin teflon discs (type DLB. 0.13 and 0.4). This shows itself to be very interesting for certain uses because it is a solid dosimeter which does not require annealing between two measurements. The reproductibility of the measurements obtained with this material, the stability of its response relative to the delay between radiation and reading (fading), its response relative to the absorbed dose plus the nature and the energy of the rays, are presented with the usual reservations made for this type of dosimetry. The authors conclude by citing a few applications where they have been able to achieve a satisfactory result with the aid of lithium borate.

Borates↗

Synthesis and properties of the tetrakis(trifluoromethyl)borate anion, [b(CF3)4]-: structure determination of Cs[B(CF3)4] by single-crystal X-ray diffraction.

Salts of the tetrakis(trifluoromethyl)borate anion, M[B(CF3)4], M=Li, K, Cs, Ag, have been prepared by two different routes for the first time. The colorless compounds are thermally stable up to 425 C (Cs salt) and soluble in anhydrous HF, water, and most organic solvents. Single crystals of Cs[B(CF3)4] were grown from diethyl ether by diffusion of CH2Cl2 vapor into the solution. The molecular structure was obtained by single-crystal X-ray diffraction. Crystal data: rhombohedral space group R3m (no. 160); a =7.883(1), c=13.847(4) A: V=748.2 A3; Z=3; T=150K; R1=0.0118, wR2=0.0290. The internal bond parameters of the [B(CF3)4] ion were compared to those of the C(CF3)4 molecule. Due to a disorder of the anions in the cesium salt, it is not possible to distinguish between T and Td symmetry by X-ray diffraction experiments alone. However, a comprehensive IR and Raman study demonstrated that in the potassium and cesium salt as well as in aqueous solution, the anion exhibits T symmetry with all CF3 groups rotated off the staggered position required for Td symmetry. The vibrational study is supported by DFT calculations, which provide, in addition to the equilibrium structure and vibrational wavenumbers, estimates of IR and Raman band intensities. The anion is resistant against strong oxidizing (e.g., F2) as well as reducing agents (e.g., Na) and is not affected by nucleophiles like C2H5O or electrophiles such as H3O+. It is very weakly coordinating, as demonstrated by the low-equilibrium CO pressure over the [Ag(CO)x][B(CF3)4] (x=1, 2) co-adducts and the formation of [Ag(CO)x][B(CF3)4] (x=3,4) at higher CO pressure. The 11B, 13C, and 19F NMR data as well as the structural parameters of the anion are compared with those for other borates containing F, CN, and CF3 ligands.

Journal Article↗

Tris-tricine and Tris-borate buffer systems provide better estimates of human mesothelial cell intermediate filament protein molecular weights than the standard Tris-glycine system.

Human mesothelial cells contain a number of well defined intermediate filament proteins (IFs) that have been completely sequenced including vimentin and the cytokeratins (K7, K8, K18, and K19). The electrophoretic migration of these IFs was monitored as a function of second dimension gel buffer composition using various systems including Tris-glycine (pH 8.3 or 9.2), Tris-glycine with 20% methanol, Tris-borate, Tris-tricine, and sodium phosphate. All of the second dimension buffer chemistries yielded patterns of sufficient resolution to identify the major cytoskeletal proteins but differed in the relative mobilities of the IFs. Using gene sequence calculated molecular weight data, the major cytoskeletal polypeptides of human mesothelial cells were ranked from highest molecular weight to lowest molecular weight. This rank order of sequence calculated molecular weights was then compared to the rank order determined form the actual migration of the polypeptides in the different gel systems. With the Tris-tricine and the Tris-borate gel systems as well as gene sequence data, KS = vimentin greater than beta-tubulin = K7 greater than K18 greater than K19 greater than actin. With the pH 8.3 and 9.2 Tris-glycine systems, as well as the sodium phosphate gel system, the rank order of the polypeptides did not correspond to gene sequence data. Adding 20% methanol to the Tris-glycine system resulted in IF migration that more closely corresponded to the gene sequence derived data. Migration position of the IFs depended upon the temperature of the second dimension separation as well. In mesothelial cells, the migration of a total of 15-25% of the polypeptides was influenced by differing buffer systems.(ABSTRACT TRUNCATED AT 250 WORDS)

Boric Acids↗

High fraction of penta-coordinated aluminium in amorphous and crystalline aluminium borates.

27Al and 11B magic-angle spinning nuclear magnetic resonance (MAS NMR) results are reported on aluminium borates of composition Al2(1 - x)B2xO3 (0 < or = x < or = 0.7). It is shown that starting from liquid precursors with hexa-coordinated Al and tri- and tetra-coordinated B, porous aluminium borates are obtained containing high fractions of penta-coordinated Al. The presence of boron in the crystalline phases stabilizes penta-coordinated Al, existing already in their amorphous precursors, and at the same time distorts the surroundings of the hexa-coordinated Al. The reversible effect of air exposure on low-coordinated Al (Al4C, Al5C) and B (B3C) proved that at least these species are situated at the surfaces of the pores. The A9B2 phase still contains a small fraction of tetra-coordinated B. The 27Al and 11B MAS NMR spectra of A9B2 show a well-resolved powder spectrum with no indication of broadening due to a distorted configuration.

Aluminum Compounds↗

Amperometric glucose biosensor with extended concentration range utilizing complexation effect of borate.

Borate buffer strongly decreases amperometric response of a glucose oxidase linked pO2 or H2O2 sensing electrode, extending substantially its linear calibration range. With increasing pH and concentration of the buffer the upper limit for glucose can be varied between 1 and 30 mmol l-1 glucose. The effect of borate ion is explained by the rapid complexation of glucose decreasing the equilibrium concentration of free beta-anomer, the specific substrate of glucose oxidase. The high loading of cross-linked enzyme inside the sensor membrane is necessary for the measurement to ensure an almost constant response factor (delta i per 1 mmol l-1) between pH 5 and 10. Analysis in stirred solution and in a flow-through system has been employed for the measurement of elevated glucose levels in heparinized human blood or plasma samples.

Biosensing Techniques↗

High-performance liquid chromatography of N-terminal tyrosine-containing oligopeptides by pre-column fluorescence derivatization with hydroxylamine, cobalt (II) and borate reagents.

A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of N-terminal tyrosine-containing oligopeptides involving methionine-enkephalin and leucine-enkephalin. The peptides are converted into fluorescent derivatives by heating in a weakly alkaline medium (pH 8.5) containing hydroxylamine, cobalt(II) ion and borate. The derivatives are separated on a reversed-phase column (TSKgel ODS-120T) by gradient elution of acetonitrile in a mobile phase containing borate buffer (pH 8.5) and tetra-n-butylammonium chloride, and then determined by fluorimetry. The derivatization provides a single fluorescent product for each N-terminal tyrosine-containing oligopeptide, but does not allow the production of fluorescent derivatives for peptides having no tyrosyl residue at the N-terminal. The method is selective and sensitive; the lower limits of detection for the N-terminal tyrosine-containing oligopeptides tested were 140-310 fmol per 100 microliters injected.

Boric Acids↗

Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate.

Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for groundwater nitrate remediation; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate reduction by Fe0 have not been well understood. A 25.0 mL nitrate solution of 20.0 mg of N L(-1) (1.43 mM nitrate) was reacted with 1.00 g of Peerless Fe0 at 200 rpm on a rotational shaker at 23 degrees C for up to 120 h in the presence of each of the organic acids (3.0 mM formic, 1.5 mM oxalic, and 1.0 mM citric acids) and inorganic acids (3.0 mM HCl, 1.5 mM H2SO4, 3.0 mM H3BO3, and 1.5 mM H3PO4). These acids provided an initial dissociable H+ concentration of 3.0 mM available for nitrate reduction reactions under conditions of final pH < 9.3. Nitrate reduction rates (pseudo-first-order) increased in the order: H3PO4 < citric acid < H3BO3 < oxalic acid < H2SO4 < formic acid < HCl, ranging from 0.00278 to 0.0913 h(-1), corresponding to surface area normalized rates ranging from 0.126 to 4.15 h(-1) m(-2) mL. Correlation analysis showed a negative linear relationship between the nitrate reduction rates for the ligands and the conditional stability constants for the soluble complexes of the ligands with Fe2+ (R2 = 0.701) or Fe3+ (R2 = 0.918) ions. This sequence of reactivity corresponds also to surface adsorption and complexation of the three organic ligands to iron oxides, which increase in the order formate < oxalate < citrate. The results are also consistent with the sequence of strength of surface complexation of the inorganic ligands to iron oxides, which increases in the order: chloride < sulfate < borate < phosphate. The blockage of reactive sites on the surface of Fe0 and its corrosion products by specific adsorption of the inner-sphere complex forming ligands (oxalate, citrate, sulfate, borate, and phosphate) may be responsible for the decreased nitrate reduction by Fe0 relative to the chloride system.

Acids↗

Electronic communication in oligometallic complexes with ferrocene-based tris(1-pyrazolyl)borate ligands.

Ferrocene-based tris(1-pyrazolyl)borate ligands 1R-Li and 1R-Tl have been synthesized and used to generate a variety of heterotrinuclear transition metal complexes, 3R-M [R = H, SiMe(3), cyclohexyl, (cyclohexyl)methyl, phenyl; M(II) = Mn, Fe, Co, Ni, Cu, Zn]. The poor solubility of 3H-M is greatly enhanced by the introduction of large organic substituents into the 4-positions of all pyrazolyl rings. The unsubstituted ligand 1H-Li and the trinuclear complex 3Cym-Cu [Cym = (cyclohexyl)methyl] have been investigated by X-ray crystallography. 1H-Li, which represents the first example of a structurally characterized lithium tris(1-pyrazolyl)borate, forms centrosymmetric dimers in the solid state. A severe Jahn-Teller distortion was observed for the (Bpz(3))(2)Cu fragment in 3Cym-Cu. Compared to the parent compounds [(HBpz(3))(2)M], the presence of uncharged ferrocenyl substituents in 3R-M tends to shift the M(2+)/M(3+) redox potential to significantly more cathodic values. The opposite is true if the ferrocenyl fragments are in their cationic state, which results in an anodic shift of the M(2+)/M(3+) transition. Most interestingly, the two ferrocenyl fragments in 3R-Cu appear to be electronically communicating.

Journal Article↗

Variable coordination modes of hydrotris(3-isopropyl-4-bromopyrazolyl)borate (Tp') in Fe(II), Mn(II), Cr(II), and Cr(III) Complexes: formation of MTp'Cl (M = Fe and Mn), structural isomerism in CrTp'(2), and the observation of Tp' (-) as an uncoordinated anion.

The syntheses of the 4-coordinate Tp'MCl complexes (where M = Fe (1), Mn (2); and Tp' = hydrotris(3-isopropyl-4-bromopyrazolyl)borate) are described. The single-crystal X-ray structures show that the metal centers have distorted tetrahedral coordination. Analogous reaction of CrCl(2)(MeCN)(2) with TlTp' gave Cr(kappa(3)-Tp')(kappa(2)-Tp') (3) as the initial product. The 5-coordinate structure was assigned by single-crystal X-ray crystallography, and it was found that the kappa(3) ligand had isomerized to hydro(3-isopropyl-4-bromopyrazolyl)(2)(5-isopropyl-4-bromopyrazolyl)borate). 3 is labile in solution: in pentane it slowly converts to the 6-coordinate isomer Cr(kappa(3)-Tp')(2) (4), whose structure was determined by X-ray crystallography. In 4 both ligands are isomerized. Both 3 and 4 display Jahn-Teller distorted structures expected for high-spin d(4) configurations. Variable temperature magnetic susceptibility measurements confirm that 1, 2, and 3 all have high-spin electronic configurations in the range 5-300 K. In benzene solution 3 decomposes; one product [Cr(kappa(3)-Tp')(2)](+)[Tp'](-) (5), was identified by X-ray crystallography. 5 contains a pseudooctahedral Cr(III) cation with both ligands in the isomerized form and an uncoordinated Tp' ligand as counterion. Mechanistic studies reveal that this reaction is light rather than heat induced. IR spectroscopy is utilized to confirm the ligand hapticity in all complexes from the value of nu(B)(-)(H), and comparison is made with similar compounds.

Journal Article↗

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↗