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PubMed2006

Structure-function correlations in Iron(II) tris(pyrazolyl)borate spin-state crossover complexes.

Iron(II) poly(pyrazolyl)borate complexes have been investigated to determine the impact of substituent effects, intramolecular ligand distortions, and intermolecular supramolecular structures on the spin-state crossover (SCO) behavior. The molecular structure of Fe[HB(3,4,5-Me3pz)3]2 (pz = pyrazolyl ring), a complex known to remain high spin when the temperature is lowered, reveals that this complex has an intramolecular ring-twist distortion that is not observed in analogous complexes that do exhibit a SCO at low temperatures, thus indicating that this distortion greatly influences the properties of these complexes. The structure of Fe[B(3-(cy)Prpz)4]2.(CH3OH) ((cy)Pr = cyclopropyl ring) at 294 K has two independent molecules in the unit cell, both of which are high spin; only one of these high-spin iron(II) sites, the site with the lesser ring-twist distortion, is observed to be low-spin iron(II) in the 90 K structure. A careful evaluation of the supramolecular structures of these complexes and several similar complexes reported previously revealed no strong correlation between the supramolecular packing forces and their SCO behavior. Magnetic and Mössbauer spectral measurements on Fe[B(3-(cy)Prpz)4]2 and Fe[HB(3-(cy)Prpz)3]2 indicate that both complexes exhibit a partial SCO from fully high-spin iron(II) at higher temperatures, respectively, to a 50:50 high-spin/low-spin mixture of iron(II) below 100 K. These results may be understood, in the former case, by the differences in ring-twisting and, in the latter case, by a phase transition; in all complexes in which a phase transition is observed, this change dominates the SCO behavior. A comparison of the Mössbauer spectral properties of these two complexes and of Fe[HB(3-Mepz)3]2 with that of other complexes reveals correlations between the Mössbauer-effect isomer shift and the average Fe-N bond distance and between the quadrupole splitting and the average FeN-NB intraligand dihedral torsion angles and the distortion of the average N-Fe-N intraligand bond angles.

Borates↗
PubMed2006

Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand.

The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta2-O(CH3)CH2CH2O-O,O)] (4a and 4b) diastereomers and [TpReO(eta2-N(CH3)CH2CH2O-N,O)] (5) and [TpReO(eta2-N(tBu)CH2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta2-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta2-N(CH2)3CHCO2-N,O)] (3) (with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic complexes.

Algorithms↗
PubMed2000

Synthesis of 10,11-dihydroleukotriene B(4) metabolites via a nickel-catalyzed coupling reaction of cis-bromides and trans-alkenyl borates.

Synthesis of 10,11-dihydro-, 10,11,14,15-tetrahydro-, and 10, 11-dihydro-12-oxoleukotriene B(4) compounds (2, 4, 5) was accomplished stereoselectively by using the nickel-catalyzed coupling reaction illustrated in Scheme 1. The C(1)-C(7) fragments, TBS ether 10a for 2 and 4 and ethyoxyethyl (EE) ether 10b for 5, were prepared in enantiomerically pure forms (>99% ee) by a modified literature procedure (ref 11a). On the other hand, boronate esters 11a and 11b, which correspond to the C(8)-C(20) parts of 2 and 4, respectively, were synthesized from (R)-epichlorohydrin (18) of 99% ee. Briefly, 18 was converted into acetylenes 24 and 32 through epoxide ring-opening with LiC triple bond CC(5)H(11)/BF(3).OEt(2) or C(7)H(15)MgBr/CuCN. Hydroboration of these acetylenes with (+)-(Ipc)(2)BH followed by reaction with MeCHO afforded the corresponding diethyl boronates, which upon ligand exchange with Me(2)C(CH(2)OH)(2) furnished boronate esters 11a and 11b in 75% and 77% yields, respectively. In a similar manner, racemic boronate ester rac-11a, an intermediate for synthesis of 5, was prepared from racemic epichlorohydrin. For synthesis of 2, borate 25 was generated from 11a (1.5 equiv) and MeLi (1.6 equiv). Without isolation, 25 was submitted to reaction with 10a (1 equiv) in the presence of a Ni(0) species at room temperature overnight to afford 26, which upon treatment with TBAF furnished 2 in 64% yield from 10a. Similarly, 11b and 10a furnished 4 in good yield. To synthesize 5, rac-11a and EE ether 10b were joined by the coupling reaction to produce 39, which was transformed into 40 by desilylation with TBAF. After hydrolysis of 40, oxidation with PDC followed by deprotection of the EE group furnished 5 in 36% yield from 40. In addition, 2 was converted into amide 3 in 92% yield.

Borates↗
PubMed2005

Study of the dative bond in 2-aminoethoxydiphenyl borate at various levels of theory: another poor performance of the B3LYP method for B-N dative bonds.

Aminoethoxydiphenyl borate (2-APB), 1, is a potent inhibitor of store-operated calcium entry channels (SOCCs). Other SOCC inhibitors are being investigated as promising pharmacological agents for a variety of conditions. Though toxic, 2-APB could be useful in the development of additional inhibitors, but its preferred binding structure must first be determined. Thus, we performed ab initio calculations to study the conformers and the strength of the dative bond of 2-APB. As a first step, we performed a series of computations at various levels of theory. We obtained vastly different dissociation energies for the dative bond depending on whether we used MP2 or B3LYP (7-10 kcal/mol different). This discrepancy has previously been observed for other B-N dative bonds by Gilbert, who found that the MP2 values were in much better agreement with experimental values (Gilbert, T. M. J. Phys. Chem. A 2004, 108, 2550-2554). Since we lacked experimental data for comparison, we performed CCSD(T) calculations and found them to have similar results to those from MP2. Thus, we conclude that MP2 is more accurate for 2-APB. The dissociation free energy at the MP2 level is 7 kcal/mol and indicates that the dative bond conformer will be the predominant structure in the gas phase. The dissociation energy is comparatively low due to the electron donation from the oxygen atom to the boron atom and due to the ring strain in the dative bond conformer.

Borates↗
PubMed2006

Mutations in sodium-borate cotransporter SLC4A11 cause recessive congenital hereditary endothelial dystrophy (CHED2).

Congenital hereditary endothelial dystrophy (CHED) is a heritable, bilateral corneal dystrophy characterized by corneal opacification and nystagmus. We describe seven different mutations in the SLC4A11 gene in ten families with autosomal recessive CHED. Mutations in SLC4A11, which encodes a membrane-bound sodium-borate cotransporter, cause loss of function of the protein either by blocking its membrane targeting or nonsense-mediated decay.

Amino Acid Substitution↗
PubMed2006

The gene responsible for borate cross-linking of pectin Rhamnogalacturonan-II is required for plant reproductive tissue development and fertilization.

Deficiencies in boron, a microelement that is essential for the growth and development of higher plants, often cause problems in reproductive growth. Rhamnogalacturonan-II (RG-II) in cell wall pectin acts as the sole receptor for boron in plant cells, forming a borate cross-linked RG-II dimer (dRG-II-B), but the physiological functions of dRG-II-B remain unknown. We have previously shown that the pectin glucuronyltransferase 1 gene NpGUT1, which is involved in the biosynthesis of RG-II sugar chains, is essential for the formation of the RG-II-B complex, resulting in tight intercellular attachment in meristematic tissues. Because NpGUT1 expression was found to be abundant in reproductive organs in addition to meristematic tissues, we analyzed the expression and functions of NpGUT1 in more detail in tobacco reproductive tissues. Specific NpGUT1 expression was detected in the tapetum of flower buds and in the pollen, pollen tube tips, and transmitting tissue of the pistils of flowers. Dexamethasone-induced expression of the NpGUT1 antisense gene in flower buds resulted in the formation of sterile flowers with aberrant development of pollen and transmitting tissue. Pollen tubes could not pass through pistils with aborted transmitting tissue, and expression of an NpGUT1 antisense gene in germinating pollen inhibited pollen tube elongation, accompanied by the absence of pectin RG-II and boron in the pollen tube tip. These results indicate that expression of NpGUT1 is required for the development and functions of male and female tissues.

Borates↗
PubMed1999

Recognition control of the nucleic acid model through conformational switching of nucleobase induced by borate ester formation of cis-2',3'-diol.

A novel nucleic acid model that possessed 5'-amino-5'-deoxyuridine at alpha- and gamma-position of L-glutamic acid through amide linkage using 5'-amino group was synthesized and the conformation and the hybridization properties were studied. The complex of alpha-PRNA with complementary DNA/RNA was more stable than the corresponding natural duplex in the absence of borate. Its recognition ability was however lost when borax was added to the solution.

Borates↗
PubMed2004

Response of a lithium gadolinium borate scintillator in monoenergetic neutron fields.

Accurate estimation of neutron dose requires knowledge of the neutron energy distribution in the working environment. Existing neutron spectrometry systems, Bonner spheres for example, are large and bulky, and require long data acquisition times. A portable system that could indicate the approximate neutron energy spectrum in a short time would be extremely useful in radiation protection. A composite scintillator, consisting of lithium gadolinium borate crystals in a plastic scintillator matrix, produced by Photogenics is being tested for this purpose. A prototype device based on this scintillator and digital pulse processing electronics has been calibrated using quasi-monoenergetic neutron fields at the low-scatter facility of the UK National Physical Laboratory (NPL). Energies selected were 144, 250, 565, 1400, 2500 and 5000 keV, with correction for scattered neutrons being made using the shadow cone technique. Measurements were also made in the NPL thermal neutron field. Pulse distributions collected with the digitiser in capture-gated mode are presented, and detection efficiency and energy resolution derived. For comparison, neutron spectra were also collected using the commercially available Microspec N-Probe from Bubble Technology Industries, which consists of an NE213 scintillator and a 3He proportional counter.

Algorithms↗
PubMed2006

Individual monitoring based on magnesium borate.

Valuable features of magnesium borate sintered solid thermoluminescence dosemeters (TLDs), such as near tissue- equivalence, high sensitivity, and good performances for X, gamma, beta and neutron dosimetry, were developed and produced by the Institute of Nuclear Sciences, Vinca. These features form the basis for using this type of TLDs successfully for legal personal dosimetry control in Serbia for the past 27 y. The dosimetric properties of this TL material are presented in this study.

Borates↗
PubMed1987

Effects of L-serine borate on antagonism of leukotriene C4-induced contractions of guinea-pig trachea.

The antagonist activity of three leukotriene D4 (LTD4) receptor antagonists and a number of bronchodilators was determined against LTC4-induced contractions of guinea-pig isolated tracheal chains in the absence and presence of the gamma-glutamyltranspeptidase inhibitor, L-serine borate (SB). The LTD4 receptor antagonists FPL-55712, L-649,923 and L-648,051 effectively antagonized LTC4 responses in the absence of SB but were ineffective in the presence of 15 and/or 45 mM SB. Salbutamol greater than isobutylmethylxanthine (IBMX) greater than dibutyryl cyclic AMP greater than aminophylline greater than nifedipine antagonized contractions to LTC4 in the absence of SB. In contrast, in the presence of SB the antagonist activity of all of these agents except nifedipine was significantly reduced. The antagonist activity of the Ca2+ entry blocker, nifedipine, was similar in the absence and presence of SB. Salbutamol and IBMX were potent functional antagonists of LTE4-induced contractions both in the absence and presence of SB. These results are consistent with the hypothesis that there are contractile LTC4 receptor mechanisms in guinea-pig trachea which are unmasked by SB and are not blocked by LTD4 receptor antagonists and which are less effectively down modulated by cyclic AMP-dependent bronchodilators.

1-Methyl-3-isobutylxanthine↗
PubMed1998

Lithium borate TLD for determining the backscatter factors for low-energy x rays: comparison with chamber-based and Monte Carlo derived values.

Recently, new backscatter factors for low-energy x rays derived from Monte Carlo calculations have been recommended in the UK code of practice for kilovoltage dosimetry published by (IPEMB). As these data, presented as a function of half-value layer, do not take account of the variation of the x-ray spectra for a given HVL, we have undertaken an experimental study in order to determine BSG for the beam qualities provided by a Darpac 2000 therapy unit. A RTL detector such as Li2B4O7:Cu and parallel-plate ion chambers specially designed for low-energy x-ray dosimetry have been used. The results obtained show very good agreement between the TLD and the Monte Carlo calculations, confirming values obtained by other authors with lithium borate TLD. On the contrary, the results obtained with plane-parallel ion chambers show discrepancies up to 9% that are discussed.

Borates↗
PubMed2007

Borate transporter SLC4A11 mutations cause both Harboyan syndrome and non-syndromic corneal endothelial dystrophy.

Harboyan syndrome, or corneal dystrophy and perceptive deafness (CDPD), consists of congenital corneal endothelial dystrophy and progressive perceptive deafness, and is transmitted as an autosomal recessive trait. CDPD and autosomal recessive, non-syndromic congenital hereditary endothelial corneal dystrophy (CHED2) both map at overlapping loci at 20p13, and mutations of SLC4A11 were reported recently in CHED2. A genotype study on six families with CDPD and on one family with either CHED or CDPD, from various ethnic backgrounds (in the seventh family, hearing loss could not be assessed because of the proband's young age), is reported here. Novel SLC4A11 mutations were found in all patients. Why some mutations cause hearing loss in addition to corneal dystrophy is presently unclear. These findings extend the implication of the SLC4A11 borate transporter beyond corneal dystrophy to perceptive deafness.

Abnormalities, Multiple↗
PubMed2000

An alternative base-pairing of catechol-bearing nucleosides by borate formation.

A chelator-type beta-C-nucleoside having a catechol ligand as the nucleobase was found to form a stable 2:1 complex with trimethyl borate, which was characterized by 1H-NMR and electrospray ionization time-of-flight (ESI-TOF) mass spectroscopies. Both phosphoramidite and phosphotriester derivatives of this nucleoside were also prepared as synthetic precursors for DNA oligomer syntheses.

Base Pairing↗
PubMed2002

Optical parametric properties of ultraviolet-pumped cesium lithium borate crystals.

We report the optical parametric properties of cesium lithium borate (CLBO) crystals pumped by UV radiation of the fourth-harmonic generation at 266 nm and the third-harmonic generation at 355 nm of a picosecond Nd:YAG laser. A special optical design was used to avoid damage to the optical elements by the UV-pumped beam at 266 nm. The optical parametric generator (OPG)/optical parametric amplifier (OPA) of the 266-nm-pumped CLBO covers the tuning range from 347 nm in the UV to 1137 nm in the near IR. The 355-nm-pumped CLBO OPG/OPA, on the other hand, is tunable from 447 to 1725 nm. The experimental tuning curves for each CLBO OPG/OPA were measured and compared with the theoretical tuning curves. With a double-pass OPG configuration and a pumping intensity of approximately 6 GW/cm2, the maximum conversion efficiency, including both the signal and the idler, was approximately 11% for the 266-nm-pumped CLBO and is greater than 16% for the 355-nm-pumped CLBO without taking into account the surface losses from the uncoated elements. The bandwidth of this double-pass CLBO OPG at various wavelengths was measured and compared with other optical parametric systems. Because of the small angular dispersion of CLBO, the bandwidth of the OPG and OPA systems is exceptionally narrow, especially for the 266-nm-pumped system. Without the use of any dispersion element, the bandwidth of the 266-nm-pumped system can be as narrow as 0.22 nm at wavelengths far from the degenerate point. Comparison between the experimental bandwidth and the theoretical calculation shows that the bandwidth of the UV-pumped CLBO OPG/OPA is limited mainly by the divergence of the pump beam.

Borates↗
PubMed2006

Borate cross-linked/total rhamnogalacturonan II ratio in cell walls for the biochemical diagnosis of boron deficiency in hydroponically grown pumpkin.

Boron (B) is an essential micronutrient for vascular plants. The function of B has been demonstrated to cross-link monomeric rhamnogalacturonan II (mRG-II) to form dimeric RG-II-borate (dRG-II-B), and thus to stabilize plant cell walls. The dRG-II-B to total RG-II ratio in the cell walls of pumpkin hydroponically grown under various low-B conditions was analyzed to evaluate its applicability to the diagnosis of plant B deficiency. The dRG-II-B ratio in cell walls ranged between approximately 0.9 in B-sufficient tissues and approximately 0.15 in severe B-deficient tissues, reflecting the B nutritional status of tissues. This result indicates that the degree of B shortage in plant tissues is very likely to be diagnosed by the dRG-II-B ratio in cell walls.

Borates↗
PubMed2005

Borate transport and cell growth and proliferation. Not only in plants.

Boron is an abundant mineral essential for the life cycle of plants and may play a role in animal development and growth. Very little is known about boron homeostasis in plant and animal cells and the physiological roles of boron in animals. The recent identification of boron transporters, BOR1 in plants and NaBC1 in mammals, and that NaBC1 functions as an electrogenic Na+-coupled borate transporter essential for cell growth and proliferation open the way to probe the roles of boron in cellular function and physiology.

Animals↗