Removal of boron(III) by N-methylglucamine-type cellulose derivatives with higher adsorption rate

To obtain adsorbents for boron(III) derived from a natural polymer, two forms (powder and fiber) of N-methylglucamine-type cellulose derivatives were newly synthesized. After the graft polymerization of two forms of cellulose with vinyl monomer having epoxy groups, the N-methylglucamine-type cellulose derivatives were obtained by the reaction of the grafted cellulose with N-methylglucamine. The adsorption capacities of the cellulose derivatives for boron(III) were the same levels as that of a commercially available N-methylglucamine-type polystyrene resin. However, the cellulose derivatives adsorbed boron(III) more quickly than the polystyrene resin. The adsorption and desorption of boron(III) with a column method using the cellulose fiber were achieved at a higher flow rate than that using the polystyrene resin. In addition, the boron(III), adsorbed on the cellulose fiber column, was quantitatively recovered with dilute hydrochloric acid in 20- and 200-fold increased concentrations. Consequently, it was found that the cellulose derivatives were superior to the polystyrene resin as adsorbents for boron(III) for treatment of a large quantity of wastewater.     

Stereoselectivity in the aldol reaction: The use of chiral and achiral oxazolines as their boron azaenolates

Chiral oxazolines, as their boron enolates derived from various boron triflates, react with aldehydes to give erythro-selectivity (97% + %) with enantiomeric purities of 50–60%. Achiral oxazolines as their boron enolates derived from diisopinocampheylborane give, on reaction with aldehydes, β-hydroxy esters with high threo-selectivity (90+%) in 77–85% ee. A variety of structurally different oxazolines were also studied and many show high erythro -selectivity.     

First-principles study of the crystal and electronic structures of α-tetragonal boron

The crystal and electronic structures of α-tetragonal (α-t) boron were investigated by first-principles calculation. Application of a simple model assuming 50 atoms in the unit cell indicated that α-t boron had a metallic density of state, thus contradicting the experimental fact that it is a p-type semiconductor. The presence of an additional two interstitial boron atoms at the 4c site made α-t boron semiconductive and the most stable. The cohesive energy per atom was as high as those of α- and β-rhombohedral boron, suggesting that α-t boron is produced more easily than was previously thought. The experimentally obtained α-t boron in nanobelt form had about two interstitial atoms at the 8i sites. We consider that the shallow potential at 8i sites generates low-energy phonon modes, which increase the entropy and consequently decrease the free energy at high temperatures. Calculation of the electronic band structure showed that the highest valence band had a larger dispersion from Γ to Z than from Γ to X; this indicated a strong anisotropy in hole conduction.     

Crystal structure of tetragonal boron related to α-AlB12

Single crystals of the so-called β-tetragonal (or tetragonal II or III) boron modification have been obtained from boron deposits prepared by hydrogen reduction of BBr₃ on tantalum filaments at 1200°C. Chemical analysis of the samples shows that this phase can be regarded as a true modification of pure elemental boron in contrast to α-tetragonal phases which require small amounts of foreign atoms to stabilize their boron framework.The lattice parameters (a = 10.14(1)Å; c = 14.17(1)Å) were obtained and refined from single crystal data. The unit cell contains four chemical units, B₂₁ · 2B₁₂ · B_2.5 resulting in d_c = 2.34 g cm^?3 (d_m = 2.36(2) g cm^?3). The systematic extinctions are compatible with space group P4₁ or P4₃.The structure was determined from 1009 independent reflexions using a model derived from the recently solved structure of α - AlB₁₂ (a = 10.161Å; c = 14.283Å; space group P4₁2₁2 or P4₃2₁2). The final R value (unweighted data) is 9.6%.Basically, the structure of this tetragonal form of boron consists of the same three-dimensional boron skeleton, built upon simple and twinned icosahedra, as that of α-AlB₁₂. However, the defective twinned icosahedral B₁₉ units in α-AlB₁₂ are now completed (B₂₁ units) in the related tetragonal boron. A number of interstitial sites, located at positions different from those occupied by aluminum in α-AlB₁₂, are totally or partially filled by boron atoms and very probably increase the stability of the boron framework.     

Addition of kinetic boron enolates generated from β-alkoxy methyl ketones to aldehydes. Density functional theory calculations on the transition structures

Herein we report that good to excellent levels of 1,5-anti stereoinduction are obtained in boron enolate aldol reactions of 1,2-syn β-alkoxy methyl ketones with achiral aldehydes, when the β-alkoxy protecting group is part of a benzylidene acetal. We have also investigated the effects of the ligands on boron, the α-, β-, and γ-substituents and the β-alkoxy protecting group on the boron enolates, using density functional theory (B3LYP) and Møller-Plesset perturbation theory (MP2) calculations.     

Isotherms,kinetics, and thermodynamics of boron adsorption on fibrous polymeric chelator containing glycidol moiety optimized with response surface method

A fibrous boron chelator containing glycidol moiety (PE/PP-g-PVAm-G) was prepared by radiation induced grafting of N-vinylformamide (NVF) onto polyethylene/polypropylene (PE/PP) non-woven sheet followed by hydrolysis and immobilization of glycidol moiety. The glycidol density was controlled by optimization of the reaction parameters using the Box-Behnken design of response surface methodology (RSM). The properties of the PE/PP-g-PVAm-G were evaluated using Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM) and energy dispersive x-ray (EDX) analysis, X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). A maximum glycidol density yield of 5.0 mmol·g⁻¹ was obtained with 11.8 vol%, 78.9 °C and 109.4 min for glycidol concentration, reaction temperature and time, respectively. The isotherms, kinetics, and thermodynamic behavior of boron adsorption on the optimized chelator were investigated. The boron adsorption was pH-dependent and attained a maximum adsorption capacity of 25.7 mg·g⁻¹. The equilibrium isotherm proceeded by Redlich–Peterson model whereas the kinetics was best expressed by the pseudo-second-order equation. The thermodynamic analysis revealed that boron adsorption is endothermic and spontaneous. The fibrous chelator demonstrated high boron selectivity and strong resistance to foreign ions with uncompromised regeneration efficiency after five adsorption/desorption cycles. The PE/PP-g-PVAm-G chelator seems to be very promising for boron removal from aqueous media.     

Some aspects for sintering of β-rhombohedral boron

The investigation of sintering conditions for magnesiothermic amorphous boron (Mg_mB_n) powder is presented. The results of chemical and X-ray analyses of magnesiothermic boron (Mg_mB_n) indicate that it consists of amorphous boron MgB₁₂ and a lesser amount of β-rhombohedral boron. The Mg_mB_n-sintering process is determined by the conditions of amorphous boron transformation into β-boron (crystallization), such as the process of decomposition of MgB₁₂ followed by formation of the “new” centers of active elementary boron. As a result of the experimental investigations of this process the following three stages—thermal decompositions, crystallization and Mg_mB_n sintering—were combined into one sintering process with the sintered bodies as a result of it.     

Electron deformation density in titanium diboride chemical bonding in TiB2

Titanium diboride, TiB₂, crystallizes in the AlB₂-type structure, hexagonal P6/mmm. The conventional, free atom crystal structure refinement led to R=2.23%, and including extinction corrections to R=1.58%. Multipole refinements with multipoles up to order four (hexadecapole) reduced the R value to 1.21%. Difference density maps revealed charge deficiencies on the boron sites and broadbands of charge accumulations between the boron atoms indicating a graphitic B-delocalization of the boron sp² hybrid orbitals.     

Investigation of zwitterionic 7-ammonium-7,9-nido-m-carborane

Zwitterionic ammonium-substituted nido m-carborane (7-NH₃-7,9-nido-carborane), a novel boron moiety for boron neutron capture therapy, was synthesized and its chemical properties were investigated. This boron cluster system showed unique properties by reacting with carbonyl groups of ketones and aldehydes to generate the corresponding iminium-substituted nido m-carboranes.     

Some physical properties of compacted specimens of highly dispersed boron carbide and boron suboxide

Structure, shear modulus and internal friction (IF) of compacted specimens of boron carbide and boron suboxide have been investigated. Microtwins and stacking faults were observed along the {100} plane systems of polycrystalline specimens of boron carbide. Electrical conductivity of the specimens was that of p-type. Concentration of holes varied from 10¹⁷ to 10¹⁹ cm⁻³. The IF was measured in the temperature range 80-300 K. It was shown that the IF of boron carbide and that of boron suboxide were characterized with a set of similar relaxation processes. Mechanisms of the relaxation processes in boron carbide and boron suboxide are discussed in terms of the Hasiguti model of interaction between dislocations and point defects.     

Synthesis of cis-3,4-diarylpiperidines and cis-3,4-diaryltetrahydropyrans

Substituted cis-3,4-diarylpiperidines and cis-3,4-diaryltetrahydropyrans are synthesized in modest overall yields starting from 4-aryl-1,2,5,6-tetrahydropyridines and 4-aryl-1,2,5,6-tetrahydropyrans via the following sequence: (1) pinacol-type ring contraction having the combination of m-chloroperoxybenzoic acid and boron trifluoride etherate, (2) Grignard addition with arylmagnesium bromide reagents and followed by boron trifluoride etherate-mediated intramolecular ring-expanded rearrangement, and (3) hydrogenation with hydrogen on 10% palladium-activated carbon. A facile synthesis of 3,4-diarylpyridines was also described by base-induced aromatization.     

A direct synthetic route to B-trifluoroborazines

B-Tris(alkylamino)-N-trialkyl-borazines and B-tris(arylamino)-N-triaryl-borazines may be prepared almost quantitatively by employing the appropriate stoichiometry in the reaction between boron trichloride and an alkyl- or aryl-amine. The borazines so formed react with boron trifluoride or boron trifluoride etherate to give good yields of the B-trifluoro-N-trialkyl- and B-trifluoro-N-triaryl-borazines. Using this methods, (CH₃NBF)₃, (p-ClC₆H₄NBF)₃ and (C₆F₅NBF)₃ have been prepared. The analogous reaction using (C₆F₅)₃B as a route to B-tris(pentafluorophenyl)borazines was unsuccesful.     

The stereochemistry of aziridine borane lithiation: diastereoselectivity and enantioselectivity

Lithiation of 1-methylaziridine borane, 1-(tert-butyldimethylsiloxyethyl)aziridine borane, or 1-(tert-butyldimethylsiloxyethyl)-2-methylaziridine borane occurs syn to the boron substituent, while lithiation of 1-(tert-butyldimethylsiloxyethyl)-2-trimethylstannylaziridine borane occurs anti to boron as well as silicon due to the steric effect of trimethylsilyl group (s-butyllithium was used in all cases). Kinetically controlled lithiation in the first three cases results from a combination of steric and electrostatic effects. Enantioselective lithiation occurs in the presence of (−)-sparteine, with product enantioselectivities near 70% ee.     

Thermoelectric properties of photo- and thermal CVD boron and boron phosphide films

The electrical properties of n-BP films newly prepared by thermal CVD in the B₂H₆-PH₃-H₂ system were improved by a deuterium lamp excitation. High-temperature electrical conductivity and thermoelectric power of amorphous boron and polycrystalline boron phosphide films grown on silica glass were measured to evaluate the thermoelectric figure-of-merit (Z). In particular, the Z-value for photo-thermal BP films was higher (10⁻⁴/K) than that of boron films, indicating that they are promising for high-temperature thermoelectric materials.     

Structural analysis of boron compounds using 11B-3QMAS solid state NMR

The structural analysis of three boron compounds, boron carbide (B₄C), silicon tetraboride (SiB₄) and hexagonal-boron nitride (h-BN), were performed using 2D ¹¹B-triple quantum MAS (3QMAS) solid state NMR capable of averaging the second-order quadrupolar interaction of ¹¹B that cause line broadening, splitting and low frequency shift of the central transition (−1/2, 1/2). The coordination number around the boron atom and structural symmetry of each boron compound is discussed by means of the isotropic chemical shift Δσ and the quadrupolar coupling constant C_Q calculated from 3QMAS spectra. Δσ of SiB₄ is quite larger than that of B₄C, which is thought to be caused by its structural distortion and distribution. Δσ of h-BN was found to be higher frequency shift obviously than that of B₄C and SiB₄ because of the difference of the boron coordination number, three-coordinated in h-BN and six-coordinated in B₄C and SiB₄. h-BN has very large C_Q compared to other two boron compounds since the h-BN forming a two-dimensional network has less structural symmetry than B₄C and SiB₄.     

Separation properties of high temperature reverse osmosis membranes for silica removal and boric acid recovery

The separation system containing thin-film polyamide reverse osmosis membrane (tf-PA RO) of high temperature was studied.In performed laboratory tests, RO silica rejection percentage was over 97%, and boron passage was about 60–65% (molecular weight cut off of 200 or 250 Da) of the solution which contained silica in the range of 1–90 ppm and boron in the range of 7500–15,000 ppm. The separation factor (SF) between boron and silica related to boron concentration could be expressed as the relation, SF = k[boron]^0.7. The separation process could be described by a mass balance model. The modeling calculation fitted the experimental results very well, within the acceptable parameters’ errors. It was proposed that the boric acid in a boric acid storage tank (BAST) of one studied pressurized water reactor (PWR) plant could be treated with such tf-PA RO. In the prediction, the silica concentration in it would be removed to about 1 ppm, and that the boron could be reused. The waste amount of boron after such treatment was predicted to be less than 1.5%.     

Spying on the boron–boron triple bond using spin–spin coupling measured from 11B solid-state NMR spectroscopy

There is currently tremendous interest in the previously documented example of a stable species exhibiting a boron–boron triple bond (Science, 2012, 336, 1420). Notably, it has recently been stated using arguments based on force constants that this diboryne may not, in reality, feature a boron–boron triple bond. Here, we use advanced solid-state NMR and computational methodology in order to directly probe the orbitals involved in multiple boron–boron bonds experimentally via analysis of ¹¹B–¹¹B spin–spin (J) coupling constants. Computationally, the mechanism responsible for the boron–boron spin–spin coupling in these species is found to be analogous to that for the case of multiply-bonded carbon atoms. The trend in reduced J coupling constants for diborenes and a diboryne, measured experimentally, is in agreement with that known for alkenes and alkynes. This experimental probe of the electronic structure of the boron–boron multiple bond provides strong evidence supporting the originally proposed nature of the bonds in the diboryne and diborenes, and demonstrates that the orbitals involved in boron–boron bonding are equivalent to those well known to construct the multiple bonds between other second-row elements such as carbon and nitrogen.     

New boron-containing 2′-deoxyadenosines

Conjugates of polyhedral boron hydrides with deoxyadenosine were synthesized by the opening of cyclic oxonium derivatives of closo-dodecaborate and cobalt bis(1,2-dicarbollide) with 2′-deoxyadenosine derivatives containing a nucleophilic group in the substituent at C(8). Biological studies of the derivatives obtained for cytotoxicity revealed that the derivatives based on closo-dodecaborate did not exhibit cytotoxicity. The conjugates obtained can be used in further biological trials as potential agents for boron neutron capture therapy of cancer.     

Li- and Mg-doping into icosahedral boron crystals, α- and β-rhombohedral boron, targeting high-temperature superconductivity: structure and electronic states

The possibility of high T_C superconductivity is suggested for lithium- and magnesium-doped icosahedral boron crystals, α- and β-rhombohedral boron. The doping of these elements was attempted by a vapor diffusion processing. Both lithium and magnesium are hardly doped into the α-rhombohedral boron, although small amounts of metallic parts are found in the sample. In only one Li-doped sample, the metallic part contained 0.02 vol% of the superconductive phase (T_C∼36 K). Magnesium was successfully doped into β-rhombohedral boron homogeneously up to 4 at% (Mg_4.1B₁₀₅), although considerable amount of impurity silicon was introduced together with magnesium. The structures of the doped samples were analyzed assuming co-doping of magnesium and silicon. The relation between the site occupancies of the dopants and the lattice expansion is discussed. The estimation of the density of states near the Fermi energy by EELS and magnetic susceptibility measurements suggested a metal transition of the β-rhombohedral boron by the doping of magnesium and silicon. The relation between the metal transition and the intrinsic acceptor level is also discussed.     

A Novel Boron-Rich Scandium Borocarbide; Sc4.5−xB57−y+zC3.5−z(x=0.27, y=1.1, z=0.2)

A novel ternary boron-rich scandium borocarbide Sc_4.5−xB_57−y+zC_3.5−z (x=0.27, y=1.1, z=0.2) was found. Single crystals were obtained by the floating zone method by adding a small amount of Si. Single-crystal structure analysis revealed that the compound has an orthorhombic structure with lattice constants of a=1.73040(6), b=1.60738(6) and c=1.44829(6) nm and space group Pbam (No. 55). The crystal composition ScB_13.3C_0.78Si_0.008 calculated from the structure analysis agreed with the measured composition of ScB_12.9C_0.72Si_0.004. The orthorhombic crystal structure is a new structure type of boron-rich borides and there are six structurally independent B₁₂ icosahedra I1—I6, one B₈/B₉ polyhedron and nine bridging sites all which interconnect each other to form a three-dimensional boron framework. The main structural feature of the boron framework structure can be understood as a layer structure where two kinds of boron icosahedron network layer L1 and L2 stack each other along the c-axis. There are seven structurally independent Sc sites in the open spaces between the boron icosahedron network layers.