237 resultados para OH^-
Resumo:
A layered double hydroxide (LDH) with chemical composition LiAl2(OH)(7) . 2H(2)O was prepared via a wet chemical route of gel to crystallite (G-C) conversion at 80 degrees C involving the reaction of hydrated alumina gel, Al2O3.yH(2)O (80 < y < 120) with LiOH (Li2O/Al2O3 greater than or equal to 0.5) in presence of hydrophilic solvents such as ethanol under refluxing conditions. The hydrothermal synthesis was carried out using the same reactants by heating to less than or equal to 140 degrees C in a Teflon-lined autoclave under autogenerated pressure (less than or equal to 20 MPa). Transmission electron microscopy showed needle-shaped aggregates of size 0.04-0.1 mu m for the gel to crystallite conversion product, whereas the hydrothermal products consisted of individual lamellar crystallites of size 0.2-0.5 mu m with hexagonal morphology. The LDH prepared through the gel to crystallite conversion could be converted into LiAl(OH)(4) . H2O or LiAl(OH)(3)NO3 . H2O by imbibition of LiOH or LiNO3, respectively, under hydrothermal conditions. Thermal decomposition of LDH above 1400 degrees C gave rise to LiAl5O8 accompanied by the evaporation of Li2O. LiAl(OH)(4) . H2O and LiAl(OH)(3)NO3 . H2O decomposed in the temperature range 400-1000 degrees C to alpha- or beta-LiAlO2. The compositional dependence of the product, the intermediate phases formed during the heat treatment and the possible reactions involved are described in detail.
Resumo:
Hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods were prepared by hydrothermal method. Dy(OH)(3) nanorods was directly obtained at 180 degrees C for 20 h after hydrothermal treatment whereas subsequently heat treatment at 750 degrees C for 2 h gives pure cubic Dy2O3. SEM micrographs reveal that needle shaped rods with different sizes were observed in both the phases. TEM results also confirm this. The TL response of hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods have been analyzed for gamma-irradiation over a wide range of exposures (1-5 kGy). TL glow peak intensity increases with gamma dose in both the phases. The activation energy (E), order of kinetics (6), and frequency factor (s) for both the phases have been determined using Chen's peak shape method. The simple glow curve shape, structure and linear response to gamma-irradiation over a large span of exposures makes the cubic Dy2O3 as a useful dosimetric material to estimate high exposures of gamma-rays. (c) 2012 Elsevier Ltd. All rights reserved.
Resumo:
Treatment of the chloro-substituted diboradiferrocene derivative 1 with Me3SiOMe and subsequent hydrolysis resulted in formation of the novel organometallic bis(borinic acid) derivative 3. The assembly of 3 into supramolecular structures via hydrogen bonding and reversible covalent boron-oxygen bond formation was explored. Upon crystallization from acetone or THF one-dimensional chains form in which molecules of 3 alternately serve as hydrogen bond donors and acceptors. The additional OH hydrogens that are not involved in hydrogen bonding within the polymeric chains undergo hydrogen bonding to the solvent molecules. Removal of the solvent was achieved at moderate temperature under high vacuum. While the polymeric chains remain intact, in the absence of the solvent as a hydrogen bond acceptor, short contacts to the Cp rings of neighboring polymer strands lead to a network-like structure. At higher temperatures, further dehydration occurs with formation of B-O-B linkages as confirmed by MALDI-TOF mass spectrometry. Oligomers with up to 15 repeating units (30 ferrocenes) were detected.
Resumo:
A new series of inorganic-organic hybrid framework compounds, Ln(2)(mu(3)-OH)(C4H4O5)(2)(C4H2O4)]center dot 2H(2)O, (Ln = Ce, Pr and Nd), have been prepared employing a hydrothermal method. Malic acid and fumaric acid form part of the structure. The malate units connect the lanthanide centers forming Ln-O-Ln two-dimensional layers, which are cross-linked by the fumarate units forming the three-dimensional structure. Extra framework water molecules form a dimer and occupy the channels. The water molecules can be reversibly adsorbed. The dehydrated structure did not show any differences in framework structure/ connectivity. The presence of lattice water provides a pathway for proton conductivity. Optical studies suggest an up-conversion behavior involving more than one photon for a neodymium compound.
Resumo:
Rod like structures of hexagonal Y(OH)(3):Ni2+ and cubic Y2O3:Ni2+ phosphors have been successfully synthesized by solvothermal method. X-ray diffraction studies of as-formed product shows hexagonal phase, whereas the product heat treated at 700 degrees C shows pure cubic phase. Scanning electron micrographs (SEM) of Y(OH)(3):Ni2+ show hexagonal rods while Y2O3:Ni2+ rods were found to consist of many nanoparticles stacked together forming multi-particle-chains. EPR studies suggest that the site symmetry around Ni2+ ions is predominantly octahedral. PL spectra show emission in blue, green and red regions due to the T-3(1)(P-3)->(3)A(2)(F-3), T-1(2)(D-1)->(3)A(2)(F-3) and T-1(2)(D-1)-> T-3(2)(F-3) transitions of Ni2+ ions, respectively. TL studies were carried out for Y(OH)(3):Ni2+ and Y2O3:Ni2+ phosphor upon gamma-dose for 1-6 kGy. A single well resolved glow peaks at 195 and 230 degrees C were recorded for Y(OH)(3):Ni2+ and Y2O3:Ni2+, respectively. The glow peak intensity increases linearly up to 4 kGy and 5 kGy for Y(OH)(3):Ni2+ and Y2O3:Ni2+, respectively. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were estimated by different methods. The phosphor follows simple glow peak structure, linear response with gamma dose, low fading and simple trap distribution, suggesting that it is quite suitable for radiation dosimetry. (C) 2014 Elsevier B.V. All rights reserved.
Resumo:
Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.
Resumo:
Computational study of X-Ha <-C and C-Ha <-X hydrogen bonds in n-alkane-HX complexes (X =F,OH, alkane =propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For n-alkane-H2O complexes both Oa <-H-C and O-Ha <-C hydrogen bonded complex have been found, while for n-alkane-HF complexes, our attempt to optimize Fa <-H-C H-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of H-F and O-H stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, X-Ha <-C hydrogen bonds are found to be stronger than C-Ha <-X hydrogen bonds.
Resumo:
Novel BioBr/Cd(OH)(2) heterostructures were synthesized by a facile chemical bath method under ambient conditions. A series of BiOBr/Cd(OH)(2) heterostructures were obtained by tuning the Bi/Cd molar ratios. The obtained heterostructures were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Optical properties were studied by UV-visible spectroscopy, diffuse reflectance spectroscopy and photoluminescence (PL). Photocatalytic studies on rhodamine B (RhB) under visible light irradiation showed that the heterostructures are very efficient photocatalysts in mild basic medium. Scavenger test studies confirmed that the photogenerated holes and superoxide radicals (O-2(center dot-)) are the main active species responsible for RhB degradation. Comparison of photoluminescence (PL) intensity suggested that an inhibited charge recombination is crucial for the degradation process over these photocatalysts. Moreover, relative positioning of the valence and conduction band edges of the semiconductors, O-2/O-2(center dot-) and (OH)-O-center dot/H2O redox potentials and HOMO-LUMO levels of RhB appear to be responsible for the hole-specificity of degradation. Photocatalytic recycling experiments indicated the high stability of the catalysts in the reaction medium without any significant loss of activity. This study hence concludes that the heterojunction constructed between Cd(OH)(2) and BiOBr interfaces play a crucial role in influencing the charge carrier dynamics and subsequent photocatalytic activity.
Resumo:
The current work reports quantitative OH species concentration in the cavity of a trapped vortex combustor (TVC) in the context of mixing and flame stabilization studies using both syngas and methane fuels. Planar laser induced fluorescence (PLIF) measurements of OH radical obtained using a Nd: YAG pumped dye laser are quantified using a flat flame McKenna burner. The momentum flux ratio (MFR), defined as the ratio of the cavity fuel jet momentum to that of the guide vane air stream, is observed to be a key governing parameter. At high MFRs similar to 4.5, the flame front is observed to form at the interface of the fuel jet and the air jet stream. This is substantiated by velocity vector field measurements. For syngas, as the MFR is lowered to similar to 0.3, the fuel-air mixing increases and a flame front is formed at the bottom and downstream edge of the cavity where a stratified charge is present. This trend is observed for different velocities at similar equivalence ratios. In case of methane combustion in the cavity, where the MFRs employed are extremely low at similar to 0.01, a different mechanism is observed. A fuel-rich mixture is now observed at the center of the cavity and this mixture undergoes combustion. On further increase of the cavity equivalence ratio, the rich mixture exceeds the flammability limit and forms a thin reaction zone at the interface with air stream. As a consequence, a shear layer flame at the top of the cavity interface with the mainstream is also observed. The equivalence ratio in the cavity also determines the combustion characteristics in the case of fuel-air mixtures that are formed as a result of the mixing. Overall, flame stabilization mechanisms have been proposed, which account for the wide range of MFRs and premixing in the mainstream as well.
Resumo:
Five stereochemically constrained analogs of the chemotactic tripeptide incorporating 1-aminocycloalkane-1-carboxylic acid (Ac(n)c) and alpha,alpha-dialkylglycines (Deg, diethylglycine; Dpg, n,n-dipropylglycine and Dbg, n,n-dibutylglycine) at position 2 have been synthesized. NMR studies of peptides For-Met-Xxx-Phe-OMe (Xxx = Ac(7)c, I; Ac(8)c, II; Deg, III; Dpg, IV and Dbg, V; For, formyl) establish that peptides with cycloalkyl residues, I and II, adopt folded beta-turn conformations in CDCl3 and (CD3)(2)SO. In contrast, analogs with linear alkyl sidechains, III-V, favour fully extended (C-5) conformations in solution. Peptides I-V exhibit high activity in inducing beta-glucosaminidase release from rabbit neutrophils, with ED(50) values ranging from 1.4-8.0 x 10(-11)M. In human neutrophils the Dxg peptides III-V have ED(50) values ranging from 2.3 x 10(-8) to 5.9 x 10(-10) M, with the activity order being V > IV > III. While peptides I-IV are less active than the parent. For-Met-Leu-Phe-OH, in stimulating histamine release from human basophils, the Dbg peptide V is appreciably more potent, suggesting its potential utility as a probe for formyl peptide receptors.
Resumo:
This paper reports a new class of photo-cross-linkable side chain liquid crystalline polymers (PSCLCPs) based on the bis(benzylidene)cyclohexanone unit, which functions as both a mesogen and a photoactive center. Polymers with the bis(benzylidene)cyclohexanone unit and varying spacer length have been synthesized. Copolymers of bis(benzylidene)cyclohexanone containing monomer and cholesterol benzoate containing monomer with different compositions have also been prepared. All these polymers have been structurally characterized by spectroscopic techniques. Thermal transitions were studied by DSC, and mesophases were identified by polarized light optical microscopy (POM). The intermediate compounds OH-x, the monomers SCLCM-x, and the corresponding polymers PSCLCP-x, which are essentially based on bis(benzylidene)cyclohexanone, all show a nematic mesophase. Transition temperatures were observed to decrease with increasing spacer length. The copolymers with varying compositions exhibit a cholesteric mesophase, and the transition temperatures increase with the cholesteric benzoate units in the copolymer. Photolysis of the low molecular weight liquid crystalline bis(benzylidene)-cyclohexanone compound reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerization and 2 pi + 2 pi addition. The EZ photoisomerization in the LC phase disrupts the parallel stacking of the mesogens, resulting in the transition from the LC phase to the isotropic phase. The photoreaction involving the 2 pi + 2 pi addition of the bis(benzylidene)cyclohexanone units in the polymer results in the cross-linking of the chains. The liquid crystalline induced circular dichroism (LCICD) studies of the cholesterol benzoate copolymers revealed that the cholesteric supramolecular order remains even after the photo-cross-linking.
Resumo:
Complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(2) (la-c), [Ru2O(O2CR)(2)(ImH)(6)](ClO4)(2) (2a,b), and [Ru2O(O2CR)(2)(4-MeImH)(6)](ClO4)(2) (3a,b) with a (mu-oxo)bis(mu-carboxylato)diruthenium(III) core have been prepared by reacting Ru2Cl(O2CR)(4) with the corresponding imidazole base, viz. 1-methylimidazole (1-MeIm), imidazole (ImH), and 4-methylimidazole (4-MeImH) in methanol, followed by treatment with NaClO4 in water (R: Me, a; C6H4-p-OMe, b; C6H4-p-Me, c). Diruthenium(III,IV) complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(3) (R: Me, 4a; C6H4-p-OMe, 4b; C6H4-p-Me, 4c) have been prepared by one-electron oxidation of 1 in MeCN with K2S2O8 in water. Complexes la, 2a . 3H(2)O, and 4a . 1.5H(2)O have been structurally characterized. Crystal data for the complexes are as follows: la, orthorhombic, P2(1)2(1)2(1), a = 7.659(3) Angstrom, b = 22.366(3) Angstrom, c = 23.688(2) Angstrom, V = 4058(2) Angstrom(3), Z = 4, R = 0.0475, and R-w = 0.0467 for 2669 reflections with F-o > 2 sigma(F-o); 2a . 3H(2)O, triclinic,
Resumo:
Several mechanisms have been proposed to explain the action of enzymes at the atomic level. Among them, the recent proposals involving short hydrogen bonds as a step in catalysis by Gerlt and Gassman [1] and proton transfer through low barrier hydrogen bonds (LBHBs) [2, 3] have attracted attention. There are several limitations to experimentally testing such hypotheses, Recent developments in computational methods facilitate the study of active site-ligand complexes to high levels of accuracy, Our previous studies, which involved the docking of the dinucleotide substrate UpA to the active site of RNase A [4, 5], enabled us to obtain a realistic model of the ligand-bound active site of RNase A. From these studies, based on empirical potential functions, we were able to obtain the molecular dynamics averaged coordinates of RNase A, bound to the ligand UpA. A quantum mechanical study is required to investigate the catalytic process which involves the cleavage and formation of covalent bonds. In the present study, we have investigated the strengths of some of the hydrogen bonds between the active site residues of RNase A and UpA at the ab initio quantum chemical level using the molecular dynamics averaged coordinates as the starting point. The 49 atom system and other model systems were optimized at the 3-21G level and the energies of the optimized systems were obtained at the 6-31G* level. The results clearly indicate the strengthening of hydrogen bonds between neutral residues due to the presence of charged species at appropriate positions. Such a strengthening manifests itself in the form of short hydrogen bonds and a low barrier for proton transfer. In the present study, the proton transfer between the 2'-OH of ribose (from the substrate) and the imidazole group from the H12 of RNase A is influenced by K41, which plays a crucial role in strengthening the neutral hydrogen bond, reducing the barrier for proton transfer.
Resumo:
Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have envelope conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.
Resumo:
Homogeneous precipitation from solution by hydrolysis of urea at elevated temperatures (T=120 degrees C) yields novel ammonia-intercalated alpha-type hydroxide phases of the formula M(OH)(x)(NH3)(0.4)(H2O)(y)(NO3)(2-x) where x=2, y=0.68 for M=Ni and x=1.85, y=0 for M=Co. These triple-layered hexagonal phases (a=3.08+/-0.01 Angstrom, c=21.7+/-0.05 Angstrom) are more crystalline than similar phases obtained by chemical precipitation or electrosynthesis. This method can be adapted as a convenient chemical route to the bulk synthesis of alpha-hydroxides.
