Synthesis of 3-oxalinolenic acid and β-oxidation-resistant 3-oxa-oxylipins

3-Oxalinolenic acid (3-oxa-9(Z), 12(Z), 15(Z)-octadecatrienoic acid or (6(Z), 9(Z), 12(Z)-pentadecatrienyloxy)acetic acid) was synthesized from 5(Z), 8(Z), 11(Z), 14(Z), 17(Z)-eicosapentaenoic acid by a sequence involving the C15 aldehyde 3(Z), 6(Z), 9(Z), 12(Z)-pentadecatetraenal as a key intermediate. Conversion of the aldehyde by isomerization and two steps of reduction afforded 6(Z), 9(Z), 12(Z)-pentadecatrienol, which was coupled to bromoacetate to afford after purification by HPLC >99%-pure 3-oxalinolenic acid in 10–15% overall yield. 3-Oxalinolenic acid was efficiently oxygenated by soybean lipoxygenase-1 into 3-oxa-13(S)-hydroperoxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid, and this hydroperoxide could be further converted chemically into 3-oxa-13(S)-hydroxy-9(Z), 11(E), 15(Z)-octadecatrienoic acid and 3-oxa-13-oxo-9(Z), 11(E), 15(Z)-octadecatrienoic acid. The 3-oxa-hydroperoxide also served as the substrate for the plant enzymes allene oxide synthase, divinyl ether synthase, and hydroperoxide lyase to produce 3-oxa-12-oxo-10, 15(Z)-phytodienoic acid and other 3-oxa-oxylipins that were characterized by MS, 3-Oxalinolenic acid was not oxygenated by 9-lipoxygenase from tomato but was converted at a slow rate into 3-oxa-9(S)-hydroperoxy-10(E), 12(Z), 15(Z)-octadecatrienoic acid by recombinant maize 9-lipoxygenase. Recombinant α-dioxygenase-1 from Arabidopsis thaliana catalyzed the conversion of 3-oxalinolenic acid into a 2-hydroperoxide, which underwent spontaneous degradation into a mixture of 6,9,12-pentadecatrienol and 6,9,12-pentadecatrienyl formate. A novel α-dioxygenase from the moss Physcomitrella patens was cloned and expressed and was found to display the same activity with 3-oxalinolenic acid as Arabidopsis thaliana α-dioxygenase-1. Lipoxygenase-generated 3-oxa-oxylipins are resistant toward β-oxidation and have the potential for displaying enhanced biological activity in situations where activity is limited by metabolic degradation.     

Effect of Ga3+ substitution on the microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics

0.67CaTiO₃–0.33La(Al_1−xGa_x)O₃ (0≤x≤0.4) (CTLAG) ceramics with pure perovskite structure were prepared by a conventional two-step solid-state reaction process. The effect of Ga³⁺ substitution for Al³⁺ on the microwave dielectric properties of the ceramics was subsequently investigated. As Ga content increased, the ionic polarizability increased and led to an increase of the dielectric constant (ε_r). Meanwhile, both the tolerance factor (t) of CTLAG ceramics and A-site bond valence were considered to have effect on the temperature coefficient of the resonant frequency (τ_f) with the increase of Ga content. Results also showed that the quality factor (Q×f ) varied with increasing Ga³⁺ content because of not only intrinsic factor but also extrinsic factors such as the bimodal grain size distribution, the variation of relative density, and the packing fraction. Excellent microwave dielectric properties with ε_r≈45.81, Q×f≈34,152 GHz, and τ_f≈3.09 ppm/°C were achieved for 0.67CaTiO₃–0.33La(Al_0.9Ga_0.1)O₃ ceramics sintered at 1420 °C for 4 h.     

Optimization of Propionic Acid Feeding for Production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in Fed-Batch Culture of Ralstonia eutropha

The feeding method of propionic acid for production of poly(3-hydroxybutyrate-co-3-hydro xyvalerate) [P(3HB-co-3HV)] by fed-batch culture of Ralstonia eutropha was optimized to achieve high cell density and high 3HV yield. Effects of different feeding strategies of propionic acid on the production of P(3HB-co-3HV) were investigated. A decline of specific synthesis rate of copolymer and the yield of 3HV unit from propionic acid were observed due to the propionic acid accumulation in culture broth when the feeding solution with high P/G(propionic acid to glucose) ratio was employed. It was further confirmed by controlling propionic acid concentration at a low level in the separate feeding of propionic acid. An optimal feeding strategy was demonstrated to reduce the propionic acid accumulation. The cell concentration, P(3HB-co-3HV) productivity and 3HV unit fraction reached to 163.9kg.m-3, 1.8kg.m-3.h-1, and 10.6%(by mass), respectively, resulting in a yield of 0.33g HV per g propionic acid.     

Effect of the addition of β-Si3N4 nuclei on the thermal conductivity of β-Si3N4 ceramics

Various microstructures of β-Si₃N₄ were fabricated, with or without the addition of β-Si₃N₄ seed particles to high-purity β-Si₃N₄ powder, using Yb₂O₃ and ZrO₂ as sintering additives, by gas-pressure sintering at 1950 °C for 16 h. The thermal conductivity of the specimen without seeds was 140 W·(m·K)⁻¹, and the specimen exhibited a bimodal microstructure with abnormally grown grains. The thermal conductivity of the specimen with 24 vol.% seed addition was 143 W·(m·K)⁻¹, and this specimen had the bimodal microstructure with finer grain size than that without the seeded material, but maintained the same amount of large grains (⩾2 μm in diameter) as in the specimen without the seeds. This finding indicates that the thermal conductivity of β-Si₃N₄ is controlled by the amount of reprecipitated large grains, rather than by the grain size of the β-Si₃N₄.     

Energy storage performance of BiFeO3–SrTiO3–BaTiO3 relaxor ferroelectric ceramics

Dielectric capacitors reveal great potential in the application of high power and/or pulsed power electronic devices owing to their ultrafast charge–discharge rate and ultrahigh power density. Among various dielectric capacitors, the environment-friendly lead-free dielectric ceramics have drawn extensive investigations in recent years. Nevertheless, the relatively small recoverable energy storage density (W_rec) is still an obstacle for their application. Herein, the (0.55−x)BiFeO₃–0.45SrTiO₃–xBaTiO₃ ternary ceramics with 0.1 wt% MnO₂ were prepared by the solid-state reaction, and achieved enhanced relaxor behavior as well as breakdown strength E_b. As a result, the x = 0.12 ceramic exhibited superior comprehensive energy storage performance of large E_b (50.4 kV/mm), ultrahigh W_rec (7.3 J/cm³), high efficiency η (86.3%), relatively fast charge–discharge speed (t_0.9 = 6.1 μs) and outstanding reliability under different frequency, fatigue, and temperature, indicating that the BiFeO₃-based relaxor ferroelectric ceramics are prospective alternatives for electrostatic energy storage.     

Determination of New α-312 MAX phases of Zr3InC2 and Hf3InC2

Present work successfully synthesized two new α-312 MAX phase compounds of Zr₃InC₂ and Hf₃InC₂ using spark plasma sintering. The crystal structure and microstructure of two new compounds were characterized by combining X-ray diffraction (XRD) and scanning electron microscopy (SEM). With typical crystal structure of MAX phase, the obvious layered features on the fracture surface of Zr₃InC₂ and Hf₃InC₂ grains were observed. The lattice parameters of these two new MAX phase compounds were confirmed as a = 3.3515(3) Å, c = 20.2515(9) Å for Zr₃InC₂, and a = 3.3370(3) Å, c = 19.9560(1) Å for Hf₃InC₂, respectively. Also, the atomic positions of Zr₃InC₂ and Hf₃InC₂ were determined as M1 at (0, 0, 0), M2 at (1/3, 2/3, 0.12774[Zr]/0.12455[Hf]), In at (0, 0, 1/4), and C at (1/3, 2/3, 0.57087[Zr]/0.54894[Hf]). Two new sets of XRD patterns of Zr₃InC₂ and Hf₃InC₂ were collected.     

Development of Fluorogenic Probes for Rapid High-Contrast Imaging of Transient Nuclear Localization of Sirtuin 3

Protein labeling using fluorogenic probes enables the facile visualization of proteins of interest. Herein, we report new fluorogenic probes consisting of a rationally designed coumarin ligand for the live-cell fluorogenic labeling of the photoactive yellow protein (PYP)-tag. On the basis of the photochemical mechanisms of coumarin and the probe–tag interactions, we introduced a hydroxy group into an environment-sensitive coumarin ligand to modulate its spectroscopic properties and increase the labeling reaction rate. The resulting probe had a higher labeling reaction rate constant and a greater fluorescence OFF–ON ratio than any previously developed PYP-tag labeling probe. The probe enabled the fluorogenic labeling of intracellular proteins within minutes. Furthermore, we used our probe to investigate the localization of sirtuin 3 (SIRT3), a mitochondrial deacetylase. Although the nuclear localization of SIRT3 has been controversial, this transient nuclear localization was clearly captured by the rapid, high-contrast imaging enabled by our probe.     

Crystallization of LiNbO3 and NaNbO3 in niobiosilicate glass–ceramics

Although glass–ceramics have been widely explored for their thermal stability and mechanical properties, they also offer unique symmetry-dependent properties such as piezoelectricity and pyroelectricity through controlled crystallization of a polar phase. This work examines crystallization of LiNbO₃ in a 35SiO₂–30Nb₂O₅–35Li₂O mol% composition and crystallization of LiNbO₃ and NaNbO₃ in a 35SiO₂–30Nb₂O₅–25Li₂O–10Na₂O mol% composition. Crystallization kinetics are examined using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory where the Avrami exponent, n, is calculated to be 1.0–1.5. Microscopical analysis shows dendritic morphology, which when combined with the JMAK analysis, suggests diffusion-controlled one-dimensional growth. Adding Na₂O to the glass composition increases the inter-diffusivity of ions which causes LiNbO₃ to crystallize faster and lowers the activation energy of transformation from 1054 ± 217 kJ/mol in the ternary composition to 882 ± 212 kJ/mol. Time-temperature-transformation diagrams are presented which show that the temperature for maximum rate of transformation for LiNbO₃ is ∼650°C and for NaNbO₃ is ∼715°C.     

Reduction of NO by CO on PdO-MoO3/γ-Al2O3 of low molybdena loading

The catalytic activity for the reduction of NO by CO of five PdO-MoO₃/-Al₂O₃ catalysts is compared in the presence of varying amounts of oxygen at reaction temperatures from 25 to 550 °C. The samples were prepared by different methods and contain about 2% of Mo and 2% Pd. Results are compared with the activities and selectivities of PdO/ -A1₂O₃ and PdO-MoO₃/-Al₂O₃ containing 2% Pd and 2% Pd + 20% Mo, respectively. All catalysts showed appreciable activity at temperatures between 300 and 550 °C and at stoichiometric ratios,R, of the oxidizing to reducing gases of 0.1 <R < 1.1. The activity of three PdO-MoO₃/ -A1₂O₃ catalysts with low concentrations of Mo and Pd was found to be significantly higher than the activity of PdO/-Al₂O₃ at 1.1 <R < 1.3 and at temperatures between 300 and 500 °C. The improved activity is ascribed to the interaction of the active metals.     

Research of the Activity of Catalysts on the Base of H3PW12O40 in Partial Oxidative Conversion of C3–C4 alkanes

Catalysts from heteropoly acid H₃PW₁₂O₄₀ and its Cs, Na, Ba, Pb, Ca, Cd, Cr, Mn, V, La salts supported on clinoptilolite, alumosilicate are highly active in oxidative conversion of propane–butane (OCPB) mixture and formation of C₂–C₄ olefins, oxygen-containing compounds at temperatures T = 100–800 °C. Optimum yields of ethylene and propylene are achieved on heteropoly acid its Cs and Cr salts. The processes of oxidative dehydrogenation (ODPB) and cracking are concurrent in formation of olefins. High activity is caused by dispersity of supported catalysts (XRD, IRS) both formation of crystal hydrates and an amorphous phase of heteropoly acid in a condition of interaction with the carrier.     

Load-dependence of Knoop hardness of Al2O3–TiC composites

Nine samples of Al₂O₃–30 wt.% TiC composites were prepared by hot-pressing the Al₂O₃ powder mixed with TiC particles. The average sizes of the TiC particles used for preparing the nine samples were different with each other. Knoop hardness measurements were conducted on these nine samples, respectively, in the indentation load range from 1.47 to 35.77 N. For each sample, the measured Knoop hardness decreases with the increasing indentation load. The classical Meyer's power law and an empirical equation proposed originally by Bückle were verified to be sufficiently suitable for describing the observed load-dependence of the measured hardness. Analysis based on Meyer's law can not provide any useful information about the cause of the observed ISE while true hardness values, which are load-independent, can be deduced from the Bückle's equation. It was found that the deduced true hardness increases with the average size of TiC particles existing in the sample.     

Electrical properties and phase of BaTiO3–SrTiO3 solid solution

It has been known that ABO₃ type perovskite ferroelectrics, such as BaTiO₃ (BTO) and SrTiO₃ (STO), form a complete solid solution. In this study, Ba_1?xSr_xTiO₃ (BST, x=0.0–1.0) solid solution were sintered by a solid-state reaction method using BTO and STO raw powders with appropriate chemical composition. The crystal structure was investigated by a Rietveld refinement method; Fullprof, using X-ray diffraction data. Within the reasonable goodness of fit, tetragonal symmetry was found in BST with x≤0.2, while BST with x≥0.4 were found to be cubic symmetry. However, Ba_0.7Sr_0.3TiO₃ was difficult to decide whether it is cubic or tetragonal because of large uncertainties after final fitting. The composition ratios calculated from the fitted occupancies match well with those measured by EDS within experimental uncertainties. Remnant polarizations of BST with x<0.3 decrease with increasing Sr concentration. Furthermore, measured phase transition temperatures and maximum dielectric constant decrease as increasing Sr concentration. Measured electrical properties of BST were match well with the structural refinement investigations.     

Effect of Si3N4 on Resistance of Magnesia Based Castable

The magnesia based curable specimens with different Si3N4 contents were casted using sintered magnesite （w（MgO）=95%） as starting material, SiO2 micro-powder as binder, 0.3%, 4% and 5% β-Si3N4 powder replacing the equal addition of magnesia powder respectively. The slag resistance test was carried out at 1550℃ for 3h using Baosteel tundish slag and static crucible method. The result indicates that： introducing Si3N4 could obviously improve the slag resistance of MgO based castable, which increased with increasing Si3N4. Dense SiO2 sintered layer formed on the surface of magnesia based castable because of the oxidation of Si3N4 addition, which can prevent the further slag penetration. In the deep inner of castable, the partial-pressure of oxygen was very low, so Si3N4 can exist stably. Meanwhile in reducing atmosphere, Si3N4 was hard to be sintered, which resulted in the loose interior structure of MgO based castable.     

3D-TEM investigation of the nanostructure of a δ-Al2O3 catalyst support decorated with Pd nanoparticles

The electron tomography technique applied in a quantitative way allowed us to characterize a heterogeneous catalyst made of Pd nanoparticles deposited on a δ-Al(2)O(3) lamellar support. In the first step, high resolution tomographic experiments carried out on several typical areas of support have confirmed the hypothesis of formation of δ-Al(2)O(3) proposed in the literature by the coalescence of lateral facets of the γ-Al(2)O(3) precursor. A bimodal porosity was also observed in the arrangement of δ-Al(2)O(3) platelets. In the second step, the Pd nanoparticles were found preferentially anchored on the lateral facets of δ-Al(2)O(3) platelets or on the defects situated on their basal planes. From a general point of view, we have demonstrated once again that the electron tomography technique implemented with nanometre resolution provides unique insight into the structure, morphology and spatial arrangement of components in a complex 3D nanostructure.     

Preparation of 3-stearoyl-D-glucose—A bread-softening agent

Summary In previous work 3-stearoyl-d-glucose was found to have superior bread softening action. This paper describes its synthesis by reaction of stearoyl chloride with 1,2∶5,6-diisopropylidene-d-glucose and subsequent deacetonation of the intermediate stearoyl diisopropylidene-d-glucose. Acetonation of the product, followed by saponification of the acyl group, produced 1,2∶5,6-diisopropylidene-d-glucose and indicated that the substance is 3-stearoyl-d-glucose.     

Effects of sintering temperature on properties of Na0·5K0·5NbO3-LiSbO3-BiFeO3 lead free ceramics

Abstract

Abstract

Lead free 0·95K_0·5Na_0·5NbO₃-0·05LiSbO₃ (KNN-LS) ceramics doped with 0·4?mol.-% BiFeO₃ (BF) have been prepared by the conventional mixed oxide method with sintering temperature at 1065-1135°C in this paper. The samples are characterised by X-ray diffraction analysis and scanning electron microscopy. The dielectric and piezoelectric properties are also investigated. The results present that initially the increase in the sintering temperature is very effective in improving the density and electric properties. However, the properties of the samples would be deteriorated as they are sintered over the optimum temperature. The KNN-LS (doped with 0·4%BF) ceramics shows excellent properties with sintering temperature at 1100°C.     

Characterization of MoO3–V2O5/Al2O3 catalysts for selective catalytic reduction of NO by NH3

MoO₃–V₂O₅/Al₂O₃ catalysts were characterized by B.E.T., XRD, LRS, XPS and TPR and the effect of MoO₃ addition to alumina supported vanadia catalysts on the catalytic activity for the selective catalytic reduction of NO by ammonia was investigated. Upon the addition of MoO₃, catalytic activity was enhanced and the particle size of V₂O₅ which is shown by the results of B.E.T., XRD and Raman spectroscopy decreased. This was one reason for increased catalytic activity. The results obtained by XPS and TPR showed that MoO₃ addition to alumina supported vanadia catalysts increased the reducibility of vanadia and this was the another reason for synergy effect between MoO₃ and V₂O₅ in MoO₃–V₂O₅/Al₂O₃ catalysts.     

Effect of SrTiO3 concentration and sintering temperature on microstructure and dielectric constant of Ba1−xSrxTiO3

The Ba_1−xSr_xTiO₃ materials have received increased attention as one of the most important materials for electroceramic components, such as high dielectric ceramic capacitors, tunable phase shifters and PTCR. In this paper, the effect of SrTiO₃ concentration and sintering temperature on the microstructure and dielectric constant of Ba_1−xSr_xTiO₃ materials at the Curie temperature have been investigated. When Ba_1−xSr_xTiO₃ materials were sintered at 1350 °C, the peak value of the dielectric constant, ϵ_max, monotonically decreased with increasing SrTiO₃ concentration. At the sintering temperature of 1400 °C the dielectric constant maximum at the T_C increased with an increase in the x value, reaching the highest value at around x=0.4 and then decreased. As sintering temperature increased to 1450 °C, ϵ_max increased with increasing SrTiO₃ concentration up to x=0.6. The dielectric properties of Ba_1−xSr_xTiO₃ materials were discussed in terms of SrTiO₃ concentration and microstructure.     

Pixelated sintering of α-Al2O3

The sintering of α-alumina by a brand new and innovative technique, called pixelated sintering (PS), is here studied. Densification and grain growth by PS of perfectly controlled granular compacts are analysed and compared to results obtained using Spark Plasma Sintering (SPS) and Pressure-Less SPS (PL-SPS). Materials are exposed to the same temperature profiles whatever the sintering technique used in order to assess the potential of PS in terms of microstructure control. It is shown that PS can be used as an alternative technique to SPS for fast sintering with the advantages of a much simpler and cost-effective set-up, as well as a better control of the localised heat input. PS also appears to be a very modular technology in the way it controls the temperature gradients allowing its implementation for multi-step sintering approaches, as well as for the fabrication of large and complex parts.