Synthesis,characterization and catalytic properties of La2−x Sr x NiO4−δ

Various compositionsx in the catalyst system La_2–x Sr _x NiO_4– have been prepared by conventional techniques and characterized by X-ray powder diffraction, electron microscopy and BET surface measurements. The catalytic properties of these catalysts have been tested in the propylene oxidation reaction. The catalytic activity can be correlated with the oxygen content and with the strontium substitution.     

New Trends and Future Opportunities in the Enzymatic Formation of C−C,C−N,and C−O bonds

Organic chemistry provides society with fundamental products we use daily. Concerns about the impact that the chemical industry has over the environment is propelling major changes in the way we manufacture chemicals. Biocatalysis offers an alternative to other synthetic approaches as it employs enzymes, Nature's catalysts, to carry out chemical transformations. Enzymes are biodegradable, come from renewable sources, operate under mild reaction conditions, and display high selectivities in the processes they catalyse. As a highly multidisciplinary field, biocatalysis benefits from advances in different areas, and developments in the fields of molecular biology, bioinformatics, and chemical engineering have accelerated the extension of the range of available transformations (E. L. Bell et al., Nat. Rev. Meth. Prim. 2021 , 1, 1–21). Recently, we surveyed advances in the expansion of the scope of biocatalysis via enzyme discovery and protein engineering (J. R. Marshall et al., Tetrahedron 2021 , 82, 131926). Herein, we focus on novel enzymes currently available to the broad synthetic community for the construction of new C−C, C−N and C−O bonds, with the purpose of providing the non-specialist with new and alternative tools for chiral and sustainable chemical synthesis.     

Growth,doping and characterization of epitaxial thin films and patterned structures of AlN,GaN, and AlxGa1−xN

Advancements in the doping of GaN and Al_xGa_1−xN thin films, and the growth of GaN and Al_xGa_1−xN structures on patterned heterostructure substrates via metalorganic vapor phase epitaxy are reported. The acceptor-type behavior of Mg-doped GaN films grown in N₂ diluents is presented. Net ionized impurity concentrations up to 8×10¹⁸ cm⁻³ and Hall mobilities up to ≈14 cm² V⁻¹ s⁻¹ were measured for Mg-doped films grown in N₂ in the as-grown condition. Donor and acceptor doping of Al_xGa_1−xN alloys was performed. Acceptor doping of Al_xGa_1−xN for x≤0.13 and donor doping for x≤0.58 were achieved for films deposited at 1100 °C. Lateral epitaxial overgrowth of GaN and Al_xGa_1−xN layers was investigated. The growth and coalescence of GaN and Al_xGa_1−xN stripes patterned in SiO₂ and/or SiN_x masks deposited on GaN, including aligned second lateral epitaxial overgrowth on initial laterally overgrown GaN layers, are discussed.     

Fatty acids,the immune response,and autoimmunity: A question of n−6 essentiality and the balance between n−6 and n−3

The essentiality of n−6 polyunsaturated fatty acids (PUFA) is described in relation to a thymus/thymocyte accretion of arachidonic acid (20∶4n−6, AA) in early development, and the high requirement of lymphoid and other cells of the immune system for AA and linoleic acid (18∶2n−6, LA) for membrane phospholipids. Low n−6 PUFA intakes enhance whereas high intakes decrease certain immune functions. Evidence from in vitro and in vivo studies for a role of AA metabolites in immune cell development and functions shows that they can limit or regulate cellular immune reactions and can induce deviation toward a T helper (Th)2-like immune response. In contrast to the effects of the oxidative metabolites of AA, the longer-chain n−6 PUFA produced by γ-linolenic acid (18∶3n−6, GLA) feeding decreases the Th2 cytokine and immunoglobulin (Ig)G1 antibody response. The n−6 PUFA, GLA, dihomo-γ-linolenic acid (20∶3n−6, DHLA) and AA, and certain oxidative metabolites of AA can also induce T-regulatory cell activity, e.g., transforming growth factor (IGF)-β-producing T cells; GLA feeding studies also demonstrate reduced proinflammatory interleukin (IL)-1 and tumor necrosis factor (TNF)-α production. Low intakes of long-chain n−3 fatty acids (fish oils) enhance certain immune functions, whereas high intakes are inhibitory on a wide range of functions, e.g., antigen presentation, adhesion molecule expression, Th1 and th2 responses, proinflammatory cytokine and eicosanoid production, and they induce lymphocyte apoptosis. Vitamin E has a demonstrable critical role in long-chain n−3 PUFA interactions with immune functions, often reversing the effects of fish oil. The effect of dietary fatty acids on animal autoimmune disease models depends on both the autoimmune model and the amount and type of fatty acids fed. Diets low in fat, essential fatty acid deficient (EFAD), or high in long-chain n−3 PUFA from fish oils increase survival and reduce disease severity in spontaneous autoantibody-mediated disease, whereas high-fat LA-rich diets increase disease severity. In experimentally induced T cell-mediated autoimmune disease, EFAD diets or diets supplemented with long-chain n−3 PUFA augment disease, whereas n−6 PUFA prevent or reduce the severity. In contrast, in both T cell- and antibody-mediated autoimmune disease, the desaturated/elongated metabolites of LA are protective. PUFA of both the n−6 and n−3 families are clinically useful in human autoimmune-inflammatory disorders, but the precise mechanisms by which these fatty acids exert their clinical effects are not well understood. Finally, the view that all n−6 PUFA are proinflammatory requires revision, in part, and their essential regulatory and developmental role in the immune system warrants appreciation.     

Antiferromagnetism and heat capacity of NaCo2−xCuxO4 ceramics

Polycrystalline samples of NaCo_2−xCu_xO₄ (x=0, 0.01, 0.03 and 0.05) were synthesized in two different ways: 1) by a mechanochemically assisted solid-state reaction method (MASSR) and 2) by a citric acid complex method (CAC). In this work we examined the influence of these synthesis routes and small Cu concentrations on magnetic properties and the heat capacity of sintered samples. The magnetic susceptibility (χ) of all samples followed the Curie-Weiss law in the temperature range between 50 K and 300 K, while a negative Weiss constant (θ) implied an antiferromagnetic interaction. According to the magnetic susceptibility data, a peak around 30 K indicating the presence of Co₃O₄ as a secondary phase appeared for all MASSR samples and CAC samples with Cu content above 1%. The effective magnetic moment (μ_eff) of CAC samples was lower than the theoretical, spin only value obtained for the Co⁴⁺ ion in the low spin state indicating the presence of low spin Co³⁺(S =0). These values were also lower compared to the values obtained for MASSR samples. The highest μ_eff of 1.75 μ_B/atom Co was obtained for the undoped MASSR sample. The heat capacity of CAC samples at 2 K decreased with Cu concentration due to lowering of the electronic specific heat coefficient (γ). The highest γ of 63.9 mJ/molK² was obtained for the undoped CAC sample. This reduction in γ values was the result of the decrease of the density of state and/or mass enhancement factor.     

Phase formation,dielectric and ferroelectric properties of CaxBa1−xNb2O6 ceramics

Lead-free Ca_xBa_1?xNb₂O₆ (CBN, 0.20≤x≤0.35) ceramics were prepared by the conventional solid state method. Effects of Ca content on the phase formation, microstructure, dielectric and ferroelectric properties for the prepared CBN ceramics were systematically studied. XRD results showed that pure CBN phase with tungsten bronze structure could be obtained from the solid solutions of BaNb₂O₆ and CaNb₂O₆ in all ceramics. Higher Ca contents favored the occurrence of grains with anisometric morphology, but no abnormal grain growth could be found in all compositions. With the increase of x, Curie temperature T_c shifted downward, whereas the maximum dielectric constant ε_m increased initially and then decreased. All the ceramics showed an intermediate relaxor-like behavior between normal and ideal relaxor ferroelectrics according to the modified Curie–Weiss law. Normal ferroelectric hysteresis loops were observed in all compositions. Both remnant polarization P_r and coercive field E_c increased initially and then decreased with the increase of x. The ceramics with homogeneous microstructure, high density and better properties were obtained at x=0.28 with ε_m=2998, T_c=234 °C, P_r=3.98 μC cm^?2 and E_c=14.03 kV cm^?1.     

Deactivation of H-mordenite and ZrO2/SO2−4 during n-butane isomerization

The catalyst deactivation in the isomerization of n-butane was studied on H-mordenite and ZrO₂ promoted by SO²⁻₄ ion. The deactivation of H-mordenite was the result of coke deposition on the catalyst pores and the deactivation of ZrO₂/SO²⁻₄ resulted from the decrease in the oxidation state of sulphur in the surface complex. The reoxidation of sulphur, producing again the SO²⁻₄ ion, led to the recovery of the catalytic activity of ZrO₂/SO²⁻₄ and coke burning resulted in the recovery of the H-mordenite activity.     

1D and 2D network of ReO4− bonded azoimidazoles

1-Alkyl-2-(arylazo)imidazoles are π-acidic, bidentate chelating molecules. In acid medium imidazole-N centers are protonated and can extract heavy anions. One such example is the binding with ReO₄⁻ in acidic medium. 1-Alkyl-2-(arylazo)imidazolium-perrehenate shows hydrogen bonded 1D network. Inclusion of H₂O into the molecular frame of 1D increases the dimensionality to 2D network.     

Fabrication and phase transition of La2−xLuxZr2O7 transparent ceramics

A series of transparent ceramics with the composition of La_2−xLu_xZr₂O₇ (x = 0−2.0) were prepared by solid-state reactive sintering in vacuum. With the increase of Lu content (x), phase transition from pyrochlore to defective fluorite occurred and a two-phase region existed in the range of x = 0.6−1.2. Grain sizes of the pyrochlore phase dominated samples (x < 0.5) were 11−14 μm, and that of the defective fluorite phase dominated samples were larger than 60 μm. However, grain sizes of the samples in the two-phase region were smaller than 3 μm. The La_0.8Lu_1.2Zr₂O₇ ceramic with the smallest grain size (∼2.5 μm) reached a highest in-line transmittance of 72.4% at 1100 nm among all the samples.     

Effects of ion polarizability and oxygen vacancy on microwave dielectric properties of fluorite-structured Ce1−xCaxO2−x

X-ray diffractometer with Rietveld refinement and Raman spectroscopy were used for phase analysis. Ca doping results in decreased ε_r (24.09–21.52), Q × f (68 914–40 110 GHz), and τ_f (−50.0 ppm/°C to −60.2 ppm/°C) all decrease, which obviously does not conform to the mutual constraint relationship among the three parameters of microwave dielectric properties. The ε_r of Ce_1−xCa_xO_2−x ceramics is affected by the ion polarizability and the Ce rattling and valence states, among which the rattling of Ce cations plays a dominant role. The presence of oxygen vacancies in Ce_1−xCa_xO_2−x ceramics explains the decrease in Q × f. The τ_ε, ε_r, and α_L are responsible for the decrease in τ_f, especially for the τ_αm-3α_L values.     

Hydrothermal synthesis and characterization of nanorods “LixV2−δO4−δ·H2O”

Nanorods “Li_xV_2−δO_4−δ·H₂O” were hydrothermally synthesized with starting agents LiOH·H₂O and V₂O₅, and reducing agent hydrazine monohydrate (NH₂NH₂·H₂O) under alkaline condition at 160 °C. The samples were characterizated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The nanorods obtained have diameters from 80 to 100 nm with length up to several micrometers. Molecular coordination and assembly mechanism can be assumed to explain the formation of one-dimensional nanorods.     

Structural,morphological and electrical properties of Ce1−xRuxO2−δ (x=0.005–0.02) solid solutions

Nanoparticles of ceria–ruthenium oxide solid solutions with composition Ce_1−xRu_xO_2−δ (x=0.005–0.02) were successfully produced by self–propagating room temperature synthesis using reaction between metal nitrates and sodium hydroxide. These compositions were characterized by X–ray powder diffraction (XRD), Raman spectroscopy, specific surface area, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X–ray spectroscopy (EDX). The experimental measurements were complemented by calculations based on the ion–packing model. XRD analysis revealed the presence of single–phase solid solutions with CeO₂ fluorite structure (regardless of dopants concentration) and Raman spectroscopy confirmed the presence of the RuO₂ phase. Electrochemical impedance spectroscopy (EIS) measurements of sintered samples at different temperatures showed that the small ionic radius dopant reduces oxygen vacancies mobility that is responsible for the conductivity of these ceramics.     

Synthesis,Characterization, and Spectroscopic Analysis of NdxY1−xTiNbO6 Microwave Ceramics

Solid solutions of Nd_xY_1−xTiNbO₆ ceramics were prepared through the solid-state ceramic route. The materials were calcined at 1250°C and sintered in the range 1400–1550°C. The structure of the system was analyzed using the X-ray diffraction and vibrational spectroscopic analysis. The morphology and the sintering behavior of the samples were analyzed using scanning electron microscopy. The dielectric constant (ɛ_r), temperature coefficient of resonant frequency (τ_f), and the unloaded quality factor (Q_u) were measured in the microwave frequency region using the cavity resonator method. The ɛ_r and τ_f increased with an increase in the concentration of Nd in the solid solutions. Nearly zero temperature coefficient of resonant frequency was obtained for the Nd_0.6Y_0.4TiNbO₆ ceramic. Samples are of high quality factor and are useful for microwave applications.     

Synthesis of lithium LiNi1−yCoyO2 from lithium carbonate,nickel oxide and cobalt carbonate and their electrochemical properties

LiNi_1?yCo_yO₂ (y = 0.1, 0.3 and 0.5) were synthesized by solid state reaction method at 800 °C and 850 °C from Li₂CO₃, NiO and CoCO₃ as starting materials. The electrochemical properties of the synthesized LiNi_1?yCo_yO₂ were investigated. As the content of Co decreases, particle size decreases rapidly and particle size gets more homogeneous. When the particle size is compared at the same composition, the particles synthesized at 850 °C are larger than those synthesized at 800 °C. Among LiNi_1?yCo_yO₂ (y = 0.1, 0.3 and 0.5) synthesized at 850 °C, LiNi_0.7Co_0.3O₂ has the largest intercalated and deintercalated Li quantity Δx at the first charge–discharge cycle, followed in order by LiNi_0.9Co_0.1O₂ and LiNi_0.5Co_0.5O₂. LiNi_0.7Co_0.3O₂ synthesized at 850 °C has the largest first discharge capacity (142 mAh/g), followed in order by LiNi_0.9Co_0.1O₂ synthesized at 850 °C (113 mAh/g), and LiNi_0.5Co_0.5O₂ synthesized at 800 °C (109 mAh/g).     

Mixed-valent structure,dielectric properties and defect chemistry of Ca1−3x/2TbxCu3Ti4−xTbxO12 ceramics

Single-phase Ca_1−3x/2Tb_xCu₃Ti_4−xTb_xO₁₂ (0.025≤ x≤0.075) (CTCTT) ceramics with a cubic perovskite-like structure and a fine-grained microstructure (1.6‒2.3 µm) were prepared using a mixed oxides method. The results revealed that mixed valence states of Cu²⁺/Cu⁺, Ti⁴⁺/Ti³⁺, and Tb³⁺/Tb⁴⁺ coexisted in CTCTT. A multiphonon phenomenon in the Raman scattering at 1148, 1323, and 1502 cm⁻¹ was reported for undoped and doped CTTO. Tb was mainly incorporated in the interior of the CTCTT grains rather than on the surface. The dielectric permittivity of CTCTT (ε_r'_RT =3590‒5200) decreased relative to CCTO (ε_r'_RT =10240) at f =1 kHz, but the dielectric loss of CTCTT (the minimum value of tan δ=0.12 at RT) increased as a result of Tb doping. The defect chemistry of CTCTT is discussed. The internal barrier layers capacitance (IBLC) model was adopted for impedance spectroscopy (IS) analysis. The activation energies of the grain boundaries (E_gb) and semi-conductive grains (E_g) for CTCTT were determined to be 0.52 eV and 104 meV, respectively. The IS and defect chemistry analyses confirmed that the decrease in the dielectric permittivity was mainly due to a decrease in conductivity in the semiconducting CTCTT grains caused by the acceptor effect of Tb⁴⁺ at the Ti site, which resulted in a decrease in the IBLC effect.     

Combustion Synthesis of PrBa2Cu3O7−δ and YBa2Cu3O7−δ cuprate materials

PrBaCuO and YBaCuO cuprate materials were prepared from cooper, barium peroxide, and yttrium/praseodymium oxide by SHS and standard solid-state synthesis. SHS reactions were carried out using relatively large cooper particles (< 63 im) to obtain small product samples (13 mm in diameter). High ambient temperature was used to stabilize a combustion front in the ignited pellets. Explored was the effect of cooper particles size, starting density, and ambient temperature on phase evolutions in synthesized materials.     

Effects of mechanical milling on preparation and properties of CuAl1−xFexO2 thermoelectric ceramics

CuAl_1?xFe_xO₂ (x = 0, 0.1, and 0.2) thermoelectric ceramics produced by a reaction-sintering process were investigated. Pure CuAlO₂ and CuAl_0.9Fe_0.1O₂ were obtained. Minor CuAl₂O₄ phase formed in CuAl_0.8Fe_0.2O₂. Addition of 10 mol% Fe lowered the sintering temperature obviously and enhanced the grain growth. At x = 0.1, electrical conductivity = 3.143 Ω^?1 cm^?1, Seebeck coefficient = 418 μV K^?1, and power factor = 5.49 × 10^?5 W m^?1 K^?2 at 600 °C were obtained. The reaction-sintering process is simple and effective in preparing CuAlO₂ and CuAl_0.9Fe_0.1O₂ thermoelectric ceramics for applications at high temperatures.     

Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

Structure and microwave dielectric properties of Ba1−xSrxMg2V2O8 ceramics

The Ba_1−xSr_xMg₂V₂O₈ (0≤x≤0.4) microwave dielectric ceramics were fabricated by a standard solid-state reaction method. The formation of a continuous solid solution within the whole composition range was identified. The ceramic samples could be well densified in the temperature range of 885–975 °C in air for 4 h. The permittivity ε_r was found to increase with increasing ionic polarizabilities. The Q×f values were believed to be closely related with packing fraction and grain refinement. The Sr²⁺ substitution contributed to a monotonous increase of the A-site bond valence, such that the τ_f value experienced a considerable variation from negative to positive values. The optimum microwave dielectric properties of an ε_r of 13.3, a high Qxf of 86,640 GHz (9.6 Hz) and a near-zero τ_f of −6 ppm/°C could be yielded in the x=0.15 sample when sintered at 915 °C for 4 h.