Research progress on classification,source,application of phytosterol esters,and their thermal oxidation stability

Phytosterol esters can effectively decrease serum cholesterol concentration in the human body and prevent cardio-cerebrovascular diseases.It was found that phytosterol esters exhibited better solubility and bioavailability than free phytosterols.In recent years,phytosterol esters have attracted increasing attention.However,during food processing,phytosterol esters are susceptible to degradation at high temperatures,resulting in certain losses and formation of potentially harmful substances for humans.This paper reviews the relevant literatures and updates on the thermal oxidation stability of phytosterol esters in recent years from the following aspects:(i)Sources,physiological activities,and applications of phytosterol esters;(ii)Oxidation mechanism of phytosterol esters;(iii)Effects of phytosterols species,the volume of addition,food matrix,heating temperature and time,and antioxidants on the thermal loss and oxidation stability of phytosterol esters.The research progress on the safety of phytosterol esters is also discussed in detail.Additionally,the prospects for future research are highlighted.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.

Synthesis,Crystal Structure,Spectroscopic Characterization,Thermal Stability and Magnetic Properties of a Dinuclear Copper(Ⅱ) Complex

A new copper（Ⅱ） complex [Cu2（MNA）2（2,2‘-bipy）2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid（MNA） and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191（11）,b = 12.8883（13）,c = 16.1114（16） A,α = 70.8090（10）,β = 80.568（2）,γ = 77.440（2）o,V = 1984.3（4） A^3,Dc = 1.551 g/cm^3,Z = 2,F（000） = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η^1：η^0 3-carboxylate groups of MNA^2-.The coordination environment of Cu（Ⅱ） ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.

Crystal Structure,Fluorescence and Thermal Stability Properties of a Dinuclear Copper(Ⅱ) Complex[Cu_2(L)_2(phen)_2]-5H_2O(H_2L = Bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid)

A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.

Hydrothermal Synthesis, Crystal Structure, Thermal Stability and Magnetic Properties of a Dinuclear Copper(Ⅱ) Complex

A new dinuclear copper（Ⅱ） complex [Cu（CH3COO）（C7H5N4）（H2O）]2·3.5H2 O has been hydrothermally synthesized with copper acetate, o-acetamidobenzoic acid and 3-（pyridin-2-yl）-1,2,4-triazole. It crystallizes in the monoclinic space group P21/c, with a = 12.0188（7）, b = 13.7993（8）, c = 8.7488（5） A, β = 101.7350（10）o, V = 1420.67（14） A3, D3 c = 1.568 g/cm, Z = 1, F（000） = 690, the final GOOF = 1.145, R = 0.0437, and w R = 0.1097. The crystal structure shows that the whole molecule consists of two copper ions bridged by two μ2-η1：η0 3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of Cu（Ⅱ） ion is Cu O2N3, giving a distorted square pyramidal geometry. The thermal stability and magnetic properties of the complex were investigated.

Effect of Low-Temperature Thermal Oxidation on the Capillary Performance of Sintered Copper Powder Wicks

In this study,a composite powder capillary wick is prepared,manufactured by sintering copper powder and surface treated by low-temperature thermal oxidation.It is used to improve the performance of the capillary wick.The forced flow method and infrared imaging method are used to test the permeability and capillary performance of the samples.The effects of different oxidation temperatures on the performance of capillary wick are investigated.The experimental results show that the wetting performance of the oxidized samples is significantly enhanced.With the increase of oxidation temperature,the permeability decreases.The capillary height and velocity of the thermally oxidized samples are significantly higher than those of the untreated capillary wick.However,the oxidation temperature needs to be adjusted to obtain the best capillary performance.The highest capillary performance is found at oxidation temperature of 300℃,with an increase of 46% compared to the untreated ones.Comparisons with other composite wicks show that the sample with an oxidation temperature of 300℃ has competitive capillary performance,making it a favorable alternative to two-phase heat transfer device.This study shows that combining low-temperature thermal oxidation technology with powder sintering is a convenient and effective method to improve the capillary performance of powder wicks.

Copper naphthalocyanine-based hole-transport material for highperformance and thermally stable perovskite solar cells

Metal phthalocyanines(MPcs) have gained considerable research attention as hole-transport materials(HTMs) in perovskite solar cells(PSCs) because of their superb stability. However, the photovoltaic performance of MPc-based HTMs in PSCs is still lagging behind their small molecule and polymeric counterparts, largely due to their relatively low hole mobility. Here, we report for the first time the application of a copper naphthalocyanine derivative(namely t Bu-Cu Nc) as a hole-transport material(HTM)in perovskite solar cells(PSCs), and systematically study its optoelectronic and photovoltaic property compared with its Cu Pc analog(t Bu-Cu Pc). Combined experiments disclose that the extension of π-conjugation from Pc to Nc core leads to not only an enhanced hole-carrier mobility associated with a stronger intermolecular interaction, but also an elevated glass transition temperature(T_g) of 252 °C. The resultant PSCs employing t Bu-Cu Nc deliver an excellent power conversion efficiency of 24.03%, which is the record efficiency reported for metal complex-based HTMs in PSCs. More importantly, the encapsulated t Bu-Cu Nc-based devices also show dramatically improved thermal stability than the devices using the well-known SpiroOMe TAD, with a T_(80)lifetime for more than 1,000 h under damp-heat stress. This study unfolds a new avenue for developing efficient and stable HTMs in PSCs.

Synthesis, Crystal Structure and Properties of a New Binuclear Copper(Ⅱ) Complex with 5-Oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic Acid(TNCA)

A new binuclear copper（Ⅱ） complex [Cu2（Hpt）2（TNCA）2（H2O）2]·4 H2O（1） has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid（TNCA） and 3-（pyridin-2-yl）-1,2,4-triazole（Hpt）. It crystallizes in the triclinic space group P-1, with a = 8.8199（18）, b = 14.278（3）, c = 15.269（3） A, α = 76.21（3）o, β = 81.07（3）o, γ = 76.07（3）o, V = 1802.7（6） A3, Dc = 1.636 g/cm3, Z = 2, F（000） = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1：η^0-3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of the Cu（1） ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu（Ⅱ） ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.

Effects of Annealing Temperature on the Properties of Copper Films Prepared by Magnetron Sputtering

Copper oxide thin films were prepared by a direct-current magnetron sputtering method followed by a thermal annealing treatment at 100-500 ℃. The obtained films were characterized by X-ray diffraction, UV-vis absorption spectroscopy, scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. With the increase of the annealing temperature, it was found that the films transformed sequentially from amorphous to single-phase Cu （100℃）, mixed-phase of Cu and Cu2O （150 ℃）, single-phase Cu2O （200 ℃）, then to mixed-phase of Cu2O and CuO （300 ℃）, and finally to single-phase CuO （400 - 500 ℃）. Further analyses indicated that the Cu/Cu2O thin films and the Cu：O thin films presented no further oxidation even on the surface in air atmosphere. Additionally, the visible-light photocatalytic behavior of the copper oxide thin films on the degradation of methylene blue （MB） was also investigated, indicating that the films with pure Cu2O phase or Cu/Cu2O mixed phases have excellent photocatalytic efficiencies.

Microstructure and properties of copper matrix composites reinforced by nano-SiC and nano-Al_2O_3 particles

Copper/silicon carbide composites （Cu/SiC） and copper/alumina composites （Cu/Al2O3） were fabricated by the powder metallurgy method. The influence of reinforcement particles contents on the relevant properties of the composites and the microstructure of Cu/SiC and Cu/Al2O3 composites were studied. The reinforcement effects of nano-SiC and nano-Al2O3 particles were compared. The experimental results show that with the increase of the amount of nano-SiC and nano-Al2O3 particles, the density of the both composites decreases, the resistivity increases, whereas the hardness increases firstly and then drops. The softening temperatures of the composites are above 700℃ which is far higher than that of the pure copper, leading to the improvement of the thermal stability of the composites at high temperatures. Considering all factors, the reinforcement effects of nano-SiC are better than those of nano-Al2O3 when their contents are the same in the copper matrix.

Photocatalytic activity of CuO nanoparticles incorporated in mesoporous structure prepared from bis(2-aminonicotinato) copper(Ⅱ) microflakes

An easy method for preparing CuO nanoparticles incorporated in a mesoporous structure was presented based on the thermal decomposition of a copper complex. The novel copper coordination compound of [Cu(anic)2]·0.75H2O (anic= 2-aminonicotinate) with the microflake morphology was synthesized through the reaction of 2-aminonicotinic acid (Hanic) and copper(II) nitrate. Using elemental analysis and Fourier transform infrared (FTIR) spectroscopy, the chemical composition of CuC12H11.5N4O4.75 was proposed. Calcination process at 550 °C for 4 h transformed the microflakes into CuO nanoparticles incorporated in a mesoporous structure. The FTIR peaks assigned to 2-aminonicotinate were completely removed after calcination, confirming CuO formation. X-ray diffraction (XRD) analysis also confirmed the generation of pure and crystalline CuO. SEM showed CuO nanoparticles with the average diameter of 75 nm. The diffuse reflectance spectrum (DRS) of the CuO nanoparticles showed a band gap energy of −1.58 eV. The degradation efficiency toward rhodamine B was almost 100 % after 5 h illumination when both CuO and H2O2 were utilized. The results show that the product can be used as an efficient photocatalyst for water treatment.

Effect of thermal oxidation on microstructures and mechanical properties of nanoporous coppers

Nanoporous copper oxides were formed by thermal oxidation of nanoporous copper at 150°C–270°C. The oxidation process of nanoporous copper was investigated by using XRD, SEM, nitrogen adsorption, HRTEM and nanoindentation. The variation of microstructures and mechanical properties was analyzed. The results showed that the content of copper oxides increased, the ligament gradually coarsened, and the mechanical properties of nanoporous structure were improved with the increase of oxidation temperature. When the oxidation temperature was below 210°C, the ligament surface was oxidized to Cu_2O, and the composite structure of Cu_2O@Cu was formed. The formation of CuO occurred since 220°C, and the composite structure of CuO/Cu_2 O@Cu was formed. CuO nanowires were grown on the ligament surface at 250°C; the specific surface area, elastic modulus and hardness of nanoporous structure are 1.37, 3.31 and 7.58 times that of the nanoporous copper, respectively.

XPS STUDIES OF OXIDATION BEHAVIOR OF NICKEL AND THERMAL STABILITY OF SURFACE OXIDES

Surface oxidation of polycrystalline nickel foil in air and pure water at different temperatures and the thermal stability of the surface oxides have been investigated by means of XPS.In ad- dition to NiO,Ni_2O_3 is formed especially after long periods of air exposure.Nickel surfaces are much less reactive to pure water than to air.The thermal stability of the surface oxides is related to oxidative temperature.The surface species of oxides formed by air exposure at temperatures below 120℃ can be reduced into nickel metal after heating the sample in vacuum at 300℃ for only 10 minutes (in the case of room temperature) to 1 h (in the case of 120℃). This reduction is caused by reaction with surface carbon contaminants.However,the surface species of nickel oxides formed by air exposure with heating at temperatures above 200℃ can not be reduced into metal after heating the sample in vacuum at 300℃ for 1h.

Highly photoreactive TiO_2 hollow microspheres with super thermal stability for acetone oxidation

TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.

Thermal oxidation of two aviation synthetic lubricant base oils

The thermal degradation of two synthetic lubricants base oils, poly-a-olefins （PAO） and di-esters （DE）, was investigated under oxidative pyrolysis condition and their properties were characterized in simulated ＂areo-engine＂ by comparing the thermal stability and identifying the products of thermal decomposition as a function of exposure temperature. The characterization of the products were performed by means of Fourier transform infrared spectrometry （FTIR）, gas chromatography/mass spectrometry （GC/MS） and viscosity experiments. The results show that PAO has the lower thermal stability, being degraded at 200℃ different from 300 ℃ for DE. Several by-products are identified during the thermal degradation of two lubricant base oils. The majority of PAO products consist of alkenes and olefins, while more oxygen-contained organic compounds are detected in DE samples based on GC/MS analysis. The related reaction mechanisms are discussed based on the experimental results.

Thermally stable ultrafine grained copper induced by CrB/CrB_(2) microparticles with surface nanofeatures via regular casting

Ultrafine-grained(UFG)/nanocrystalline materials possess novel properties. Refining as-solidified grains of metals to the ultrafine and even nanometer scale by nanoparticles via slow cooling has been recently discovered. Here, we report that microparticles(CrB and CrB_(2)) with surface nanofeatures can also enable ultrafine/nano grains via slow cooling. CrB/CrB_(2) microparticles, formed by coalescence of nanoparticles in Cu matrix, display surface nanofeatures, which induce substantial grain refinement and stabilization down to the ultrafine/nano scale. The UFG Cu/Cr B and Cu/CrB_(2) samples exhibit exceptional thermal stability, comparable to UFG Cu induced by nanoparticles, without coarsening after annealing at 600°C for 1 h. The microhardness, strengths, and Young's moduli of the Cu/Cr B and Cu/CrB_(2) samples are significantly enhanced over pure Cu. This discovery has great potential to advance the mass production UFG/nanocrystalline for widespread applications.

Synthesis, Crystal Structure and Thermal Stability of a New Binuclear Cu(Ⅱ) Complex with 2-Benzoylbenzoic Acid as the Ligand

A new complex Cu2（o-C6H5COC6H5COO）4（C10H8N2）2（H2O）2 with 2-benzoylben- zoic acid and 2,2′-bipyridine as ligands has been synthesized in mixed methanol and water solvent. Crystal data are as follows： monoclinic, space group Co, a = 14.0133（14）, b = 16.0409（16）, c = 30.372（3） A, β = 100.8950（10）°, V = 6704.1（12） A3, Dc = 1.364 g/cm3, Z = 8,μ（MoKa） = 0.704 mml, F（000） = 2840, the final R= 0.0552 and wR = 0.1431. In the crystal structure, the whole molecule consists of two copper ions, four 2-benzoylbenzoic acid molecules, two 2,2′-bipyridine molecules and two water molecules. Each central copper ion is coordinated with two nitrogen atoms from one 2,2′-bipyridine molecule and three oxygen atoms from two 2-benzoylbenzoic acids and one water molecule, respectively, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.

Synthesis,Crystal Structure and Thermal Stability of Complex [Cu(C_(14)H_(10)O_4)(C_(12)H_8N_2)_2]·2H_2O

The title complex has been synthesized with 2,2＇-biphenyl dicarboxylic acid and 1,10-phenanthroline（phen）in the solvent mixture of water and methanol.It crystallizes（C38H28CuN4O6,Mr = 700.1）in triclinic,space group P1 with a = 1.0868（2）,b = 1.2175（2）,c = 1.6206（3）nm,α = 110.161（2）,β = 102.605（3）,γ = 93.667（2）o,V = 1941.6（6）nm3,Dc = 1.198 g/cm3,Z = 2,F（000）= 722,R = 0.0558 and wR = 0.1208.The crystal structure shows that the copper atom is coordinated with one oxygen atom from 2,2＇-bphenyl dicarboxylic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules,forming a distorted square-pyramidal coordination.The TG analysis shows that the title complex is stable under 160.0 ℃.

Crystal Structure and Thermal Stability Properties of a New 1D Chain Cu(Ⅱ)Coordination Polymer with2,3-Pyridinedicarboxylic Acid as the Ligand

A new 1D chain copper coordination polymer [CuE（H2L）2（C10HsN2）（HEO）2]n＇3n（H20） with 2,3-pyridinedi carboxylic acid （H2L） and 2,2＇-bipyridine （2,2＇-bipy） as ligands has been synthesized in the mixed ethanol and water solvents. Crystal data for this complex are as follows： monoclinic, space group P2Jc, a = 7.7713（7）, b = 27.478（3）, c = 13.2621（13）/1,, fl = 100.6940（10）, V= 2782.8（5） A3, Dc = 1.722 g/cm3, Z = 4, p = 1.61 mm-1, F（000） = 1472, the final R = 0.0363 and wR = 0.0933. In the crystal structure, the whole molecule consists of two cooper ions, two H2L, one 2,2＂-bipy molecule and six water molecules. Each central copper ion is coordinated with three oxygen atoms from two H2L and one water molecule, two nitrogen atoms from one 2,2＇-bipy molecule and two H2L, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.