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21.
Jason R McCarthyPatricia J Melfi Steven H CapettaChristian Brückner 《Tetrahedron》2003,59(46):9137-9146
The use of AgII as a removable template in synthetic porphyrin chemistry is described. Mild procedures for the insertion of AgII into chlorins and the demetallation of the [chlorinato]AgII complexes are delineated. The UV-vis spectra of the novel [chlorinato]AgII complexes are discussed. The diol cleavage products of [meso-tetraphenyl-2,3-diolchlorinato]silver(II) under a number of conditions are characterized and compared to those resulting from the cleavage of the corresponding free base diol chlorin or its NiII complex, highlighting the unique templating effect of AgII. The scopes and limits of electrospray ionization mass spectrometry (ESI-MS) for the analysis of AgII chlorins is described. The use of AgII as a templating metal is superior over NiII or ZnII for the preparation of free base pyrrole-modified porphyrins along metal templated pathways. 相似文献
22.
Isabelle FavierElisabet Duñach 《Tetrahedron》2003,59(10):1823-1830
Mandelic acid and some aryl substituted derivatives were oxidised under molecular oxygen and a catalytic amount of Bi(0). The corresponding aldehydes and/or the carboxylic acids were obtained selectively depending on the nature of the substituent. Aldehydes and α-keto acids were oxidised under the same Bi(0)/O2 system and α-keto acids were proposed as intermediates in the formation of benzoic acid derivatives. 相似文献
23.
Kinetics of CO oxidation on the surface of heterophase catalysts. Modeling by the Monte Carlo method
The Monte Carlo method has been used to simulate CO oxidation on a lattice consisting of various alternating patches: M1, where s(CO)>s(O2) and M2, where s(CO)2). The reaction is shown to proceed over all the surface at low temperature as COads spillover from M1 to M2 and backwards. 相似文献
24.
2-Trifluoromethyl-4H-thiochromene-4-thione obtained from 2-trifluoromethyl-4H-thiochromen-4-one and P2S5 reacts with aromatic amines, hydrazine hydrate, phenylhydrazine, and hydroxylamine at the C(4) atom of the chromene ring
to give the corresponding anils, azine, hydrazones, and oxime of thiochromone. 2-Trifluoromethyl-4H-thiochromen-4-one is oxidized by hydrogen peroxide in AcOH into 4-oxo-2-trifluoromethyl-4H-thiochromene 1,1-dioxide and reduced by NaBH4 to 2-trifluoromethyl-4H-thiochromen-4-ol or cis-2-(trifluoromethyl)thiochroman-4-ol. When treated with hydrazine hydrate, thiochromen-4-one gives 3(5)-(2-mercaptophenyl)-5(3)-trifluoromethylpyrazole.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 504–509, March, 2006. 相似文献
25.
The kinetics of growth of thin (14 to 40Å) oxide layers on lead-indium alloys was investigated ellipsometrically, using: 3000Å thick films at 23°C; and oxygen exposures at 760 torr for times ranging from five minutes to five days. Assuming that the oxide layer is comprised of a two-phase mixture of PbO and In2O3 having a negligible extinction coefficient made it possible to estimate the oxide composition from the ellipsometrically-obtained oxide refractive index. Under these oxidizing conditions, the volume fraction of PbO in the oxide mixture decreases from a value of unity for pure lead to zero for alloys containing more than 30 at. percent In, in agreement with the Auger Electron Spectroscopy results of Chou and coworkers. The oxidation rate equals a exp (X1/X), where α and X1 will be seen to vary complexly with alloy composition. A theoretical explanation of these results is also presented. 相似文献
26.
Reem S. Alnefaie Mohamed Abboud Abdullah Alhanash Mohamed S. Hamdy 《Molecules (Basel, Switzerland)》2022,27(10)
Nickel oxide powder was prepared by simple calcination of nickel nitrate hexahydrate at 500 °C for 5 h and used as a catalyst for the oxidation of cyclohexane to produce the cyclohexanone and cyclohexanol—KA oil. Molecular oxygen (O2), hydrogen peroxide (H2O2), t-butyl hydrogen peroxide (TBHP) and meta-chloroperoxybenzoic acid (m-CPBA) were evaluated as oxidizing agents under different conditions. m-CPBA exhibited higher catalytic activity compared to other oxidants. Using 1.5 equivalent of m-CPBA as an oxygen donor agent for 24 h at 70 °C, in acetonitrile as a solvent, NiO powder showed exceptional catalytic activity for the oxidation of cyclohexane to produce KA oil. Compared to different catalytic systems reported in the literature, for the first time, about 85% of cyclohexane was converted to products, with 99% KA oil selectivity, including around 87% and 13% selectivity toward cyclohexanone and cyclohexanol, respectively. The reusability of NiO catalyst was also investigated. During four successive cycles, the conversion of cyclohexane and the selectivity toward cyclohexanone were decreased progressively to 63% and 60%, respectively, while the selectivity toward cyclohexanol was increased gradually to 40%. 相似文献
27.
Yerdos Ongarbayev Ainur Zhambolova Yerbol Tileuberdi Zulkhair Mansurov Cesare Oliviero Rossi Pietro Calandra Bagdat Teltayev 《Molecules (Basel, Switzerland)》2022,27(10)
This paper considers the effect of aging processes on viscoelastic characteristics of vacuum residue oxidation products modified with crumb rubber. Viscoelastic properties were compared to original bitumen raw material-vacuum residue and vacuum residue oxidation products during short-term and long-term aging. The complex shear modulus of the vacuum residue and its oxidation products decreased with an increase in temperature. Short-term aging resulted in increased shear modulus for all samples.The vacuum residue oxidation product modified with crumb rubber had the maximum values of the rutting parameter and fatigue parameter. There was an expansion of the temperature range of plasticity: for the vacuum residue oxidation product with crumb rubber, its value was 67.2 °C. The curves of the black diagram of the modified vacuum residue oxidation product are shifted towards smaller phase angles with the increase in the shear modulus, which indicates the increase in the stiffness and elasticity of the rubber bitumen binders. The vacuum residue oxidation product modified with crumb rubber corresponded to the rubber bitumen binder of the grade RBB 60/90, according to its physical and mechanical indicators. 相似文献
28.
Kyung-Hyun Cho 《Molecules (Basel, Switzerland)》2022,27(13)
Human serum amyloid A (SAA) is an exchangeable apolipoprotein (apo) in high-density lipoprotein (HDL) that influences HDL quality and functionality, particularly in the acute phase of inflammation. On the other hand, the structural and functional correlations of HDL containing SAA and apoA-I have not been reported. The current study was designed to compare the change in HDL quality with increasing SAA content in the lipid-free and lipid-bound states in reconstituted HDL (rHDL). The expressed recombinant human SAA1 (13 kDa) was purified to at least 98% and characterized in the lipid-free and lipid-bound states with apoA-I. The dimyristoyl phosphatidylcholine (DMPC) binding ability of apoA-I was impaired severely by the addition of SAA, while SAA alone could not bind with DMPC. The recombinant human SAA1 was incorporated into the rHDL (molar ratio 95:5:1, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC): cholesterol: apoA-I) with various apoA-I:SAA molar ratios from 1:0 to 1:0.5, 1:1 and 1:2. With increasing SAA1 content, the rHDL particle size was reduced from 98 Å to 93 Å, and the α-helicity of apoA-I:SAA was decreased from 73% to 40% for (1:0) and (1:2), respectively. The wavelength maximum fluorescence (WMF) of tryptophan in rHDL was red-shifted from 339 nm to 345 nm for (1:0) and (1:2) of apoA-I:SAA, respectively, indicating that the addition of SAA to rHDL destabilized the secondary structure of apoA-I. Upon denaturation by urea treatment from 0 M to 8 M, SAA showed only a 3 nm red-shift in WMF, while apoA-I showed a 16 nm red-shift in WMF, indicating that SAA is resistant to denaturation and apoA-I had higher conformational flexibility than SAA. The glycation reaction of apoA-I in the presence of fructose was accelerated up to 1.8-fold by adding SAA in a dose-dependent manner than that of apoA-I alone. In conclusion, the incorporation of SAA in rHDL impaired the structural stability of apoA-I and exacerbated glycation of HDL and apoA-I. 相似文献
29.
Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L1NHC)2](PF6)2; 3, [Ni-(L2NHC)2](PF6)2; 4, [Ni-(L3NHC)](PF6)2; 7 and [Ni-(L4NHC)](PF6)2; 8, (where L1NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L2NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L3NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L4NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle. 相似文献
30.
介绍了以Ta/Ta2O5/Cu为结构的平板MIM电容器的制备方法和性能测试,探究金属Cu直接作为钽电解电容器阴极层的可行性。通过阳极氧化法在钽箔表面制备非晶态的Ta2O5薄膜,以化学镀铜、磁控溅射镀铜两种镀铜工艺制备Ta/Ta2O5/Cu结构,并对所得结构进行结构表征和性能测试。实验结果表明:不同镀铜方式制备的Ta/Ta2O5/Cu结构在电学性能测试过程中都没有表现出电容特性,正负极之间的电阻仅有0.7Ω;以金属Cu直接作为钽电容器的阴极层会导致金属铜在测试过程中被氧化成铜离子从而进入Ta2O5介质层中,进而导致Ta2O5的击穿,因此金属铜不适合直接作为钽电容的阴极层。 相似文献