Chen Yuanyin

A Direct Synthesis of Aromatic Nitriles from Methylaromatic Compounds by Ammoxidation on DC-108 Catalyst

Abstract Aromatic nitriles were prepared from corresponding methylaromatic compounds by ammoxidation on DC-108 catalyst, giving 51-89% in yield. This method is simple and convenient without pollution.

Liquid crystalline behavior and fluorescent property of calix[4]arene containing azobenzene photochromic group

The reaction of 4′-hydroxy-4-methyl azobenzene (1) and 1,6-dibromohexane afforded 6-bromo-1-((4-((4-met hylphenyl)azo)phenyl)oxy)hexane (2), which further reacted with p-tert-butylcalix[4]arene to give the calix[4]arene derivative (3) whose lower rim had been modified by the azobenzene photochromic group. The structure of 3 was characterized by 1H-nuclear magnetic resonance (NMR) and electrospray ionization-mass spectrometry (ESI-MS). The fluorescence intensity of compound 3 was two to four times higher than that of compounds 1 and 2 as the azobenzene group concentration in the range of 1.6 × 10−5 to 8.0 × 10−4 mol/L, indicating that the fluorescence quantum yield of the azobenzene group had been improved through being attached to the calix[4]arene skeleton. The liquid crystalline behavior of compound 3 was studied by polarized microscopy (POM) and differential scan calorimeter (DSC). Compound 3 exhibited the enchased texture of a smectic liquid crystal from 209.4°C to 219.5°C on heating, while 2 exhibited a liquid crystalline phase from 87.4 to 83.2°C on cooling. It was found that the calix[4]arene skeleton was a good platform for conformation immobilization of azobenzene photochromic group and the formation of liquid crystalline.

Positron Annihilation Mechanism Correlated with Microstructure of C60-Contained Chitosan

Positron annihilation lifetime spectra measurements were performed on C60-containing chitosan as a function of temperature ranging from 290 to 380 K. Both the ortho-positronium annihilation lifetime τ3 and its intensity I3 increase with increasing temperature, however, the values of I3 in C60-containing chitosan are smaller than that in pure chitosan, and the slope of τ3 with temperature is also suppressed after C60 linked. The existing three models for positron annihilation in polymer have been compared to analyze the experiment result. It is realized that only the spur reaction model, combined with the free volume model, can explain it satisfactorily. The ortho-positronium lifetime and intensity were affected by the local physicochemical environment of material, i.e., free-volume structure, electron scavenging and trapping sites, etc. The linked C60 that play a significant chemical inhibition and quenching role on positronium formation and annihilation is first observed. The microstructure change brought by C60 group has also been discussed.

Electrocatalytic oxidation of H2O2 at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10−2 mol/L NaClO4+1.0×10−3 mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10−5−1.0×10−4 mol/L with a detection limit as low as 1.0×10−6 mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H2O2 at 1.0×10−5 mol/L. The modified electrode was used successfully in rainwater analysis.

Ammoxidation of substituted toluenes on silica-supported VPO catalysts

The ammoxidation of substituted toluenes to their corresponding nitriles over silica-supported vanadium phosphorus oxide (VPO/SiO2) catalysts has been studied. the effects of carrier silica, the addition of phosphorus, the substituents and the loadings have been discussed. Compared with unsupported VPO, the VPO/SiO2 catalysts have higher catalytic activity for ammoxidation of substituted toluenes and much lower reaction temperature. XRD shows that vanadium phosphorus oxides exist as amorphous phase and disperse to a high degree on the silica surface in 10% loading catalyst. When the loadings are over 10%, the crystalline α-VOPO4 would emerge, which would decrease the yield and selectivity. Additional phosphorus can form composite oxides with vanadia and play concerted catalytic function, which increase the selectivity of nitriles remarkably. Different substituents or same substituents on different positions have different influences because of the variant electronic stability of intermediates, the hindered accessibility of methyl group or the chemisorption state of the substrate molecule on the electrophilic catalyst surface.

3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO2 catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO2 catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH3/DCT in the feed gas and the space velocity (v1) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH3):n(air)=1:7:30 andv1=250 h−1. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO2 catalyst.

Porous spherical cellulose composites coated by aluminum (III) oxide and silicone: Preparation, characterization and adsorption behavior

Porous spherical cellulose composite (PSCA) coated by aluminum (III) oxide was prepared and modified by organosilicone. SEM images of the surface morphology of the bead cellulose shows that it has spherical shape and abundant porous structure on its surface. The mapping images, of aluminum and silicon of the composite (PSCAS) present aluminum (III) oxide and silicone are uniformly dispersed on the surface. The adsorption behavior of PSCAS toward metal ions was determined.

Synthesis and characterization of [60]fullerence ferrocenylmethyl derivatives

Two new [60]fullerene ferrocenylmethyl derivatives have been prepared via different approaches and characterized by UV-Vis, FT-IR, NMR, FAB-MS spectra and VPO. The second approach, i.e. reacting fullerene with ferrocenylmethyl azide directly, was never reported as yet.

Cellulose Beads Modified by Histidine:Preparation and Adsorption Behavior

Porous cellulose beads modified by histidine (PCBH) were prepared. The adsorption capacity of PCBH for divalent Mg(II), Cu(II), Pb(II) and Hg(II) ions were determined. The effects of the temperature, the initial pH value, the concentration of metal ion and PCBH ligand on the adsorption of Cu(II) Hg (II) were discussed. The adsorption process fitted to Freundlich adsorption isotherms for both metal ions. Adsorption rate constants were also found.

Synthesis and characterization of new calix[4]arene amino acid ester derivatives and their metal extraction properties

A new type of calix[4]arenes containing amino acid ester derivatives has been synthesized. Their1H NMR characteristics are discussed. Metal ion extraction experimental has shown that calix[4]arene amino acid esters (2a, 2b) possess good extraction efficiency for transition metal ions (Cu2+, Ni2+, Zn2+) and poor extraction efficiency for alkali metal ions (Na+, K+).