Table of Content

10 November 2009, Volume 30 Issue 11

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Content of Chemical Journal of Chinese Universities Vol.30 No.11(2009)

2009, 30(11):  0. 

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下期目次预览

2009, 30(11):  0. 

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Articles

Preparation and Characterization of Novel Nanometer Materials V₁₀O₂₄·12H₂O

SUN Juan-Ping, WU Guang-Ming*, ZHANG Ming-Xia, CUI Chao-Jun, YANG Hui-Yu, ZHANG

2009, 30(11):  2107-2111. 

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The novel mixed-valence vanadium oxide V₁₀O₂₄·12H₂O nano-structure were prepared by Sol-Gel process with the industrial V₂O₅ powder as the starting materials and a simple peroxyde reaction route in this paper, and the formation mechanism has been clarified. XRD, TEM, TG-DSC, FTIR and XPS measurements were used to obtain structure and infrared vibration of the V₁₀O₂₄·12H₂O. The analyses showed that the V₁₀O₂₄·12H₂O have a nano-structure with porous, and the diameter about 40—60 nm. The infrared absorption properties were discussed based on the vibration model and the change of bond length before and after reaction. It has reveal that shift of the absorption peaks of the V₁₀O₂₄·12H₂O was caused by the lattice expansion and formation of low valence vanadium ion in V₁₀O₂₄·12H₂O. This mixed-valence vanadium oxide has a nanoporous structure which make it a potential candidate to be used as cathode in lithium-based batteries.

Fabrication of LaFeO₃ Micro-nanofiber by Electrospinning

JI Hong-Wei, ZHOU De-Feng*, ZHOU Xian-Feng, LIU Hai-Tao, MENG Jian

2009, 30(11):  2112-2115. 

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Perovskite structure LaFeO₃ Micro-nanofiber was successfully fabricated via electrospinning combined with sol-gel technology. The samples of LaFeO₃ micro-nanofiber were characterized by thermogravimetry-differential thermal analysis(TG-DTA), X-ray diffraction(XRD), Fourier transform infrared(FTIR), X-ray photoelectron spectroscopy(XPS) and field emission scanning electron microscopy(FE-SEM) technology, respectively. The results show that the perovskite structure LaFeO₃ crystals begin to form at 390 ℃, accompanied by a small amount of weak La₂O₂CO₃ and Fe₂O₃ hybrid, the orthogonal perovskite structure LaFeO₃ micro-nanofiber is obtained by calcining at 600 ℃, the distribution of fiber diameter is between 300 and 600 nm, the average fiber diameter is about 420 nm with an average grain size of 28 nm.

Monovacant Keggin POM Modified by Complex of Metal and N-containing Ligand

WANG Tao, PENG Jun*, WANG Dan-Dan, LIU Hong-Sheng, TIAN Ai-Xiang, WANG Yong-Hui

2009, 30(11):  2116-2118. 

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A new monovacant polyoxometalates-based complex H₄[Cu(phen)(H₂O)][Cu(phen)][α-SiW₁₁O₃₉]·3H₂O was synthesized under conventional conditions. In compound 1, two independent other than dimerized copper-phenanthroline graups are fused to the oxggen atoms in the vacant site of the mono-lacunary polyanton in parallel. It crystallizes in the triclinic space group P1 with a=1.3624(2) nm, b=1.4133(2) nm, c=2.0470(3) nm, α= 97.840(3)°, β=95.117(3)°, γ=112.483(3)°, V=3.5645(10) nm³, D_c=3.006 g /cm³, Z=2. Structure of compound 1 was characterized via elemental analysis, IR, single crystal XRD and cyclic voltammetry methods.

Synthesis of High Ordered Mesoporous Silica SBA-16 Within Columnar Alumina Pores

FU Wen-Sheng*, LI Zu-Lin, ZHOU Xiao-Min, ZHANG Xun-Yan, HU Jia-Jia, NIU Yu-Ling

2009, 30(11):  2119-2122. 

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One-dimensional nano-scaled mesoporous silica was synthesized within anodic alumina membrane pores surfactant by Pluronic F127. In contrast to soaking the AAM into the precursor solution way, we use pressure-induced infiltration approach and it has advantages that mesoporous silica hardly forms on the surface of AAM. Nano-fiber with highly uniform structure was arranged along anodic alumina cavity. The hexagonal pore structure is visible on both fiber edges with the diameters of the pores being about 12 nm. The effects of the ratio of chemical reagent and the reaction time on the mesostructure was also investigated. The resulting hybrid mesoporous membrane could be used for enzyme catalytic and nanofluidic systems.

Damaging Effects of Photoexcited TiO₂ Nanoparticles on Gastric Cancer SGC-7901 Cells

XIA Chun-Hui, YU Wen-Xue*, WANG Bai-Qi, WANG Yu, WANG Lu, HUANG Hai-Tao

2009, 30(11):  2123-2126. 

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Damaging effects of photoexcited TiO₂ nanoparticles on gastric cancer SGC-7901 cells were investigated. The influences of nanosized TiO₂ content, and irradiation time on cancer inhibition were systematically studied, and the inhibition mechanism was primarily discussed. The results demonstrate that photoexcited TiO₂ nanoparticles exhibit good inhibition effects on gastric cancer SGC-7901 cells, and this process follows appro-ximately first-order reaction rule. While the concentration of TiO₂ nanoparticles is about 300 μg/mL, the damaging effects are rather remarkable. In addition, the exhibition forms of gastric cancer SGC-7901 cells are apoptosis and necrosis in killing experiments. Taken together, damaging effects of photoexcited TiO₂ nanoparticles on gastric cancer SGC-7901 cells might be attributed to the reactive oxygen species formed on the TiO₂ nanoparticles surface.

Synthesis and Luminescent Properties of YVO₄∶Sm³⁺ Red Phosphor by Molten Salt Synthesis Method

LIU Rong, LIANG Yu-Jun*, WU Xiao-Yong, LI Yong-Zhou, GONG Yan-Sheng

2009, 30(11):  2127-2130. 

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Luminescent materials YVO₄∶Sm³⁺ were successfully prepared using NaNO₃ as the molten salt by molten salt synthesis(MSS) method. The phosphors obtained were treated with different calcination temperatures and doping concentrations to get better luminescent properties. The uniformity of phase of Sm³⁺ doped YVO₄ phosphor was checked by X-ray diffraction(XRD) technique. In addition, the dependence of the luminescence intensity on doping concentrations and annealing temperatures were discussed. The results show the characteristic emissions of the doped rare earth ions(Sm³⁺) in YVO₄ hosts. The emission at 647 nm due to ⁴G_5/2-⁶H_9/2 transition of Sm³⁺ ions was improved drastically by MSS method than other methods. All samples show red emission and the best red light emission is observed with YVO₄∶Sm³⁺(Sm³⁺ molar fraction 1%) after calcinated at 500 ℃ for 5 h.

Synthesis, Characterization and Near-infrared Photoluminescence of Ytterbium(Ⅲ) Monoporphyrinate Complexes

FU Shi-Tao, ZHANG Zhi, YU Kai-Chao, WONG Wai-Kwok, LI Zao-Ying*

2009, 30(11):  2131-2135. 

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A series of ytterbium(Ⅲ) monoporphyrinate complexes(2a—2e), bearing different substituents on meso- or β- position, were synthesized and characterized via UV-Vis, ¹H NMR, high-resolution mass spectra and elemental analysis. The photoluminescent properties of the complexes, especially in the near-infrared region, were studied in detail. Related quantum yield and fluorescence lifetime show that the energy is transferred to the excited state of ytterbium(Ⅲ) ion caused by excitation of the π→π* transitions of porphyrinate, which led to strong NIR emission. The light-emitting efficiency of the complexes with electron-donating substi-tuents on meso-position is better than that of complexes with electron-withdrawing substituents, while the complex with bromide on β-position possesses the poor ability of light-emitting.

Reconstructed Synthetic and Characterization of a Insoluble Polyoxometalate Coordination Polymer

WANG Li*, CAI Wei, OU Guang-Nan

2009, 30(11):  2136-2138. 

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A general reconstructed synthetic strategy for ionic liquids-supported the insoluble polyoxometalate coordination polymer was proposed. A insoluble polyoxometalate(POMs) coordination polymer 1, [{La(H₂O)₅(dipic)}{La(H₂O)(dipic)}]₂{Mo₈O₂₆}·10H₂O was successfully reconstructed by electrolyzing in ionic liquids on conducting glasses coated with indium tin oxide(ITO) electrode. The polyoxometalate coordination polymer is insoluble in aqueous solution and usual organic solutions, but soluble in the ionic liquid [RMIM][HT] or [RMIM][HP]. The reconstructed synthetic polyoxometalate coordination polymer was characterized via XPS and XRD techniques. The result show the XRD pattern of the deposited POMs on ITO electrode has the same crystal structure as the polyoxometalate coordination polymer 1, which imply that the crystal structure of the deposited POMs on ITO electrode keeps the same as the original POMs compound. It was favored the compound 1 reconstructed by the electrolyzing in an ionic liquid.

Methanol-induced Conformation Change of Myoglobin in Basic Solution

JIANG Dan, CHU Yan-Qiu, CHEN Nan-Sheng, DING Chuan-Fan*

2009, 30(11):  2139-2145. 

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This paper reports the methanol-induced conformation change of myoglobin in basic solution. According to the results of mass spectrometry, we found that the conformation of myoglobin(Mb) changed in different volume fractions of methanol at pH=11.0, 11.4, 12.0. And both of the methanol concentration and pH value have some effect. Mb exists as hMb at pH=11.0, aMb at pH=12.0, aMb at pH=11.4 except in 30% volume fraction of methanol solution. Using negative ion mass spectrometry mode, Mb all show mainly as aMb. More information of Fe ion′s coordination and electron spin state were found via CD spectrometry and UV-Vis Soret absorption.

Syntheses of Fluorescence Probe 5-[2-(1H-imidazol-1-yl)-2-oxoethyl]benzo[b]acridin-12(5H)-one and Its Application for the Determination of Aliphatic Amines with LC-APCI-MS

FU Yan-Yan, SUN Zhi-Wei, ZHAO Huai-Xin, BAI Xin-Wei , SUO You-Rui , ...

2009, 30(11):  2146-2153. 

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2-{12-Oxobenzo[b]acridin-5(12H)-yl}-acetic acid(BAAA) reacted with coupling agent N,N′-carbonyldiimidazole(CDI) to form an activated amide intermediate 5-[2-(1H-imidazol-1-yl)-2-oxoethyl]benzo[b]acridin-12(5H)-one(IEBA), which was a novel fluorescence probe. The amide intermediate(IEBA) reacted preferably with amines in DMF solvent in the absence of catalysts to give the high yields of derivatives, which not only have high fluorescence sensitivity but also have strong ionizable ability. The optimum excitation and emission wavelengths were at λ_ex/λ_em=272 nm/505 nm. The percent ionization δ values in aqueous acetonitrile and aqueous methanol were in the range of 0—57.32% and 0—62.14%, respectively. The fluorescence detection limits of twelve amine derivatives(at a signal-to-noise ratio of 3) were in the range of 0.15—0.50 ng/mL. The online APCI-MS detection limits were at levels of 1.43—8.51 ng/mL(S/N=3).

Direct Binding of Reaction Pb²⁺ to Calmodulin by Square Wave Polarography and Cyclic Voltametry

LIU De-Long*, WU Yan-Huan, GUO Hui-Fang, BAI Juan, SUN Da-Ye

2009, 30(11):  2154-2158. 

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Calmodulin(CaM) is a highly conserved Ca²⁺ binding protein ubiquitously found in animals and plants, which is involved in a large variety of cellular functions. The presence of many other metal ions in the physiological and nonphysiological environment such as heavy metal ions suggests that CaM might be binding other metal ions than Ca²⁺, which might influnce CaM′s function. It is important to investigate the general metal ion binding properties of CaM. Based on high sensitivity of square wave polarographic signal of Pb²⁺, the direct binding reaction of Pb²⁺ to CaM was studied by square wave polarography(SWP). The complexing specie, Pb²⁺-CaM, was detected for the first time by SWP in the Pb²⁺-CaM system, and electrochemical reaction characterization was done by cyclic voltammetry. Two reduction peaks were detected in SWP polarograms obtained at different concentration ratios of Pb²⁺ to CaM at pH=6.5, indicating that two electroactive species of Pb²⁺ exist, the reduction peak potentials of two species are in the range of -0.44—-0.47 V and -0.73—-0.77 V vs. SCE, respectively. The peak with a maximum at ca. -0.44—-0.47 V is corresponding to the reduction of free Pb²⁺ under our experimental conditions and the peak with a maximum at ca. -0.73—-0.77 V, clearly more negative than that for the reduction of free Pb²⁺, allows us to interpret it as due to the reduction of Pb²⁺ complexed by CaM. Moreover, prior to the addition 10 times of Pb²⁺, two peak currents increase gradually with the increasing of the Pb²⁺ concentration. At higher metal ion concentration(10—16 times), the peak currents of free Pb²⁺ increased linearly with a higher value of the slope, while the peak currents of the complexing specie, Pb²⁺-CaM, reached maximal and constant. The polarographic titration curves of the two species show that there are ten binding sites in CaM at pH=6.5. Furthermore, the reduction species of Pb²⁺-CaM system was confirmed by cyclic voltammetry with Controlled Growth Mercury Electrode(CGME). One couple of the free Pb²⁺ redox waves were observed clearly in the cyclic voltammogram, and only the reduction peak of the complexing specie of Pb²⁺-CaM system was detected. The results obtained in the paper show a direct evidence for the mechanism of the toxicity of Pb²⁺ by CaM mediating.

Preparation of a Fragment Imprinted Polymer for Recognition of Triazole Pesticides and Its Application to Solid-phase Extraction

PENG Chang, LIU Wei-Juan, ZHANG Chun-Tao, ZHANG Ling*, ZHANG Zhi-Chao*

2009, 30(11):  2159-2164. 

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A series of fragment imprinted polymers for selective recognition of seven triazole pesticides(triadimefon, diniconazole, paclobutrazol, uniconazole, tebuconazole, triadimenol and bitertanol) were prepared through fragment imprinting technique, utilizing various benzene derivatives as the alternative-template. Results of batch binding experiments show that the fragment imprinted polymer(M1) with 2-nitrophenol as the template exhibit the highest recognition ability for the tiazoles. In light of the effects of the structures of the triazoles on the adsorption capacity of the fragment imprinted polymer, the recognition mechanism is proposed as follows: the terminal phenyl group of the tiazoles enters a cavity in the fragment imprinted polymer, while the tiazoles′ hydroxyl standing outside the cavity forms hydrogen bond between with the nitrogen atom of the functional monomer 4-vinylpyridine standing outside the cavity; the former is the key factor affecting the recognition of the fragment imprinted polymer. Finally, the polymer(M1) was used as the sorbent of solid-phase extraction. For the molecularly imprinted solid-phase extraction(MISPE) procedure, the loading, washing and elution conditions were optimized. The optimized MISPE procedure was applied to the clean-up of the matrix solid-phase dispersion(MSPD) extracts from soil samples for the determination of the above-mentioned triazole pesticides. The clean-up of MISPE was proved. Recoveries of MSPD-MISPE extracts from soil samples spiked at three levels were 75%—102%, with good precision(RSD=3%—9%, n=5). The lowest limits of detection(the ratio of signal to noise=3) ranged from 0.9—15 μg/kg. This study highlights the potential of the novel method combining the simplicity of MSPD with the high selectivity of MISPE for extraction of trace compounds from complex matrices.

Electrochemical Behavior of Rutin in [bmim]BF₄ Ionic Liquid and Influence Factors

DONG She-Ying*, WANG Yuan, HUANG Ting-Lin, ZHOU Yuan-Zhen, ZHENG Jian-Bin

2009, 30(11):  2165-2169. 

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In the medium hydrophilic ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([bmim]BF₄), the electrochemical behaviors of rutin(Rt) were studied by linear sweep voltammetry and cyclic voltammetry. The influences of scan rate, accumulation time and temperature on the electrochemical cha-racteristics of Rt were also discussed. The experimental results indicated that the electrode process of Rt was a quasi-reversible process with absorption, and the electron transfer number was 2. The standard rate constant k_s of Rt was 0.126 s^-1 in [bmim]BF₄. The effects of water or ethanol on the electrochemical behavior of Rt were investigated systematically. With the increasing of amount of water or ethanol, the peak potential of Rt shifted negatively and the peak current increased, and water affected the system more obviously than ethanol. In the [bmim]BF₄-H₂O system, a linear dependence of oxidation current on Rt concentration was obtained in the range of 4.0×10^-5—1.4×10^-4 mol/L, the detection limit was 1.0×10^-5 mol/L. This method could be applied to the determination of rutin content.

Ultrasensitive Electrochemical Assay for the Detection of p53 Sequence Based on the Aggregation of Gold Nanoparticles

ZHENG Jing, SHEN Bi-Jun, CHENG Gui-Fang*, FENG Wan-Juan, HE Pin-Gang, ......

2009, 30(11):  2170-2174. 

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An ultrasensitive and high specific electrochemical assay for the detection of human tumor suppression p53 gene has been developed. Two DNA sequences were designed, and the combined sequences were complementary to that of the target p53 sequence, one was immobilized on the magnetic nanoparticles for capturing the target p53 sequence, the other was labeled with gold nanoparticles as probe. The ultrasensitive detection was achieved by the aggregation of gold nanoparticles with introducing thiocyanuric acid into the system to form the network like structure, and the detection limit could go down to 2.24×10^-17 mol/L for the wild type p53 sequence. The discrimination between the mutant type p53 DNA and the wide type p53 DNA was studied with the proposed assay.

Interaction Between Pymetrozine and Bovine Serum Albumin

XU Wei, WU Xia*, ZHOU Hai-Ping, LIU Xiao-Yu, YANG Jing-He, FAN Jin-Yong, ......

2009, 30(11):  2175-2179. 

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The interaction between pymetrozine(Py) and bovine serum albumin(BSA) was investigated by spectroscopy methods, including fluorescence, ultraviolet absorption(UV) and far-UV circular dichroism(CD) spectroscopies. The quenching mechanism of fluorescence was suggested as static quenching according to the Stern-Volmer equation. The thermodynamic parameters enthalpy change(ΔH) and entropy change(ΔS) were calculated, which suggested that the binding power between pymetrozine and bovine serum albumin was hydrogen-bond and van der Waals force. According to the Förster non-radiation energy transfer theory, the binding average distance(r=2.4 nm) between donor(BSA) and acceptor(Py) was obtained. Furthermore, the investigations of the synchromous fluorescence and CD spectra of the system reveal that the conformation of BSA is changed in the presence of Py.

Dot Immunofiltration Assay for Quantitative Detecting cTnI Using Quantum Dots

FAN , SONG Jian, BI Li-Rong, ZHOU Guang-Yu, ZHANG Hao, WEI Jing-Yan

2009, 30(11):  2180-2183. 

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Quantum dots have physical and optical properties that make them useful tools for high-resolution labeling immunoassay. In this work, a rapid and simple method of quantitative immunoassay for Cardiac troponin I(cTnI) was developed with quantum dots-labeled antibodies. The monoclonal antibodies of cTnI(2F11) could be labeled with CdTe quantum dots and the coupled product(CdTe-2F11) were characterized by SDS-PAGE. The result of immunofiltration assay indicats that the CdTe-2F11 maintains the antibody activity. The cTnI at the different concentrations in NC membrane could react with CdTe-2F11 and be detected with ImageMaster to analyze the fluorescence intensity of the immunodotting. The results show that the detection limit of cTnI is 120 ng, and there is a good linear relation between concentration of cTnI and the fluorescence intensity(R²=0.9966).

Synthesis, Crystal Structure and Anion Recognition of 1,8-Di(pyrrole-2-carboxamino)-3,6-dichlorocarbazole

SU Dong-Dong, NIU Hao-Tao, WANG Ying, HE Jia-Qi*, CHENG Jin-Pei

2009, 30(11):  2184-2188. 

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Due to the fundamental roles that anions play in a wide range of chemical and biological processes, numerous efforts have been devoted to the design of receptors capable of selectively binding and sensing anions. Herein, carbazole derivative (1) bearing two model amides was synthesized by coupling 1,8-diamino-3,6-dichlorocarbazole with pyrrole-2-carbonylchloride in the presence of triethylamine. The structure of compound 1 was characterized by X-ray crystallography. The anions recognition of the compound 1 was studied by the UV-Vis and fluorescent spectra method in highly polar solvent of DMSO. The results show that strong anion binding is observed for H₂PO₄^-. Obvious fluorescence “switched on” behavior is observed upon addition of H₂PO₄^- to receptor 1, which can be used to discriminate H₂PO₄^- from the other anions. ¹H NMR analysis revealed that all the five NH of receptor 1 were involved in the hydrogen bonding interactions with the anions leading to a conformation exchange during the anion binding.

Isolation, Purification and Structural Analysis of Polymannuronic Acid from Undaria pinnatifida

WANG Cai, SHI Song-Shan, HONG Qi-Ming, WANG Shun-Chun*, WANG Zheng-Tao, ......

2009, 30(11):  2189-2192. 

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UPPS03 and UPPS04 were obtained from Undaria pinnatifida by water extraction, DEAE-Sepharose Fast Flow, Sephacryl S-300 and Sephacryl S-200 gel permeation chromatography. HPGPC shows that both of them are homogeneous polysaccharides with an average molecular weigh of 3.6×10⁴ and 1.1×10⁴, respectively. The structural features of UPPS03 and UPPS04 were characterized with sugar composition analysis, periodic acid oxidation and Smith degradation, reduction of uronic acid, methylation analysis, IR and NMR. The results indicate that they are all linear polysaccharide with β-1,4-linked polymannuronic acid, and this is the first report of polymannuronic acid isolated from Undaria pinnatifida.

Design of Generic Haptens for O,O-Diethyl Phosphorothioate Pesticides and Recognition Properties of Antibodies

XIE Gui-Mian, SUN Yuan-Ming, XU Zhen-Lin, LI Yong-Xiang, LEI Hong-Tao, ......

2009, 30(11):  2193-2198. 

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Class-specific polyclonal antibodies for O,O-diethyl phosphorothioate pesticides had been generated. A series of generic haptens were synthesized and coupled to bovine serum albumin(BSA) and ovalbumin(OVA) for immunogens and coating antigens, respectively. New Zealand rabbits were immunized with immunogens to obtain corresponding polyclonal antibodies. The effects of hapten structure on antibodies properties and hapten heterology on ELISA sensitivity were also investigated. The results show that haptens with simple spacer-arm can generate antibodies with desired properties, and hapten heterology can improve ELISA sensiti-vity significantly. The polyclonal antibody PAb-H1 shows high sensitivity to seven commonly used O,O-diethyl phosphorothioate pesticides in an indirect competitive ELISA using a heterologous coating antigen(H6-OVA). The 50% inhibition value(IC₅₀) is 0.013 mg/L for coumaphos, 0.348 mg/L for parathion, 0.022 mg/L for quinalphos, 0.035 mg/L for triazophos, 0.751 mg/L for phorate, 0.850 mg/L for dichlofenthion and 1.301 mg/L for phoxim, respectively. And the limit of detection(LOD) is lower than MRLS of all the seven O,O-diethyl phosphorothioate pesticides in food and agricultural products . Thus, this indirect ELISA with high sensitivity can potentially be used to develop commercial ELISA kits for a sensitive and rapid detection of O,O-diethyl phosphorothioate pesticides residues.

Highly Efficient Synthesis of Two Hyaluronan Trisaccharide Analogues for Potential Hyaluronic Acid Synthases Inhibitors

WEI Guo-Hua*, DU Yu-Guo, Khushi L. Matta

2009, 30(11):  2199-2203. 

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The syntheses of two hyaluronan trisaccharide analogues, naphthyl O-(3-methoxy-β-D-glucopy-ranosyluronic acid)-(1,3)-O-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1,4)-O-β-D-glucopyranosyluronic acid and naphthyl O-(3-methoxy-2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1,4)-O-(β-D-glucopyranosyluronic acid)-(1,3)-O-2-acetamido-2-deoxy-β-D-glucopyranoside, were described. Construction of the target molecules was achieved through a combination of BF₃·Et₂O/toluene system and trichloroacetimidate glycosylation methodology. This is the first report on the synthesis of the 3-methoxyl derivatives, which represent the smallest fragments that incorporate all the structural features of polymeric hyaluronan and can be used for potential hyaluronic acid synthases inhibitors.

Aggregation and Self-coiling of Biomimetic Linear Donors and Foldamers Incorporating 1,5-Dioxonaphthyl

ZHOU Qi-Zhong*, ZHAO Shu-Min, LIU Shi-Yong

2009, 30(11):  2204-2209. 

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A series of foldamers and linear donors containing 1,5-dioxonaphthyl group were synthesized. The influence of the Critical Aggregating Concentrations(CAgCs) of the donors was detected with steady state fluorescence method. Aggregation of the donors was correspondent to the φ value of DX-H₂O or CH₃CN-H₂O binary solvent. In DX-H₂O or CH₃CN-H₂O binary solvent, intermolecular or intramolecular π-π stacking improved aggregation. Otherwise, intramolecular folding also enhanced aggregation. The self-coiling enlarged with decrease of the φ value and with the increased number of 1,5-dioxonaphthyl group in the molecules.

Fast Fabrication of Superhydrophobic Surfaces on Aluminum by the Comibined Method of Chemical and Electrochemical Corrosion

ZHANG Qin*, ZHU Yuan-Rong, HUANG Zhi-Yong

2009, 30(11):  2210-2214. 

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This paper presents a quick method for creating hierarchical micro/nano-structure on aluminum to achieve water-repellent surface. The method includes two steps i.e. chemical etching and electrochemical corrosion. SEM results show that the micro-structure can be easily obtained by means of chemical etching and nano-structure can be attained using electrochemical corrosion. And the micro/nano-sructure surface can be fabricated within 20 min by the two-step method. Compared to one-step electrochemical oxidization, this me-thod make the processing-time 1—2 order shorter and current density 1 order smaller. Meantime, it is una-ffected by the aluminum crystalline with respect to chemical etching. The two-step method is hopeful to be used in industry and expected to other metals for preparing super-hydrophobic surfaces.

Influence of the Precursor Phase Transition on the Catalyst Activity in Slurry Methanol Synthesis

LI Zhong*, GUO Qi-Hai, ZHANG Xiao-Bing, ZHENG Hua-Yan, FAN Hui, XIE Ke-Chang

2009, 30(11):  2215-2221. 

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The CuO/ZnO/Al₂O₃ catalyst precursor were prepared by co-current precipitation and the crystal composition and phase-transition of the precursor prepared at different aging temperature were investigated in order to study the effect of the crystal composition and phase-transition of the precursor on the catalyst activity for slurry methanol synthesis. The results show that phase-transition of precursors are prominent influence on catalytic activity for slurry methanol synthesis. The (Cu,Zn)₂CO₃(OH)₂ and(Cu,Zn)₅(CO₃)₂(OH)₆ crystal phase are critical precursor to produce the catalytic active centre. The degree of substitution between Cu²⁺ and Zn²⁺ is increased with increasing Cu²⁺/Zn²⁺ entering crystal lattices of Zn₅(CO₃)₂(OH)₆/Cu₂(CO₃)(OH)₂, and the ratio of copper to zinc in Rosasite and Aurichalcite is unchangeable. The calcined catalyst has more specific surface area and strong interaction between CuO-ZnO, and gets high activity in slurry methanol synthesis.

Removal of Sulfur Compounds from Simulated Oil with Oxidation by Quaternary Ammonium Peroxotungsto Phosphate Catalysts

CUI Bao-Chen*, LIU Shu-Zhi, LIU Wei, WANG Bao-Hui

2009, 30(11):  2222-2225. 

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Catalytic oxidation desulfurization of thiophene-type sulfides, benzothiophene(BT) and dibenzothiophene(DBT), in simulated oil using H₂O₂ as oxidant and quaternary ammonium peroxotungsto phosphate as the catalyst was investigated. Effect of amount of catalyst, reaction temperature, reaction time and oxidant/oil volume ratio on catalytic oxidation desulfurization was investigated. The results show that the conversions of dienzothiophene and benzothiophene reach above 96.48% and 99.42% respectively, under the conditions of amount of catalyst 0.48%, H₂O₂/Oil volume ratio of 1∶50, temperature of 60 ℃ after reaction 60 min. The kinetic study indicate that catalytic oxidation desulfurization of simulated oil over peroxy phosphotungstic acid is pseudo first-order reaction.

Cobalt-containing Hydrotalcites Derived Catalysts for Simultaneous Removal of NO_x and Soot

WANG Zhong-Peng*, ZHANG Zhi-Xiang, SHANGGUAN Wen-Feng

2009, 30(11):  2226-2232. 

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Cobalt-containing mixed oxides(CAO) were prepared by thermal decomposition of hydrotalcite-like precursors with Co/Al molar ratio varying from 2 to 7. The catalytic activity of the CAO was investigated for the simultaneous catalytic removal of NO_x and diesel soot particulates by temperature-programmed reaction(TPR) technique in a fixed-bed flow reactor. The relationship between the catalyst structure and performance were clarified through ICP, BET, SEM and XPS measurements. The results show that all catalysts exhibit a nonstoichiometric spinel phase. Oxygen species present on the catalyst surface included lattice oxygen, the adsorbed oxygen and(or) the surface hydroxyl species, which acted for different mechanisms in soot oxidation. The catalytic activity was influenced by both Co/Al ratio and calcinations temperature. 4CAO-800 with the Co/Al molar ratio of 4 and calcinations temperature of 800 ℃ show the best activity with a low ignition tempe-rature(t_i=290 ℃) and high selectivity to N₂ formation(S_N2/C=3.5%). During the NO_x-soot reactions, a re-dox mechanism and a spillover mechanism may occur simultaneously for the catalytic soot oxidation.

Linear Relationship Between the Partial Charges of H and O Atoms in Carboxyl of Substituted Benzoic Acid and the Hammett Constants

LI Hua-Yi*, HU You-Liang

2009, 30(11):  2233-2239. 

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The linear dependence between the partial charges of H1, O2 and O3 atoms in carboxyl of substituted benzoic acid and Hammett constants was analyzed by density functional theory(DFT). Different density functional and partial charge computation methods[B3LYP/6-311G*/(NBO, Mulliken), (BLYP, BP, PWC)/DNP/(Hirshfeld, Mulliken)] were used to evaluate the above linear relationship. It was found that BLYP/DNP/Hirshfeld had high accuracy and high computational speed. Seventy substituted benzoic acid compounds were computed. The results show that the linear correlation coefficient between the partial charges of H1, O2 and O3 atoms and σ_p and σ_m is higher than 0.98. The best linear relationship occurred between the partial charge of O2 atom and Hammett constant. The partial charge of O2 atom could be used as substitute of Hammett constant in the quantitative structure property analysis and to predict Hammett constant.

Preparation of Mn-Fe/ZrO₂-TiO₂ Monolith Catalyst and Its Properties for Low-Temperature NH₃-SCR Reaction

LIN Tao, XU Hai-Di, LI Wei, ZHANG Qiu-Lin, GONG Mao-Chu, CHEN Yao-Qiang*

2009, 30(11):  2240-2246. 

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The catalytic properties of the monolith ZrO₂-TiO₂ supported Mn-based catalysts were studied for NH₃-SCR reaction at low temperature. The catalysts were characterized by specific surface area measurements(BET), X-ray diffraction(XRD), oxygen storage capacity(OSC) , temperature programmed reduction(TPR) and X-ray photoelectron spectroscopy(XPS). The results indicate that, compared to the catalysts supported on TiO₂ ,the catalysts supported on ZrO₂-TiO₂ have higher surface area, more steady structure, more OSC, stronger redox properties as well as higher concentration of surface Mn and have good activity at low temperature and excellent stability at high temperature. After Mn-Fe/ZrO₂-TiO₂ is calcined at 700 ℃, the light-off tempe-rature of the catalyst is 182 ℃ and NO conversion is 78% at a high space velocity of 55000 h^-1, and the catalyst is water-resistant. It shows great potential for practical application.

Preparation and Modification of TiO₂ Thin Film Electrode in Dye-sensitized Solar Cell and Its Photoelectrochemical Properties

LI Li, ZHANG Gui-You, CHEN Ren-Jie, Dorina Walther, CHEN Shi, WU Feng

2009, 30(11):  2247-2251. 

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The tetraisopropyl titanate was used as titaniume source to prepare the TiO₂ nanomaterial by the hydrothermal method. The TiO₂ crystal is anatase. In order to enhance the electrode′s photoelectrochemical performance, the metal nickel doping and superficial gable neodymium oxide were used. The experimental results indicate that the nanometer TiO₂ pellets have all the same shape and a particle size of approximately 17—18 nm. After nickel doping, the granularity increased obviously, but still maintained the even condition and the vesicular structure. Compared with the ordinary TiO₂ thin film electrode, the metal doping and the superficial gable is helpful for separating the electron and the hole. The solar cell′s short circuit photoelectric current enhanced by 16% and the electro-optic transfer efficiency enhanced by 17%.

Density Functional Theory Study on Interaction of CO2 with Metal Surface Carbon Species in Synthesis of Acetic Acid from CH4/CO2 on Co-Pd Catalysts

ZHANG Ri-Guang, HUANG Wei*, WANG Bao-Jun

2009, 30(11):  2252-2257. 

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The insertion reactions of CO₂ with M—H(M=Co, Pd) and Pd—CH₃ were systematically investigated by the first-principle DFT-GGA calculations. The mechanisms of CO₂ reacting with M—H and Pd—CH₃ were obtained for the direct synthesis of acetic acid from CH₄/CO₂ by a two-step reaction sequence on Co—Pd catalysts. The calculation result showed that the pathway that CO₂ inserts into Co—H bonds forming HCOO—Co was the most advantageous in dynamics for all four designed reaction paths. However, HCOO was linked with Co in bi-dentate form, whose binding energy was very large, so the desorption of HCOO hardly taken place and formic acid was little produced. Meanwhile, the pathway that CO₂ inserts into Pd—CH₃ bonds forming H₃CCOO—Pd was secondly preferential pathway favored in dynamics. The binding energy between H₃CCOO and Pd was small, and desorption of H₃CCOO easily occurred, so the main product was acetic acid. While methyl formate was inhibited by dynamics. The calculated result was in accordance with the experimental facts.

Synthesis, Structure Characterization and Thermochemistry of Anhydrous Lithium Benzoinate

HE Dong-Hua, DI You-Ying*, YANG Wei-Wei, KONG Yu-Xia, DAN Wen-Yan, TAN Zhi-Cheng

2009, 30(11):  2258-2262. 

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Benzoic acid and lithium hydroxide with the analytical grade were chosen as the reactants, and the lithium benzoinate was synthesized by means of hydrothermal synthesis. XRD, FTIR and elementary and chemical analyses were applied to characterize its composition and structure. Low-temperature heat capacities of the compound were measured via a precision automated adiabatic calorimeter over the temperature range from 80—400 K. A polynomial equation of the heat capacities as a function of the temperature was fitted by the least square method. A reasonable thermochemical cycle was designed on the basis of the preparation reaction of the substance, 0.1 mol/L of HCl solution was chosen as the calorimetric solvent, and the standard molar enthalpies of dissolution for the reactants and products of the hydrothermal reaction in the selected solvents were measured by an isoperibol solution-reaction calorimeter, respectively. The enthalpy change of the preparation reaction was determined as Δ_rH_m⁰=-(9.75±0.27) kJ/mol from the standard molar enthalpies of dissolution. Eventually, the standard molar enthalpy of formation of anhydrous lithium benzoinate was derived to be Δ_fH_m⁰=-(307.82±0.57) kJ/mol by Hess′s law.

Isothermal Vapor-liquid Equilibria for the Binary System Maleic Anhydride+Di-n-butylsebacate

ZHU Rong-Jiao, LIU Shu-Can, JI Jia, TIAN Yi-Ling*

2009, 30(11):  2263-2267. 

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Vapor-liquid equilibrium(VLE) data for maleic anhydride(MAN) and its absorption solvents are important for developing and researching the MAN production process. Isothermal VLE data for MAN and di-n-butylsebacate(DBS) binary system at 413.15, 433.15 and 453.15 K were determined with a modified ebulliometer in this work. Saturated pressure of pure DBS and MAN were measured and their Antoine constants were obtained. The experimental results were correlated and calculated using the NRTL model. The UNIFAC model was also used to predict the VLE data. At the same time, the parameters of the NRTL model for the MAN(1)+DBS(2) binary system were obtained. And the predicted results show a good agreement between the correlated data and the experimental data.

Docking Studies on the Interaction of Imidazolines and Potassium Ion Channel-Kir6.2

ZHANG Rui, LING Bao-Ping, MENG Xiang-Hua, WANG Zhi-Guo, ZHANG Chang-Qiao, ......

2009, 30(11):  2268-2273. 

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Kir6.2, a key component of the ATP-sensitive potassium channel(K_ATP), can directly interact with imidazolines, a kind of potential antidiabetic drug. This paper explored the interaction of Kir6.2 with imidazoline molecules by applying AutoDock software. The docking results reveal the binding sites of the seven imidazolines on Kir6.2. For Efaroxan, Clonidine, Cibenzoline and Bl11282, polar residues, H175, K67and W68, constitute the binding pocket; while Rx871024, Alinidine and Ly389382, lies in a hydrophobic pocket which is composed of nonpolar residues, F168, M169 and I296. Efaroxan, Clonidine, Cibenzoline and Bl11282 interact with Kir6.2 mainly by forming hydrogen bonds, but for Rx871024, Alinidine and Ly389382, the hydrophobic interaction is the most important mode of action. These binding sites and the interaction modes can interpret the inhibition of these imidazoline drugs to some extent, and this research may provide theoretical support in the pharmacological study of imidazolines regulating the secretion of insulin.

Theoretical Studies on the Structural and Optoelectronic Properties of F-Substituted Silole Derivatives

YANG Gui-Xia, HUANG Zong-Hao*, YANG Pei-Pei, XIN Yi, JIANG Zi-Jiang, ......

2009, 30(11):  2274-2278. 

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The geometrical and optoelectronic properties of 1,1-dimethy-2,3,4,5-tetraphenylsiole(PSP) and its eight F-substituted derivatives were investigated via Density Functional Theory(DFT) method at B3LYP/6-31(d) level. Calculation results show that the F-substitution′s position on side chain plays a key role on the geometric and optoelectronic properties of PSP. In addition, the increase of the substitutions′ number can enhance the related effects. Substitutions on ortho and para positions will bring significant impact on the molecular configurations. An increase of HOMO-LUMO energy gap and a blue-shift spectrum can be observed after substitution. Substitutions on meta positions show an obvious induction and electron withdrawing effects .At the same time, LUMO energy level decreases and the increase of electron affinity are favorable for the electron injection.

Density Functional Theory Study on the Surface Reaction Mechanism of Atomic Layer Deposited Ta2O5 on Si(100) Surfaces

REN Jie1*, ZHOU Guang-Fen1, GUO Zi-Cheng1, ZHANG Wei2*

2009, 30(11):  2279-2283. 

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The surface reaction mechanism of atomic layer deposited(ALD) Ta2O5 on silicon surfaces was studied via density functional theory. The ALD process is designed into two sequential half-reactions, i.e., TaCl5 and H2O half-reactions. Both of them proceed through an analogous trapping-mediated mechanism. By comparing with the reactions of TaCl5 on the H-terminated silicon surfaces, we find that it is both kinetically and thermodynamically more favorable for the reactions of TaCl5 on the hydroxylated silicon surfaces. In addition, we also find that it is energetically unfavorable for the H2O half-reactions.

Theoretical Studies of Electronic Structures and Spectroscopic Properties of [M(N)X₂]^-(M=Ru, Os; X=S₂C₆H₄, mnt)

LI Ming-Xia, ZHOU Xin, ZHANG Hong-Xing*, FU Hong-Gang, SUN Chia-Chung

2009, 30(11):  2284-2287. 

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Ruthenium(Ⅵ) nitrido complexes and osmium(Ⅵ) nitride complexes [M(N)X₂]^-(M=Ru, Os; X=S₂C₆H₄, mnt) were investigated theoretically to explore their electronic structures and spectroscopic properties. The ground-state geometry structures of complexes 1—4 were optimized by the DFT method(B3LYP). The calculated geometry parameters are in agreement with experimental values. Absorption spectra for complexes 1—4 in CH₃CN solution are predicted at the TD-DFT/B3LYP level. The solvent effects are seriously considered using the conductor-like polarizable continuum model(CPCM). For complexes 1—4, in CH₃CN solution, the low-energy absorptions have a mixed LMCT/LLCT character, while the high-energy absorptions are attributed to the ILCT/LLCT.

Letter

Sonication-mediated Film Assembly of Gold Nanoparticles at a Water/Hexane Interface Used as a SERS Substrate

MA Juan, LU Jun-Jun, LU Ling-Hui, HU Jia-Wen*, PAN Jian-Gao, XU Wei-Qing

2009, 30(11):  2288-2290. 

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We reported sonication-mediated film assembly of gold nanoparticles at a water/hexane interface used as a surface-enhanced Raman scattering(SERS) substrate. Gold colloids/hexane biphasic system was emulsified by sonication, and then the emulsions were left undisturbed to allow natural breaking emulsions. In the end, gold nanoparticle films were formed at the interface. The interfacial nanoparticle films can be easily transferred onto a Cu grid and Si wafer for transmission electron microscopy(TEM) and SERS characterizations, respectively. TEM image shows that the as-formed gold nanoparticle films are of a monolayer structure without notable aggregates. SERS measurements indicate that when the gold nanoparticle films were used as SERS substrates to detect 4-MPY, the detection limit can be reached to 1×10^-8 mol/L.

Articles

Synthesis and Controlled Drug Release of Amphiphilic Graft Copolymers PEO-b-PGL-g-PCL

MAO Jing, GAN Zhi-Hua*

2009, 30(11):  2291-2296. 

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Water-soluble diblock copolymers PEO-b-PGL with well controlled composition were synthesized by sequential anionic ring-opening copolymerization of ethylene oxide(EO) and glycidol(GL). ε-Caprolactone(CL) was further initiated by the pendant hydroxyl group of each GL unit in PEO-b-PGL copolymer to synthesize amphiphilic graft copolymers PEO-b-PGL-g-PCL with well defined grafting architecture. The self-assembly behavior of PEO-b-PGL-g-PCL graft copolymers was investigated with pyrene as a probe for the determination of critical micelle concentrations(cmc). Meanwhile, doxorubicin as a model drug was encapsulated into PEO-b-PGL-g-PCL micelles, and its release behavior controlled by diffusion and enzymatic degradation was stu-died. The influences of composition and grafting structure in PEO-b-PGL-g-PCL copolymers on self-assembly, drug loading and release were discussed.

Preparation of Resin Transfer Moldable Phenylethyl-terminated Imide Oligomers

YU Xiao-Hui, ZHAO Xiao-Gang, LIU Chang-Wei, DANG Guo-Dong, WANG Yun-Liang

2009, 30(11):  2297-2300. 

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Two kinds of novel phenylethynyl terminated imide oligomers were prepared with BABB, APBP and PEPA. The melt viscosity stability of the oligomers and thermal stability, mechanical properties of cured resins were studied in this paper. The results show that the oligomers can be used to prepare the high perfor-mance resin-based composite materials via resin transfer molding(RTM) due to their low melt viscosities(about 1 Pa·s) and excellent stability at 200 ℃. The cured resins exhibit excellent thermal stability and mechanical properties.

Control of Large-scale Wettability Using Micro-amounts of Selective Solvents

ZHAO Tian-Yi, ZHANG Yong, LIU Huan, WANG Shu-Tao, ZHANG Zhi-Jie*, JIANG Lei

2009, 30(11):  2301-2305. 

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A simple approach was used to control the large-scale wettability of polymer-coated surfaces merely by adding micro-amounts of selective solvents of different polarity to tri-block copolymer solutions. An amphiphilic tri-block copolymer, poly(ethylene oxide)-poly(dimethylsiloxane)-poly(ethylene oxide)(PEO-PDMS-PEO), was used to form micelles and reverse micelles by adding micro-amounts of a selective solvent to the initial solution. The micellar and reverse micellar film coatings show different wettability from hydrophilic to hydrophobic, and even from superhydrophilic to superhydrophobic when micro-scale roughness is involved. The structures of the micelles and reverse micelles were studied by transmission electron microscopy and ato-mic force microscopy, and the surface chemical composition of the film coatings was determined by X-ray photoelectron spectroscopy(XPS). The results reveal that the main cause of differences in wettability is the diffe-rent surface chemical compositions induced by the different structures of micelles and reverse micelles.

Syntheses and Properties of Directly Crosslinked Sulfonated Poly(arylene ether sulfone)s for Proton Exchange Membrane Fuel Cells

BI Hui-Ping, CHEN Shou-Wen*, WANG Jia-Li, ZHANG Xuan, GAO Zhi-Lin, ZHANG Sha,...

2009, 30(11):  2306-2310. 

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A series of crosslinked sulfonated poly(arylene ether sulfone)s were synthesized from 4,4′-difluorodiphenyl sulfone(DFDPS), 4,4′-biphenol(BP), 3,3′-disulfonate-4,4′-difluorodiphenyl sulfone(SDFDPS) and 1,3,5-trihydroxy benzene(THB) by nucleophilic substitution polycondensation reactions. The trifunctional crosslinker of THB was in the mass fraction range of 3%—7%. The structures of the polymers were confirmed by ¹H NMR and FTIR. The membranes were obtained by solution casting. The properties of the membranes including the ion exchange capacity(IEC), water uptake, diamensional change, mechanic property and proton conductivity were investigated. The results show that the water swelling is decreased after the cross-linking treatment. For the CSPAES membrane of M(6/4-6), with IEC of 2.43 meq/q, it show proton conductivity of 260.5 mS/cm in water at 60 ℃, which is almost twice to that of Nafion 112.

Preparation, Protein Adsorption and Blood Compatibility of Polyelectrolyte Multilayers with Different Surface Properties

PENG Cai-Yu, TONG Wei-Jun, HAN Bao-San, WANG Zhao-Hai, GAO Chang-You*, ......

2009, 30(11):  2311-2318. 

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Poly(styrene sulfonate)/poly(allylamine hydrochloride) multilayers were assembled on silicone wafers via the technique of layer-by-layer assembly. Their surfaces were further modified either physically or chemically with bovine serum albumin(BSA), heparin and polyethylene glycol(PEG). Protein adsorption on these surfaces was investigated by quartz crystal microbalance(QCM), ellipsometry and atomic force microscopy(AFM). The dynamic adsorption process of BSA on these multilayers was monitored by QCM, revealing that the adsorption equilibrium was rapidly achieved within 3 min on the control and heparin adsorbed multilayer surfaces, and within 5—10 min on the chemically bonded BSA and PEG surfaces, but more than 80 min on the BSA physically modified surface. After adsorption of BSA or fibrinogen, all the modified multila-yers became smoother due to the effect of “surface valley adsorption”. Ellipsometry characterization found that the adsorbed mount of BSA, fibrinogen and plasma proteins on all the modified multilayers were smaller than that of the unmodified control multilayers. The platelet adsorption on the multilayers was analyzed by SEM, revealing that the number of the adsorbed platelets on all the modified surfaces except of the heparin modified one was significantly reduced. The prothrombin time(PT) of all the modified multilayers was prolonged compared with that of the unmodified multilayers, but there was no significant difference between all the samples.

Preparation and Characterization of the CS/BSA Composite Micropatterns on Silicon Surfaces

XIE Jia, LU Xiong*, ZHANG Hong-Ping, ZHOU Xian-Li, QU Shu-Xin, FENG Bo, WENG Jie

2009, 30(11):  2319-2325. 

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Chitosan/Bovine serum albumin(CS/BSA) composite micropatterns were successfully fabricated on silicon surfaces by micro-transfer molding method. The micropatterned CS/BSA composite films were stu-died by optical microscopy and fluorescent microscopy. A quantitative test was carried out to characterize the antibacterial properties of the CS/BSA composite films. The results show that the micropatterned CS/BSA composite films are effectively against E. coli and Staphylococcus albus. MC3T3-E cell culture test indicated that micropatterned CS/BSA composite films could strongly direct the orientation of cells. Moreover, the micropatterned CS/BSA composite films could promote the cell adhesion, spreading, proliferation and differen-tiation. Thus, the micropatterned CS/BSA composite film fabricated by micro-transfer molding method has good antibacterial properties and cell compatibility.

Photochromic Properties of Spirooxazine Compound in Acrylic Polyurethane Lacquer Film

WANG Li-Yan, ZHANG Guo*, LIU Xiu-Qi, ZHANG Hai-Quan, XIAO Li-Guang, ......

2009, 30(11):  2326-2330. 

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A UV-curable acrylic polyurethane (UV-PUA) lacquer film containing spirooxazine(SO) compound was prepared. Photochromic properties of the spirooxazine in the lacquer film and polymethyl methacrylate (PMMA) film were studied in details. It was found that the acrylic polyurethane lacquer film containing SO turned to blue, purple from colorless during the UV curing process. After removing UV light source, the film discolored to pink gradually and could change reversibly between pink and purple; while SO-PMMA film could change reversibly between colorless and blue. Ultraviolet irradiation of the UV-SO-PUA film led to double absorption peaks (520 nm and 600 nm) in the visible region of UV-Vis absorption spectra, while ultraviolet irradiation only led to single peak (605 nm) for the SO-PMMA film. The stability of open form of SO in UV-PUA film was better than in SO-PMMA film at room temperature. The fatigue resistance of SO in UV-PUA film was much better than those of it in PMMA film. UV-SO-PUA film didn't appear the fatigue phenomenon after ultraviolet irradiation of 16 h. The SO in UV-PUA film show excellent photochromic properties and this character is not reported.