Table of Content

10 April 2012, Volume 33 Issue 04

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Content

Cover and Content of Chemical Journal of Chinese Universities Vol.33 No.4(2012)

2012, 33(04):  0. 

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Letter

Synthesis of Organically-modified Layered Double Hydroxides by Direct Decarbonation

XU Kong-Li, CHEN Guang-Ming, SHEN Jian-Quan

2012, 33(04):  649-651.  doi:10.3969/j.issn.0251-0790.2012.04.001

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A convenient direct decarbonation method was developed to prepare organically-modified layered double hydroxides using LDH-CO₃ as raw material. The resulting products were characterized by powder X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). The results show that the LDH-DS and LDH-DBS with high crystallinity and high purity are successfully obtained, and their morphology and sizes are unchanged.



Article: Inorganic Chemistry

Preparation and Characterization of Radially Porous Silica and the Core-shell Structure

QI Juan-Juan, XU Dong-Yao, CAI Qiang, ZHANG Wei

2012, 33(04):  652-656.  doi:10.3969/j.issn.0251-0790.2012.04.002

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At room temperature and in water-ethanol-ethyl ether solution with adding amino-modified solid silica, radially porous silica and the core-shell structure were synthesized using hexadecyltrimethylammonium bromide(CTAB) as template, tetraethylorthosilicate(TEOS) as silica source and ammonia solution as catalyst. Scanning electron microscopy(SEM), transmission electron microscopy(TEM), small angle X-ray diffraction technique(XRD), Nitrogen adsorption-desorption isotherms and the corresponding pore size distribution were used to characterize the samples. Results show that spheres with diameters of ca. 0.4-1 μm are obtained, the hierarchical and radial pores with the size from 3 nm to tens of nanometres are on the sample surface, and the BET surface area of the sample is 996 m²/g. The mechanism of radially porous silica and influential factors of core-shell structure were also discussed.



Preface

One-step Synthesis of Iron-functionalized Ordered Mesoporous Materials with High Catalytic Performance in Friedel-Crafts Alkylations

GAO Qian, XIU Yang, LI Guo-Dong, CHEN Jie-Sheng

2012, 33(04):  657-662.  doi:10.3969/j.issn.0251-0790.2012.04.003

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Iron functionalized mesoporous silicon dioxide with various n(Si)/n(Fe) ratios were synthesized via a one-pot synthesis process using soclium docecyl sulfate(SDS) and N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine(N-TPE) as anionic surfactant and co-structure-directing agent, respectively. Various techniques such as XRD, N₂ adsorption, TEM, UV-Vis, XPS and ESR were employed to characterize the products. The presence of iron species with tetrahedral coordination in the well-ordered mesoporous framework was confirmed. The catalytic performance was evaluated through the Friedel-Crafts benzylation of benzene by benzyl chloride. Under the optimized reaction condition, FeMS(40) exhibited superior catalytic performance with 100% yield of diphenylmethane within 2 min at 60 ℃.



Synthesis, Characterization and Relaxation Property of Oligomeric Gadolinium Complex Based on Amide Derivetives of DTPA

HAO Zhi-Feng, WU Ya-Hong, WANG Zhao-Yang, HUANG Zhuo-Liang, YU Jian, YU Lin

2012, 33(04):  663-667.  doi:10.3969/j.issn.0251-0790.2012.04.000

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An oligomeric complex was prepared via assembly reaction of oligomeric diethylenetriamine-N,N′-di(acetyl-p-aniline)-N,N′,N″-triacetic acid [H₃L]_n with GdCl₃ in DMF-H₂O mixed solvent. The composition unit of the complex was confirmed to be [GdL(H₂O)]·4H₂O after characterized by Fourier transform infrared spectroscope(FTIR), elemental analysis, ¹H NMR, thermal gravimetric and differential thermal analysis(TG-DTA), which showed that every unit of the oligomeric ligand was coordinated to one metal ion. The longitudinal relaxivity time T₁ of oligomeric Gd complex and Gd-DTPA(DTPA is diethylene triamine pentaacetic acid ) were tested by inversion recovery. The results indicated that the relaxivity R₁ of the oligomeric Gd complex was 8.526 mmol·L^-1·s^-1, which was greater than small molecular weight complex Gd-DTPA(4.370 mmol·L^-1·s^-1).



Synthesis of Metal Organic Framework MIL-101 with Acetate as Mineralization Agent

GUO Jin-Tao, CHEN Yong, JING Yu, WANG Chong-Qing, MA Zheng-Fei

2012, 33(04):  668-672.  doi:10.3969/j.issn.0251-0790.2012.04.005

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Pure Material Institut Lavoisier-101(MIL-101) sample was directly synthesized without any purification treatment using sodium acetate as mineralization agent. The synthesized samples were characterized by powder X-ray diffraction(XRD), specific surface area, pore size distribution and thermogravimetric(TG) analyses and were compared with the MIL-101 synthesized with hydrofluoric acid as mineralization agent. The results show that sodium acetate is superior to hydrofluoric acid as mineralization agent and the specific surface area and pore volume of the two samples are further improved by purification treatment. The aperture information of MIL-101 samples were calculated accurately via the non-local density functional method(NLDFT). The MIL-101sample synthesized with sodium acetate as mineralization agent is stable above 300 ℃, slightly lower than the MIL-101 sample synthesized with hydrofluoric acid as mineralization agent.



Analytical Chemistry

Simultaneous Determination of Mercury(Ⅱ) and Silver(Ⅰ) Ions in Water by Near-Infrared Spectroscopy with Preconcentration by Thiol-functionalized Polysilsesquioxane Microspheres

NING Yu, CAI Wen-Sheng, SHAO Xue-Guang

2012, 33(04):  673-677.  doi:10.3969/j.issn.0251-0790.2012.04.006

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A method for simultaneous determination of metal ions in water samples was developed using adsorption preconcentration and near-infrared diffuse reflectance spectroscopy(NIRDRS). A high capacity adsorbent of thiol-functionalized polysilsesquioxane microspheres(PMPSQ) was prepared for preconcentration of Hg²⁺ and Ag⁺ in aqueous solutions. After adsorbing the analytes onto the adsorbent, NIRDRS was measured and partial least squares(PLS) models were established for fast and simultaneous quantitative prediction. Because the interaction of the ions with the functional groups of the adsorbent can be revealed from the spectra, the models built with the water samples were proven efficient enough to predict Hg²⁺ and Ag⁺ in a range of 0.16—1.80 mg/L and that of 0.15—1.70 mg/L respectively. The wavenumber changes of C—H group are thought to be the quantitative basis.



Detection of E.coli O157: H7 Using Mannose-functionalized Hydrogels

ZHOU Li-Xia, HE Ding-Geng, HE Xiao-Xiao, QING Zhi-He, WANG Ke-Min, CAO Jie

2012, 33(04):  678-682.  doi:10.3969/j.issn.0251-0790.2012.04.007

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By combining hydrogel with the nucleic acid dye SYBR Green Ⅰ, we have engineered mannose-functionalized hydrogel for E.coli O157: H7 detection based on multivalent binding of Con A. In this method, the hydrogel was first synthesized using acrylamide, N,N-dimethylacrylamide and N-acryloxysuccinimide, employing ammonium persulfate(APS) as the catalyst and etramethylethylenediamine(TEMED) as the accelerator. Then, the mannose was conjugated to the surface of the prepared hydrogel. After preparing the functional hydrogel, the sample was incubated with the hydrogel for 1 h and then stained with a nucleic acid dye SYBR Green Ⅰ. Finally the labeled E.coli O157: H7 was determined by the fluorescence in vivo imaging. The detection of E.coli O157: H7 was successfully carried out in buffer and bacterial mixture, respectively. This assay allowed the detection of E.coli O157: H7 in PB buffer as low as 3.7×10¹ Cells/mL within 2 h.



Fluorescence Quenching Method for the Determination of Carbazochromum with Halide Fluorescein Dyes

GAN Xiao-Juan, LIU Shao-Pu, LIU Zhong-Fang, HU Xiao-Li

2012, 33(04):  683-688.  doi:10.3969/j.issn.0251-0790.2012.04.008

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In pH=6.6 Britton-Robinson(BR) buffer medium, a 1: 2(molar ratio) compound of dichlorofluorescein(DCF), dibromofluorescein(DBF) or diiodofluorescein(DIF) with carbazochromum(CBZC) was formed by electrostatic attraction, aromatic stacking interaction and van der Waals’ force, which led to fluorescence quenching of above halide fluorescein dyes, and the maximum quenching wavelength were located at 533 nm(DCF), 536 nm(DBF) and 560 nm(DIF), respectively. Fluorescence quenching value(ΔF) is proportional to the concentration of CBZC in a certain range. Fluorescence quenching method for the determination of CBZC has high sensitivity, detection limits are 3.3 ng/mL(CBZC-DCF system), 5.7 ng/mL(CBZC-DBF system) and 129.6 ng/mL(CBZC-DIF system), respectively. The effect of coexisting substances, the optimum conditions of the reaction and influencing factors were investigated. The results show this method has good selectivity. This method was successfully applied to the quick determination of CBZC in serum and urine samples. Judging from the effect of temperature, fluorescence lifetime determination and the Stern-Volmer plots, the quenching of fluorescence is a static quenching process.



Preparation of Monodisperse and High-purity Silica Packing Materials

YANG Jun-Jiao, ZHANG Shuo

2012, 33(04):  689-694.  doi:10.3969/j.issn.0251-0790.2012.04.009

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Using silicon powder as silica source, monodisperse and high-purity nano-silica sol was synthesized under catalysis of aqueous ammonia and ammonia gas. The urea-formaldehyde polymer/SiO₂ composite microspheres were prepared after polymerization-induced colloid aggregation(PICA) method in acidic media, and the spherical silica packing material was produced after calcining at high temperature. The purity of monodisperse nano-silica sol was tested by inductively coupled plasma mass spectrometry(ICP-MS), and the size and shape of the composite microspheres were characterized by scanning electron microscope(SEM). The performance of silica packing material was evaluated by non-chromatographic method(BET) and chromatographic method. The results show that the silica packing material has high purity, uniformity and high mechanical strength.



Sensitive Sensor for Mercury Ion in Aqueous Solution by "Naked-eye" and Fluorescence Recognition

WU Xiao-Li, LAI Jin-Ping, ZHAO Yi-Bing

2012, 33(04):  695-699.  doi:10.3969/j.issn.0251-0790.2012.04.010

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A sensitive and selective Nile blue-based optical sensor 1-benzoyl-3-{2-[9-(ethylamino)-10-methyl-9H-benzo[α ]phenoxazin-5-ylamino]ethyl}thiourea hydrochloride(NBET) in aqueous solution for Hg²⁺was synthesized. The maximum absorption peak of the probe molecule appeared at 640 nm, and decreased upon the addition of Hg²⁺ in 0.05 mol/L Tris-HCl buffer solution at pH=7.4, a new peak of absorption at 556 nm was observed. The color of the solution changed from light blue to light purple. There was neglectable change upon the addition of other metal ions. Fluorescence monitoring revealed a fluorescence quenching of the probe’s characteristic emission at 660 nm upon the addition of Hg²⁺. The probe possessed the advantages of near-infrared excitation and emission and high fluorescence quantum yield in aqueous solution and offer an opportunity to detect Hg²⁺ by a "naked-eye" manner. Limit of detection of fluorescence spectral for Hg²⁺ was found to be 0.005 μmol/L in aqueous solution.



Mechanism and Concentration of Phenylpropionic Acids by Ionic Liquid Dispersive Liquid Phase Microextraction

WANG Qian, BU Wei, CHEN Xuan, BAI Xiao-Hong

2012, 33(04):  700-706.  doi:10.3969/j.issn.0251-0790.2012.04.011

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The ionic liquid dispersive liquid phase microextraction(ILDLPME) was developed and its mechanism was investigated; ILDLPME coupled with high performance liquid chromatography(HPLC) was introduced for the determination and evaluation of five kinds of low abundance phenylpropionic acid compounds of Rhizoma typhonii from different origins. The main parameters affecting the performance of ILDLPME were optimized. Under the optimized parameters, the linear ranges were 1.28×10^-3-2.60 μg/mL for caffeic acid, 1.28×10^-4-2.60 μg/mL for p-hydroxycinnamic acid and ferulic acid, 1.28×10^-3-4.00 μg/mL for cinnamic acid and p-methoxycinnamic acid, respectively; the limits of detection were 0.13, 0.01, 0.01, 0.13 and 0.13 ng/mL, respectively; the intra and inter RSD were less than 9.7%, the mean recoveries of analytes in traditional Chinese medicines were between 86.9% and 112.6%, the enrichment factors were in the range of 56.0-159.3 for ILDLPME. By analysis and comparison the UV spectra of phenylpropionic acids before and after ILDLPME, the extraction mechanism of the charge transfer superamolecule of carboxyl-ionic liquid(CTSMCIL) was proposed. CTSMCIL-HPLC provide dependably theoretic foundation and experimental evidence for establishing quality control method in Rhizoma typhonii.



Preparation, Characterization and Evaluation of Magnolol-bonded Silica Gel Stationary Phase for Reversed-phase Liquid Chromatography

LI Lai-Sheng, CHEN Hong, MA Hai-Ping, FANG Yi-Shan

2012, 33(04):  707-713.  doi:10.3969/j.issn.0251-0790.2012.04.012

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Cortex magnoliae officianalis is a Chinese herbal medicine, which has anti-bacterial function. Magnolol is the main pharmacological component. A new magnolol-bonded silica gel stationary phase(MSP) for reversed-phase liquid chromatography was prepared using 3-mercaptopropyl trimethoxysilane(KH-590) as the coupling reagent. The chemical structure of MSP was characterized by Fourier transform infrared spectroscopy(FTIR), elemental analysis(ES) and thermogravimetric analysis(TGA). With the purpose of evaluating the chromatographic performance and elucidating the related retention mechanism on the new packing material, some alkylbenzene homologues, five pyridines, six aniline compounds and eight aromatic carboxylic acids were used as neutral, basic and acidic probes, respectively. The results showed that MSP could be considered as a reversed-phase liquid chromatographic stationary phase, which was similar to ODS column. The principle of the chromatographic separation for most analytes on MSP column involved hydrophobic interaction. Moreover, MSP is a packing material that has versatile chromatographic functions. The chromatographic results indicated that hydrophobic interaction, hydrogen bonding interaction, π-π interaction and dipole-dipole interaction between the bonded phase and analytes play significant roles in the retention of some basic compounds and aromatic carboxylic acids, and better selectivity and separation have been presented on MSP column. Various action sites of mognolol could contribute to the fast separations of many polar aromatic compounds.



Transmembrane Delivery of Rich Arginine Peptide Modified Gold Nanoparticles

SHAN Hong-Yan, YU Bo, SUN Lin-Lin, WANG Zhen-Xin

2012, 33(04):  714-717.  doi:10.3969/j.issn.0251-0790.2012.04.013

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The transmembrane behavior of rich arginine(R) peptide modified gold nanoparticles was studied. The functionalization of the gold nanoparticles was achieved by the conjugation of transmembrane peptide RRRRRRRR(R₈) with peptide CALNN stabilized gold nanoparticle through the standard streptavidin-biotin chemistry. The transmembrane delivery of the model compound, fluorescein, was studied by confocal scanning laser microscope. The result suggests that the R₈ modified gold nanoparticles can be used as an excellent vector for transporting extracellular materials into cells with low cellular cytotoxicity.



Influence of the Combustion Interface Using Auxiliary Gas on the Carbon Isotope Analysis of Organic Compounds

JIA Wang-Lu, LIU Jin-Zhong, PENG Ping-An

2012, 33(04):  718-724.  doi:10.3969/j.issn.0251-0790.2012.04.014

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Combustion reactor is considered to be one of the critical factors in detecting sensitivity and resolution of organic compounds for carbon isotope analysis, yet the reasons are not well understood. This study focused on combustion reactors using additional auxiliary gas, one of the two most commonly used reactors applied in commercial instruments. Various alkanes and aromatic compounds were subjected to carbon isotope analysis with several types of combustion reactor to illustrate in detail the effects of the reactor on the chromatography of organic compounds. Relatively small quantities of catalyst packed into the reactor, which result in a high linear velocity of carrier gas and an eliminated diffusional broadening of the analytes in the reactor, could improve the peak resolutions of various compounds. However, the improvements could be gained on the peak resolutions, by various types of reactors, are limited. In comparison, the sensitivities for organic compounds might vary greatly with a number of factors, which is mainly attributed to the changes in split ratio at the open split that is closely related with the total flow rate of carrier gas in the reactor.



Organic Chemistry

Synthesis and Properties of a Dicarbazolyl Tetraphenylethylene Multi-functional Luminophor

CHI Zhen-Guo, HE Ke-Qiang, LI Hai-Yin, ZHANG Xi-Qi, XU Bing-Jia, LIU Si-Wei, ZHANG Yi, XU Jia-Rui

2012, 33(04):  725-731.  doi:10.3969/j.issn.0251-0790.2012.04.015

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The development of organic fluorescent materials was of great interest for both fundamental research and practical applications. Piezofluorochromic or piezochromic fluorescent material was a "smart" material of which fluorescent properties were changed in response to external pressure stimuli. However, piezofluorochromic materials depended on the change of physical molecular packing modes were remaining extremely rare. In this work, a new discarbazolyl tetraphenylethylene compound was synthesized. The chemical structures of the derivative was determined by ¹H NMR, MS and elemental analyses, and its properties were investigated by PL, TGA, DSC and CV methods. The results show that the compound possess piezofluorochromic properties as well as aggregation-induced emission enhancement effect. The PL intensity and quantum yield in DMF/H₂O with high water fraction were about 171, 100 times higher than those in pure DMF, respectively. The piezofluorochromic nature was generated through phase transformation from crystalline state(450 nm) to amorphous state(480 nm) under the external stimuli. The organic light emitting diode(OLED) device fabricated with the compound as non-doped emitters exhibited good performances with a maximum brightness of 2438 cd/m², a maximum current efficiency of 2.87 cd/A, and a maximum power efficiency of 1.81 lm/W. It is indicated that the compound is a multi-functional luminophor.



Synthesis and Characterization of Curcumin Bridged Porphyrins as Photosensitizers

HUANG Qi-Mao, WANG Si-Wei, LI Qing, PAN Wei, DENG Peng-Xing, ZHOU Hong, PAN Zhi-Quan

2012, 33(04):  732-737.  doi:10.3969/j.issn.0251-0790.2012.04.016

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Photodynamic therapy(PDT) is a promising modality with minimally invasive approach to the clinical treatment of oncology generally based on the activation of photosensitizers, as they can utilize the administration and selective accumulation in cancer tissues to form cytotoxic reactive oxygen species such as singlet oxygen when followed by exposure to suitable visible light, causing tissue injury and cell death. To improve this treatment, new efficient photosensitizers were synthesized and tested for their important role in PDT. Porphyrins have considerable attractive properties in biological systems derived from unique characteristic π-system and coordinating metals, which can be used for a broad range of applications, and modification of porphyrins to tune or change the properties has been investigated extensively. To develop new porphyrin photosensitizers of PDT, four novel porphyrin compounds containing structural unit of natural product curcumin were synthesized using 2-(2-hydroxy-naphthyl)-5,10,15,20-tetraphenyl porphyrin and its Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) complexes as starting materials. In these compounds, porphyrin and small molecule curcumin with anticancer activity were bridged by 1,6-dibromo-hexane. These compounds were characterized by UV, ¹H NMR, IR, MS, and elemental analysis. Based on the confirmation, their cleavage abilities to pBR322 plasmid DNA were investigated by gel electrophoresis under photo irradiation and in dark, respectively. The results show that the novel porphyrin compounds as potential photosensitizers have both obvious photosensitive cleavage activity and effective binding interaction with DNA.



Design, Synthesis and Biological Activities of New Ryanodine Receptor Pesticides Based on Ugi Reaction

LIU Peng-Fei, ZHOU Sha, XIONG Li-Xia, YU Shu-Jing, ZHANG Xiao, LI Zheng-Ming

2012, 33(04):  738-743.  doi:10.3969/j.issn.0251-0790.2012.04.017

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Chlorantraniliprole, invented by DuPont company in 2001, is a new type of insecticide with high efficiency, low toxicity, broad-spectrum insecticidal activity which act at Ryanodine receptor of target insects. Both flubendiamide and chlorantraniliprole contain two amide groups in different locations of the structure, and this could be of great significance in insecticidal activity. Referring to their structural composition, a series of novel α-phenyl-α-amide-amide compounds was designed and synthesized. We changed chlorantraniliprole’s β-amino-acid-amide to the α-phenyl-α-amide-amide. The Ugi reaction was carried on to uphold diversity in the molecular. A series of compounds was obtained and bio-assayed and their structure-activity relationship was discussed. Also, their structures were characterized by ¹H NMR, elemental analysis and HRMS. The preliminary results of biological activity experiment show that the compounds at 200 mg/L exhibit some insecticidal activity against Mythimna separate(7h); the compounds also exhibit some fungicidal activity against Physalospora piricola(7q) and Alternaria solani(7e).



Synthesis and α-Glucosidase Inhibitory Activity of Oleanolic Acid Derivatives

SONG Zhi-Cheng, WANG Shi-Sheng, SONG Qi-Ling, SHU Tao, ZHAO Wei-Jie

2012, 33(04):  744-749.  doi:10.3969/j.issn.0251-0790.2012.04.018

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The natural pentacyclic triterpene compound, oleanolic acid, has a series of biological activities, such as antitumor, anti-HIV, hypoglycemic and liver protective activities, but its relatively weak activities and low bioavailability limit its clinical applications. In order to investigate the hypoglycemic activity of oleanolic acid derivatives, sixteen derivatives were synthesized by modification of oleanolic acid at C2, C3 and C28 positions via oxidation, esterification, cyclization, Mannich reaction and so on. Their structures were determined by physicochemical properties, MS and NMR data. Their in vitro inhibitory activities against α-glucosidase were tested. The results show that all the tested compounds exhibit α-glucosidase inhibitory activities in various degrees at the concentration of 200 μg/mL. Among them, 3-oxo and 28-ester derivatives(2, 5—7) show lower inhibitory activity than oleanolic acid. The preliminary analysis of structure-activity relationship revealed that the free carboxyl group at C28 was indispensable and hydroxyl or other hydrogen-bond donor groups at C3 contributed to increase inhibitory activity.



Synthesis of A-Ring Functional Derivatives of 18β-Glycyrrhetinic Acid and Their Antiproliferative Effect in Tumor Cells

GAO Zhen-Bei, HU Jun, KANG Xiao, XU Chuan-Lian, JU Yong

2012, 33(04):  750-754.  doi:10.3969/j.issn.0251-0790.2012.04.019

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Thirteen analogues of 18β-glycyrrhetinic acid were synthesized using various chemical methods and one of them exhibited certain cytotoxicity against cell-lines of HL60 cells, K562 cells, BEL-7404 cells and MDA-MB-231, respectively, via MTT method. The results show that compound 5 with C＝C bond in the A-ring of 18β-glycyrrhetinic acid has markedly antiproliferative effect on these four tumor cells compared with 18β-glycyrrhetinic acid. K562 cells with nuclear apoptotic bodies were observed after staining with Hoechst 33258 and AO/EB with flourescence microscope.



Isolation and Structural Characterization of a New Neutral Polysaccharide from Chrysanthemum indicum L.

JIN Hong-Ying, SHI Song-Shan, WANG Shun-Chun, WANG Zheng-Tao, HU Zhi-Bi

2012, 33(04):  755-760.  doi:10.3969/j.issn.0251-0790.2012.04.020

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Chrysanthemum indicum L. was used as a heat-clearing and detoxication herb in traditional Chinese medicine. The studies indicated that the polysaccharide played a critical role in its medical effects, but there was no report about the details of the structural features of the homogenous polysacchatide from Chrysanthemum indicum L. In order to identify the structural features for the quality control, systematical studies of Chrysanthemum indicum L. were performed. A water soluble neutral polysaccharide(CIP-C) was obtained from Chrysanthemum indicum L. by hot water extraction, precipitation with ethanol, separation and purification through DEAE-Sepharose Fast Flow ion exchange chromatography and Sephacryl S-200 gel permeation chromatograph. By means of GC-MS, NMR, partially acid hydrolysis and methylation reaction, the structure of CIP-C was identified. The results show that CIP-C is a heteropolysaccharide, which is mainly composed of D-Man, D-Glc and D-Gal, with a small quantity of D-Fuc, L-Ara and D-Xyl. The backbone of CIP-C is linked by β(or α)-D-1,4-Man, β-D-1,6-Glc and β-D-1,4-Gal. In addition, T-Araf, 1,5-Araf and T-Gal, 1,4-Gal, 1,3,6-Gal, 1,3,4,6-Gal may be linked as an arabinan branch and an AGI arabinogalactan branch. In this paper, CIP-C was firstly reported as a new neutral branched polysaccharide from Chrysanthemum indicum L.



Synthesis and Properties of Novel Photochromic Bispirooxazine

PANG Mei-Li, LOU Zhi-Gang, PANG Cheng-Cai, YANG Tao-Tao, MENG Ji-Ben

2012, 33(04):  761-767.  doi:10.3969/j.issn.0251-0790.2012.04.021

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At present, the photochromic compounds in terms of molecular switches have attracted much attention of many researchers. As an important class of molecular switch system, spirooxazines have gradually aroused widespread concern. The common single spirooxazines have defects such as lack of coordination position, weak affinity between the molecules, poor molecule recognition selectivity, and low sensitivity. On the contrary, bispirooxazines have the advantages of more coordination position, stronger affinity between the molecules, higher molecule recognition selectivity, and higher sensitivity. In this paper, a series of bispirooxazines was designed, synthesized and characterized by ¹H NMR, ¹³C NMR, IR as well as HRMS. The photochromic properties of compounds 5a—5c in different solutions(trichloromethane, dichloromathane and cyclohexane) and polymer films(PMMA and PVB) were studied with the aid of UV absorption spectrometry. The thermal decay process of the compounds 5a—5c in different polymer films were recorded and analyzed and the kinetic process were fitted and discussed. The results show that these compounds have good photochromic properties and favorable fatigue resistance. These properties are helpful for their potential use in material, molecular switch and biological probe area.



Physical Chemistry

Surface Photovoltage Properties of Deep Level in ZnO/Cu₂O Heterojunction Films

WANG Rong, SHI Zhan-Hua, CAI Fang-Gong, YANG Feng, JIA Yong-Fang, LI Ying, CHENG Cui-Hua, ZHAO Yong

2012, 33(04):  768-771.  doi:10.3969/j.issn.0251-0790.2012.04.022

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ZnO/Cu₂O heterojunction films with triangular pyramid surface morphology were electrodeposited potentiostatically on the FTO. The morphology and crystalline phase of obtained films were characterized by field emission scanning electron microscopy(FESEM) and X-ray diffraction(XRD). The surface photovoltage properties of Cu₂O and ZnO/Cu₂O heterojunction films were investigated through surface photovoltage spectrum(SPS), field-induced surface photovoltage spectrum(FISPS) and phase spectrum(PS). The results show that compared to Cu₂O films, the surface photovoltage response of the ZnO/Cu₂O heterojunction films are extended to 600—800 nm. According to the principle of SPS, FISPS and PS, the extended photovoltage response is ascribed to the transition of deep level in Cu₂O which is enhanced by the interfacial electric field between ZnO and Cu₂O in the direction from ZnO to Cu₂O. The photoinduced electron-hole pair germinates from deep level transition of Cu₂O in ZnO/Cu₂O heterojunction films can disassociate and transmit efficiently by the aid of this strong interfacial electric field.



Resonance Raman Spectroscopic and Density Functional Theory Investigations of Excited State Structural Dynamics of 2-Acetyl-1-methylpyrrole(2-Ac-NMP) and Its Solvent Effect

XU Zong-Ping, ZHAO Yan-Ying, WANG Hui-Gang, ZHENG Xu-Ming

2012, 33(04):  772-780.  doi:10.3969/j.issn.0251-0790.2012.04.023

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Resonance Raman spectra of 2-acetyl-1-methylpyrrole(2-Ac-NMP) were obtained with seven excitations covering the A- and B-band absorptions of the UV spectra. The electronic excitations and the Franck-Condon region structural dynamics of 2-Ac-NMP were studied with the resonance Raman spectroscopy and density functional theory calculations. The A- and B-band absorptions are assigned as the π→π^* transitions on the basis of the TD-B3LYP/6-311++G(d,p) level of theory computations. The resonance Raman spectra displayed the Raman intensity in the fundamentals, overtones and combination bands of about 13 vibrational modes(for A-band) or 8 vibrational modes(for B-band), predominately in the C＝O stretch mode(ν₈), C3-C4-C5 anti-sym.stretch+C2-C6 stretch(ν₁₄) and ring CH in-plane bend(ν₁₈). This indicates that the Franck-Condon region S_π structural dynamics of 2-Ac-NMP is mainly along the C＝O stretch and ring defor-mation and ring CH in-plane bend coordinates. In a certain solvent and under different excitation wavelengths, the relative intensity of the ν₈ versus the ν₁₄ displays an interesting change that is from intense to weak and then to intense again as the excitation wavelengths goes from longer to shorter. This intensity variation directly reflects the S_n/S_π state-mixing or curve-crossing in Franck-Condon region. Solvents can efficiently tune the Franck-Condon region S_n/S_π state-mixing or curve-crossing processes.



Synergistic Catalysis of Fe₂O₃ and TiF₃ Additives on the LiBH₄-MgH₂ Composite

ZHANG Hui, ZHOU Yi-Xi, SUN Li-Xian, CAO Zhong, XU Fen, LIU Shu-Sheng, ZHANG Jian, SONG Li-Fang, SI Xiao-Liang, JIAO Cheng-Li, WANG Shuang, LI Zhi-Bao, LIU Shuang, LI Fen

2012, 33(04):  781-785.  doi:10.3969/j.issn.0251-0790.2012.04.024

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Five systems(2LiBH₄-MgH₂, 2LiBH₄-MgH₂-10%Fe₂O₃, 2LiBH₄-MgH₂-10%TiF₃, 2LiBH₄-MgH₂-5%Fe₂O₃-5%TiF₃ and 2LiBH₄-MgH₂-10%Fe₂O₃-10%TiF₃) were prepared by ball milling. They were investigated through thermogravimeteric analysis(TG), diffraction scanning calorimetric(DSC), powder X-ray diffraction(XRD), Fourier transformed infrared spectrometer(FTIR) and pressure-content-temperature(PCT). The addition of Fe₂O₃ and TiF₃ improved the hydrogen release property of the LiBH₄-MgH₂ complex system effectively. Especially, the codoped system(2LiBH₄-MgH₂-10%Fe₂O₃-10%TiF₃) starts to release hydrogen at around 110 ℃ and can release as much as 9.6%. Besides, the results of PCT show that the codoped system(2LiBH₄-MgH₂-5%Fe₂O₃-5%TiF₃) can release about 8.6% hydrogen within 10 min at 400 ℃. The properties of the codoped system are better than the other two single doped systems, which partly incarnated the synergistic catalysis of Fe₂O₃ and TiF₃.



Preparation and Properties of Electrolyte Li[CF₃BF₃] as a Novel Conductive Salt

HAN Hong-Bo, GUO Jun, FENG Shao-Wei, NIE Jin, ZHOU Zhi-Bin

2012, 33(04):  786-793.  doi:10.3969/j.issn.0251-0790.2012.04.025

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A novel lithium salt, Li[CF₃BF₃], was prepared and structure-elucidated by ¹H NMR and elemental analysis. The impurities contents in Li[CF₃BF₃] were determined by ion chromatography. The physicochemical and electrochemical properties of 1 mol/L Li[CF₃BF₃] in ethylene carbonate/ethyl methyl car-bonate/dimethyl carbonate(EC/EMC/DMC)(volume ratio 5: 3: 2) were extensively investigated by differential scanning calorimetry(DSC), electrochemical impedance spectroscopy(EIS), cyclic voltammogram(CV) and scanning electron microscope(SEM). The results indicate that the Li[CF₃BF₃]-containing electrolyte is much more conductive than that of LiBF₄ and show an anodic stability up to 5.91 V(vs. Li⁺/Li) and highly reversible deposition-dissolution process on the Ni electrode, and is passivated effectively toward the Al anodic collector. The correlations between conductivities and temperatures or Li[CF₃BF₃] concentrations and between viscosities of the electrolytes and Li[CF₃BF₃] concentrations were also studied, respectively. Moreover, charge/discharge test of Li/graphite half-cells suggests that the Li[CF₃BF₃] based electrolyte was compatible well with graphite electrode.



Theoretical Studies on Charge Transfer Properties of Carbazole Derivative DiPICz

SUN Guang-Yan, LI Hai-Bin, GENG Yun, DUAN Yu-Ai, TANG Xiao-Dan, SU Zhong-Min, ZHOU Zi-Yan

2012, 33(04):  794-799.  doi:10.3969/j.issn.0251-0790.2012.04.026

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Organic π-conjugated semiconductor materials have been extensively used in organic light-emitting diodes(OLEDs). Among them, carbazole derivatives are commonly used as hole-transporting materials. Here, the electronic structure and transport properties of Dibenzo[2,3:5,6]pyrrolizino[1,7-bc]indolo-[1,2,3-lm]carbazole(DiPICz) were investigated systematically by means of semiclassical Marcus charge transfer theory at the density functional theory level. The results indicate that the mobility of electron is 5.81 × 10^-2 cm²·V^-1·s^-1, which is two orders of magnitude higher than that of hole(6.02×10^-4 cm²·V^-1·s^-1), indicative of abnormal electron-transporting materials. We further proved that both the small electron internal reorganization energies and the character of higher-order molecular packing in its single crystals were crucial to good electron transport properties. In the ‘herringbone’ packing of DiPICz crystal, the presence of typical slipped face-to-face packing and the formation of weak hydrogen bonds such as C-H…N and C-H…π interactions cause two dimensional electron transport networks, which play an important role in electron transport.



Molecular Simulations of Adsorption and Separation of H₂S and N₂ Mixture by Single Wall Carbon Nanotubes

QIAO Zhi-Wei, REN Shu-Hua, ZHOU Jian

2012, 33(04):  800-805.  doi:10.3969/j.issn.0251-0790.2012.04.027

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Adsorption and separation of 1: 99(volume ratio) H₂S/N₂ mixture by single wall carbon nanotubes were studied using the grand canonical Monte Carlo(GCMC) method at a range of nanotube diameters, pressures and temperatures. It is demonstrated that the selectivity towards H₂S increases and then decreases with increasing nanotube diameter and the selectivity is highest for (11,0) carbon nanotube which is due to the synergy of geometry effect and energy effect. It is shown that under different operation conditions, the adsorption isotherm and selectivity can vary significantly. At 100 kPa, the amount of adsorbed of H₂S in (11,0) carbon nanotube and the selectivity towards H₂S firstly increase and then decrease with increasing temperatures. Moreover, at 300 K, with increasing pressures, the adsorbed amount of H₂S and the selectivity towards H₂S decrease. The simulation findings in this work would be helpful for the design and development of sulfur removal processes.



Self-assembly of Phthalocyanine-carbon Nanotubes Dispersed in Micelle and Light Induced Long-lived Charge Separation State

SHAO Xiao-Na, ZHANG Xian-Fu

2012, 33(04):  806-812.  doi:10.3969/j.issn.0251-0790.2012.04.028

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To mimic the primary process in photosynthesis, tetrasulfonated zinc phthalocyanine(ZnPcS₄) and single-walled carbon nanotubes(SWCNT) were assembled to noncovalent electron donor-acceptor(D-A) complex assisted by sodium dodecyl sulfate(SDS) micelle, which disaggregate both SWCNTs and phthalocyanines in aqueous solution. The D-A complex is featured by the new absorption at 707 nm and completely non fluorescence, due to the efficient intra-molecular photo induced electron transfer revealed by both steady state and time resolved fluorescence spectra. The charge separation state(CSS) was observed by laser flash photolysis and showed a long lifetime of 42 μs observable by kinetic analysis. The long-lived CSS is due to the triplet electron transfer which is made possible by the low oxidation potential of the phthalocyanine(good donor) and the low reduction potential of SWCNT(good acceptor). The result shows that SWCNT may be applied in artificial photosynthesis.



Polymer Chemistry

Effect of Hydrogen Bonding on Water States in Sorbitol Modified PVA System

WANG Xi, LI Li, CHEN Ning, WANG Qi

2012, 33(04):  813-817.  doi:10.3969/j.issn.0251-0790.2012.04.029

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Two-dimensional correlation ATR-FTIR spectroscopy was used to study the hydrogen bonding and the water states during the diffusing process of water into poly(vinylalcohol)(PVA) matrix. The effect of sorbitol on water states was also studied by DSC analysis. The results show that the addition of sorbitol into PVA changes the hydrogen bonds in system and apparently influences the water states and water evaporation behavior by forming strong hydrogen bonding with water. Consequently, the free water in system gradually reduces and the water evaporation temperature shifts to higher values, which is beneficial to the stable thermal processing of modified PVA.



Large Amplitude Oscillatory Shear Rheology of Laponite Gels

YANG Yan-Rui, SUN Wei-Xiang, HUANG Li-Zhen, SHU Rui-Wen, TONG Zhen

2012, 33(04):  818-822.  doi:10.3969/j.issn.0251-0790.2012.04.030

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Effect of salt concentration on the rheology behavior of Laponite suspension was investigated with large amplitude oscillatory shear(LAOS) rheology. Nonlinear viscoelasticity of Laponite suspensions was demonstrated by the related amplitude I_3/1, the minimum-strain modulus(G_M), large-strain modulus(G_L), minimum-strain rate viscosity(η_M), and large-strain rate viscosity(η_L). I_3/1 increased gradually with γ₀ for the samples with low NaCl concentration. As the concentration of NaCl increased, I_3/1 increased abruptly with γ₀ and reached a plateau value. The relationship of G_M and G_L parameters with γ₀ showed no difference among samples with different NaCl concentrations. The η_M and η_L parameters exhibited a large peak in the relationship with γ₀, which differed significantly among samples with different NaCl concentrations. The higher the NaCl concentration was, the higher the peak value was. These results suggested that the nonlinear viscoelasticity of Laponite gels depended on their network structure. By increasing NaCl concentration, the electrostatic interaction between Laponite particles was screened and the distance between Laponite particles was reduced, leading to a more condensed gel network. This network was easily broken under LAOS, showing obvious nonlinear viscoelasticity.



Synthesis and Properties of Fluorine-Containing Electron Beam Curing Polyurethane Acrylate

XU Hai-Tao, LI Jing, LIANG Hong-Bo, XIONG Lei, GAO Ge

2012, 33(04):  823-827.  doi:10.3969/j.issn.0251-0790.2012.04.031

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The fluorine-containing electron beam curing polyurethane acrylate was prepared by hexamethy-lene diisocyanate triplolymer, hydroxyethyl acrylate and hydroxyl fluorine-containing acrylate. The expected products were proved by FTIR and ¹H NMR. The rheological properties of the two-phase mixed system of the product and solvent, electron beam curing behavior and the properties of the cured coating were studied. The results show that the thixotropy of the mixed system has positive thixotropy, the absolute viscosity follows Sedden formula, and the viscous flow activation energy is about 44.8 kJ/mol. Electron beam cured coating has fine thermal stability, hardness, adhesion and glossiness.



Planar Donor-acceptor Copolymers for Bulk Heterojunction Solar Cells

QIN Rui-Ping, SONG Gui-Lin, JIANG Yu-Rong, BO Zhi-Shan

2012, 33(04):  828-832.  doi:10.3969/j.issn.0251-0790.2012.04.032

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Two planar conjugated copolymers poly2,8-{5,11-diisooctylindolo[3,2-b]carbazole}-4,7-di[2,5-thiophene]-5,6-dioctyloxy-2,1,3-benzothiadiazole(QP-2) and poly2,8-{5,11-dioctylindolocarbazole}-4,7-di[2,5-thiophene]-5,6-dioctyloxy-2,1,3-benzothiadiazole(QP-3) with main chain donor-acceptor alternating structures were synthesized and their photophysical and photovoltaic properties were investigated. Photovoltaic cells based on polymer QP-3 gave a power conversion efficiency(PCE) of 2.59%, an open circuit voltage(V_OC) of 0.72 V, a short circuit current density(J_SC) of 9.24 mA/cm², and a fill factor(FF) of 0.38. The results show that the polymer without branched alkyl side group performs better and they have better crystallinity in solid film.



Chemical Structure and Performance of a Novel Polyimide-urethane Composite Reverse Osmosis Membrane Material

LIU Li-Fen, MAO Pei-Qing, XU De-Zhi, ZHANG Lin, GAO Cong-Jie

2012, 33(04):  833-837.  doi:10.3969/j.issn.0251-0790.2012.04.033

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The common aromatic polyamide composite reverse osmosis(RO) membrane is easy to be oxidated. Chlorine resistance polyimide-urethane RO membrane material by interfacial polymerization technology was prepared with N,N′-dimethyl-m-phenylenediamine(DMMPD) as a key functional monomer which reacted with 5-choroformyloxyisophthaloyl chloride(CFIC). The surface chemical structures of membrane active layer were analyzed by combination of attenuated total reflectance infrared(ATR-IR) and X-ray photoelectronic spectroscopy(XPS), and the chlorine resistance performance of membrane was also measured. Furthermore, the relationship between chemical structure of membrane active layer and chlorine-resistant performance was analyzed.



Molecular Recognition Mechanism of Chiral (S)-Ibuprofen’s Hydrogen Bonds Self-assembly Imprinted Polymer

SUN Yan, WANG Bing

2012, 33(04):  838-842.  doi:10.3969/j.issn.0251-0790.2012.04.034

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A series of imprinted polymer was synthesized using chiral (S)-ibuprofen with a single polarity group as the template molecular. The calculated results of UV indicated the complex ratio of host-guest was 1: 1. IR analysis result revealed in the pre-assembly process and re-adsorption process, the blue-shifted hydrogen bonds and red-shift hydrogen bonds were formed between template molecule and functional monomer, respectively. The isotherm results indicated that the specificity binding capacity was 37.92 μmol/g, and the imprinted factor of the polymer was 3.06. The chiral separation experiment indicated that compared with (R)-ibuprofen, (S)-ibuprofen template polymer exhibited significant adsorption selectivity for (S)-ibuprofen. Also, the separation factor was 1.79.



Preparation of Chitosan Lactate Sponges with Uniform Vertical Pores and Fitted Analysis of Release Medicine Model in vitro

YU Fei, XI Ting-Fei, ZHANG Shu-Jiang, ZHANG Zhi-Xiong, LAI Chen

2012, 33(04):  843-849.  doi:10.3969/j.issn.0251-0790.2012.04.035

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Chitosan lactate(LCH) was obtained by reacting with lactic acid based on chitosan(CH). The products were found to be superior to original chitosan as far as water solubility was concerned. With the structure-directing agent tertiary butyl alcohol(TBA) in the vertical temperature controlled device, uniform and vertical pores structure in sponges were obtained upon freeze-drying. Different diameter form sponge samples were made by controlling the concentration of TBA. Then, drug delivering model of sponges samples with degradation and dissolution function was studied with erythromycin as model drug in vitro. The results demonstrate that drug delivering process of sponge samples is divided into two stages: matrix dissolution controlled-release stage and drug after-diffusion stage. Matrix dissolution controlled-release stage is very good to fit the couarraze drug delivering model.



Effect of γ-Ray Irradiation on Chain Structure and Crystallization Behavior of Isotactic Polypropylene

ZHOU Li-Juan, ZHANG Xiu-Qin, LI Rong-Bo, SU Yun-Lan, ZHAO Ying, XU Duan-Fu

2012, 33(04):  850-855.  doi:10.3969/j.issn.0251-0790.2012.04.036

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The structure and crystallization behavior of isotactic polypropylene(iPP) irradiated by γ-ray, were investigated by a combination of gel permeation chromatography(GPC), Fourier transform infrared spectroscopy(FTIR) and differential scanning calorimetry(DSC). The results indicated that γ-ray irradiation led to the formation of hydroxyl and carbonyl groups on iPP main chains as well as the degradation of iPP macromolecules. As the irradiation dose was lower than 50 kGy, the crystallization temperature(T_c) of irradiated iPP increased slightly with the increase of irradiation dose. However, the T_c of irradiated iPP decreased obviously, when the irradiation dose is above 50 kGy, and the melting peak of iPP moved to lower temperature and split into two peaks. The overall isothermal crystallization kinetics of unirradiated and irradiated iPP were analyzed by the Avrami equation. The values of Avrami exponent n are close to 3, indicating that iPP nucleates in the heterogeneous manner regardless of the crystallization temperature and the irradiation dose. The DSC data indicated that the overall crystallization rates decrease with the increase of crystallization temperature and radiation dose. The relationship between chain structure change and crystallization rate was discussed.



Morphology Analysis of POSS and the Influence on Compatibility and Mechanical Properties of the Hybrid Materials

BAI Xue-Tao, SUN Guo-En, GUAN Dong-Bo, MU Jian-Xin, LIU Bo, JIANG Chun-Mei, ZHANG Chun-Ling

2012, 33(04):  856-860.  doi:10.3969/j.issn.0251-0790.2012.04.037

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Octavinyl-polyhedral oligosilsesquioxanes(OVPOSS) was synthesized via hydrolysis and condensation reaction. The organic-inorganic hybrid materials were produced with OVPOSS and polymethylmethacrylate(PMMA) self-curing resins. The hybrid materials were characterized with FTIR, XRD, TEM, SEM, DSC, plastic ball indentation hardness tester, high-temperature friction, wear tester and memory-type cantilever beam impact testing machine. Particularly, morphology and compatibility properties of hybrid materials and OVPOSS particles were discussed. The results indicated that the size of OVPOSS crystal structure began to reduce with the addition particles in the hybrid materials. The compatibility properties show that phase separation occurs in the hybrid systems with higher content of POSS.