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Interfacial behaviors of PMMA-PEO block copolymers at the air/water interface

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Science china chemistry 2005年第6期48卷 567-573页

作者： CHENG Caixia1, JIAO Tifeng2. TANG Rupei1, LIU Minghua2.& XI Fu1 1. State Key Laboratory of Polymer Physics and chemistry, Joint Laboratory of Polymer Science and Materials, {3. of chemistry, Chinese academy of sciences, Beijing 100080, china 2. CAS Key Laboratory of Colloid and Interface Science, {3. of chemistry, Chinese academy of sciences, Beijing 100080, china State Key Laboratory of Polymer Physics and chemistry Joint Laboratory of Polymer Science and Materials Institute of Chemistry Chinese Academy of Sciences Beijing China CAS Key Laboratory of Colloid and Interface Science Institute of Chemistry Chinese Academy of Sciences Beijing China

Diblock copolymer of PMMA2.1-b-PEO114 and triblock copolymer of PMMA12.-b- PEO2.7-b-PMMA12. were synthesized and their interfacial properties at the air-water interface were investigated, where both blocks of polyethylene oxide (PEO) and poly(methyl methacrylate) (PMMA) are surface active but the former is soluble in water while the latter is not. Both the block copolymers could form monolayers with two obvious transition regions. The first transition point is around 10 mN/m, which could be assigned to the pancake-brush change of the PEO chains. The other is around 18 mN/m, which could be ascribed to the condensed packing of PMMA. The surface morphological changes during the compression of the Langmuir monolayers are inves-tigated by using the AFM and SEM methods for the films deposited at different surface pressure or molecular areas. At a lower surface pressure, a typical morphology of PEO-con- taining lipopolymers is observed. Upon compression, sphere-dominant morphologies were observed. While the diblock copolymer is easy to folding, the triblock copolymer is in favor of formation of circular domains through vesiculation.

关键词： PMMA-PEO, block copolymers, monolayer, Langmuir-Blodgett films, AFM.

Mass Spectrometric Evidence of Heparin Disaccharides for the Catalytic Characterization of A Novel Endolytic Heparinase

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Acta Biochimica et Biophysica Sinica 2004年第12期36卷 840-844页

作者： Yapeng CHAO1,3. Shaoxiang XIONG2. Xiulan CHENG1, and Shijun QIAN1* 1institute of Microbiology, Chinese academy of {2., Beijing 100080, china 2.enter of Mass Spectrometry, institute of chemistry, Chinese academy of {2., Beijing 100080, china 3.raduate School of the Chinese academy of {2., Beijing 10003., china institute of Microbiology Chinese Academy of SciencesBeijing 100080 China Graduate School of the Chinese academy of sciencesBeijing 10003. China Center of Mass Spectrometry Institute of Chemistry Chinese Academy of SciencesBeijing 100080 China

Heparinase from different sources can eliminate heparin or/and heparan sulfate into various low-molecular weight heparins with different characteristics. Porcine intestinal mucosa heparin was de- graded into a series of oligosaccharides by a novel heparinase from the species Sphingobacterium. Disaccha- ride components from the digests were separated and purified by ultrafiltration and HPLC. Five major peaks appeared as three types according to their retention time. The mass spectrometry of peak I mainly gave the non-sulfated disaccharide with the mass of 3.9 Da. Peak II and III were indicated as two major monosulfated disaccharides with molecular mass of 417 and 459 Da respectively. Moreover, the peak III represented an N- acetyl disaccharide. Both peak IV and V showed the same mass of 496 Da, hinting that they were disulfate- substituted disaccharides. No trisulfate-substituted disaccharides were detected in the mixture of the heparin digest though they were abundant in the heparin structure. The results revealed that the heparinase might specifically cut the sites with low sulfated domain in heparin.

关键词： electrospray ionization-mass spectrometry heparin disaccharides heparinase high perfor- mance liquid chromatography Sphingobacterium sp.

SYNTHESIS AND CHARACTERIZATION OF NEW STABILIZERS WITH OPTIMAL MOLECULAR WEIGHT

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Chinese Journal of Polymer Science 2001年第4期19卷 341-350页

作者： Jiang-qing Pan institute of chemistry Chinese {2. of {3., Beijing 100080 china 中科院化学所北京

Over 2.x 10(8) tons of polymers are produced every year, and a large portion of polymers faces the degradation problem. There are many effective methods to protect polymers against degradation and the addition of stabilizers to polymer remains the most convenient and effective way of enhancing polymer life and performance. In this article, a series of effective stabilizers with optimal molecular weight (MW), including common, monomeric and polymeric stabilizers (antioxidant and light stabilizer) were synthesized using isocyanation, controlled isocyanation, hydrosilylation, epoxide addition, macroreaction of stabilizing functional compounds and polymerization of monomeric stabilizers. The structure and performance of these new stabilizers were characterized by using IR, NMR, MS, UV-spectra, XPS and elemental analysis. The current development of stabilizer synthesis was also reviewed.

关键词： preparation of stabilizer antioxidant hindered amine light stabilizer isocyanation hydrosilylation

Bio-regeneration of p-complexation desulfurization adsorbents

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Science china chemistry 2005年第6期48卷 538-544页

作者： LI Wangliang1,2. XING Jianmin1, XIONG Xiaochao1,2. SHAN Guobin1,2.& LIU Huizhou1 1. Laboratory of Separation Science and Engineering, {3. of Process Engineering, Chinese academy of {2., Beijing 100080, china 2. Graduate School of the Chinese academy of {2.,Beijing 10003., china Laboratory of Separation Science and Engineering Institute of Process Engineering Chinese Academy of Sciences Beijing China Graduate School of the Chinese academy of sciences Beijing China

The coupling of adsorption desulfurization and biodesulfurization is a new approach to produce clean fuels. Sulfur compounds are firstly adsorbed on adsorbents, and then the ad-sorbents are regenerated by microbial conversion. p-Complexation adsorbent, Cu(I)-Y, was ob-tained by ion exchanging Y-type zeolite with Cu2. and then by auto-reduction in helium at 450℃ for 3.h. Dibenzothiophene (DBT) was used as a model compound. The effects of cell concentra-tion, volume of oil phase, the ratio of aqueous phase to adsorbent on DBT desorption by a bac-terium were studied. The amounts of DBT desorbed and 2.HBP produced can be apparently increased with addition of n-octane. BDS activity can be improved by increasing cell concentra-tion and the ratio of water-to-adsorbent. 89% of DBT desorbed from the adsorbents can be converted to 2.HBP within 6 h and almost 100% within 2. h, when the volume ratio of oil-to-water was 1/5 mL/mL, the cell concentration was 60 g·L?1, and the ratio of adsorbent-to-oil was 0.03.g·mL?1. The amount of 2.HBP produced was strongly dependent on the volume ratio of oil-to- water, cell concentration and amount of adsorbent. Adsorption capacity of the regenerated ad-sorbent is 95% that of the fresh one after being desorbed with Pseudomonas delafieldii R-8, washed with n-octane, dried at 100℃ for 2. h and auto-reduced in He.

关键词： adsorption desulfurization p-complexation adsorbents bio-regeneration Pseudomonas delafieldii desorption.

Structures and physical properties of rigid polyurethane foams with water as the sole blowing agent

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Science china chemistry 2006年第4期49卷 363-370页

作者： LI Xiaobin1,2. CAO Hongbin1 & ZHANG Yi1 1. institute of Process Engineering, Chinese academy of {2., Beijing 100080, china 2. Graduate School of the Chinese academy of {2., Beijing 10003., china institute of Process Engineering Chinese Academy of Sciences Beijing China Graduate School of the Chinese academy of sciences Beijing China

Rigid polyurethane foams blown by varying water level were prepared in this study. The structures and physical properties of rigid polyurethane foams blown by water were measured with FT-IR, universal testing machine (Instron3.65), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). The results show that polyurea and polybiuret were the typical charac- teristics, and the cream time and gel time were shorter for the fully water blown rigid foams than that for the fully cyclopentane blown foams. The density of foam samples decreased from 45.0 kg/m3.to 2..4 kg/m3.with the increase of water level from 3.pph to 7 pph. Compressive strength exhibited the similar behavior with density. The average cell size of foam samples ranged from 2.1 μm to 3.6 μm with the increase of water level from 3.pph to 7 pph, respectively. At the same time, poorer dimen- sional stability was encountered with the increase of average cell size due to fast diffusion rate of CO2.out of the foam. The results of thermal analysis show that the glass transition temperature (Tg) shifted to a higher temperature with the increase of isocyanate level when more water was used as chemical blowing agent.

关键词： polyether polyol, polyurethane rigid foam, compressive strength, dimensional stability, cell size, glass transition temperature.

Fluorescence dynamics of interactions between polyamide PyPyPyβDp and DNA

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Science china chemistry 2006年第1期49卷 75-80页

作者： ZHANG Huijuan1,2. WANG Jin3. WU Yishi1, YUAN Gu3. AI Xicheng1, WANG Li4 & ZHANG Jianping1 1. State Key Laboratory for Structural chemistry of Unstable and Stable Species, institute of chemistry, Chinese academy of sciences, Beijing 100080, china 2. School of Life Science and Technology, Beijing institute of Technology, Beijing 100081, china 3. College of chemistry and Molecular Engineering, Peking University, Beijing 100080, china 4. Center for Condensed Matter Physics, institute of Physics, Chinese academy of sciences, Beijing 100080, china Correspondence should be addressed to Ai Xicheng and Zhang Jianping State Key Laboratory for Structural chemistry of Unstable and Stable Species Institute of Chemistry Chinese Academy of Sciences Beijing China School of Life Science and Technology Beijing Institute of Technology Beijing China College of chemistry and Molecular Engineering Peking University Beijing China Center for Condensed Matter Physics Institute of Physics Chinese Academy of Sciences Beijing China

The photophysical properties of the polyamide PyPyPyβDp (PPP) were investigated by means of steady-state absorption and fluorescence spectroscopies, as well as time-resolved fluo-rescence spectroscopy. It was found that the excited-state properties of PPP are very sensitive to solvents. In TKMC buffer PPP exhibited weak fluorescence with a decay time constant of 16 ps, while with the decrease of the solvent polarity PPP showed the blue-shifted peak position, increased inten-sity and lengthened life-time for its fluorescence behavior. In the presence of calf thymus DNA, it was observed that the fluorescence intensity was enhanced and the fluorescence lifetime increased from 16 to 3.0}ps for PPP, which verified that PPP bound into the minor groove of DNA duplex.

关键词： polyamide (PPP), calf thymus DNA (ctDNA), time-resolved fluorescence spectroscopy, recognition dynamics.

Theoretical study on the reaction mechanism of(CH_3._3.O+CO

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Science china chemistry 2005年第1期48卷 18-24页

作者： ZHAO Hongmei1,2.3. SUN Chengke1,4, ZHANG Rongchang3. XI Hongmin3.& LI Zonghe1 1. Department of chemistry, Beijing Normal University, Beijing 100875, china 2. The Laboratory of Molecular Reaction Dynamics, {2. of chemistry, Chinese academy of sciences, Beijing 100080, china 3. Department of chemistry, Beihua University, Jilin 13.0}13. china 4. Department of chemistry, Qujing Normal University, Yunnan 655000, china Department of chemistry Beijing Normal University Beijing China The Laboratory of Molecular Reaction Dynamics Institute of Chemistry Chinese Academy of Sciences Beijing China Department of chemistry Beihua University Jilin China Department of chemistry Qujing Normal University Yunnan China

The reaction mechanism of (CH3.3.O with CO has been theoretically investigated using density-functional theory (DFT) calculations at B3.YP/6-3.G* level. In order to get more reliable energy values the single-point energy is evaluated at CCSD (T)/6-3.++G** level. The results show that the reaction is multi-channel and the reaction of (CH3.3.O radical with CO mostly produces (CH3.3. + CO2. The reaction could play a role in eliminating air pollution.

关键词： DFT, B3.YP, (CH3.3.O, radical.

The Juancheng chondrite──A new meteorite falling recently in china

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Chinese Science Bulletin 1998年第21期43卷 1834-1837页

作者： CHEN Yongheng 1,2. WANG Daode+2.and WANG Ruitian+3.. Department of chemistry, Guangzhou Normal University, Guangzhou 510400, {3. 2. Guangzhou {2. of Geochemistry, Chinese academy of sciences, Guangzhou 510640, {3. 3. Heze Bureau of Seismolo Department of chemistry Guangzhou Normal University Guangzhou China Guangzhou institute of Geochemistry Chinese Academy of Sciences Guangzhou China Heze Bureau of Seismology Shandong Province Heze China

The Juancheng chondrite, a new meteorite falling recently in Juancheng County, Shandong Province, china, is classified as an H5 (S2. chondrite based on the compositions of olivine (Fa= 19.2. σ Fa=0.46) and low-Ca pyroxene (Fs=16.9, σ Fa=0.4). The plagioclase in the Juancheng chondrite is rich in CaO, indicating a relatively high metamorphic temperature the parent body underwent.

关键词： Juancheng ordinary chondrite new meteorite.

Study on the coating of nano-scale SiO_2.film on the surface of nanocrystalline Mg-Al layered double hydroxides

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Science china chemistry 2005年第2期48卷 107-114页

作者： ZHANG Zejiang1,2.3. MEI Xiujuan2. XU Chenghua1 & QIU Fali1 1. Chengdu institute of Organic {3., Chinese {2. of sciences, Chengdu 610041, china 2. Sichuan Fire Research institute of Public Security Ministry, Chengdu 61183., china 3. Graduate School of the Chinese {2. of sciences, Beijing 10003., china Correspondence should be addressed to Zhang Zejiang (email: zzjzzjzz@***) Chengdu institute of Organic chemistry Chinese Academy of Sciences Chengdu China Sichuan Fire Research institute of Public Security Ministry Chengdu China Graduate School of the Chinese academy of sciences Beijing China

The coating process of a nano-scale SiO2.film on the nanocrystalline Mg-Al layered double hydroxides via a sol-gel process was investigated. The uniform and dense SiO2.ilm with a thickness of about 5 nm on the nano-LDHs particles was characterized by the solubility test in the dilute HNO3.or HCl acid, TEM and FT-IR, XRD, TG and DSC. The chemical shifts of binding en- ergies of Al 2., Mg 2., Si 2. and O 1s on the coated particles indicate that the coating of the SiO2.nano-film on the surface of the nano-LDHs proceeds through the formation of Mg-O-Si and Al-O-Si bonds. The thermal analysis shows that both the SiO2.coated nano-LDHs and the nano-LDHs have a similar mass loss process, in which there are three obvious stages of mass loss in the temperature range of 40—700℃. Furthermore, the more the coatedamount of SiO2.n the surface of the nano-LDHs is, the less the mass loss of the samples is at 700℃.The nano- LDHs have two obvious endothermic peaks at 2.4.67℃ and 43..13., whose corresponding heat absorption capacities are 412.2. J/g and 3.6.3. J/g, respectively. In contrast, the coated nano-LDHs have only one endothermic peak at 2.3.60℃ with a heat absorption capacity of 2.1.2. J/g.

关键词： layered double hydroxides, nanocrystalline, silica, coating.