Abstract:The innovation and benefits of five awards and winners of the Presidential Green Chemistry Challenge(PGCC)Awards Program in 2011 are reviewed. Those awards and winners of the US Presidential Green Chemistry Challenge Awards in 2011are introduced :（1）Greener Synthetic Pathways Award: Genomatica. Production of Basic Chemicals from Renewable Feedstocks at Lower Cost（2）Greener Reaction Conditions Award: Kraton Performance Polymers, Inc. Polymer Membrane Technology.（3）Designing Greener Chemicals Award: The Sherwin-Williams Company. Water-based Acrylic Alkyd Technology.（4）Small Business Award: BioAmber, Inc. Integrated Production and Downstream Applications of Biobased Succinic Acid.（5）Academic Award: Professor Bruce H. Lipshutz, University of California, Santa Barbara. Towards Ending Our Dependence on Organic Solvents.

Abstract:Brucea javanica (Simaroubaceae) is a medicinal plant traditionally used in Southern of China to treat several diseases. In order to enlarge the medication parts, the constituents of essential oils which extracted with microwave-assisted hydrodistillation (MAHD) and hydrodistillation (HD) from Brucea javanica were analyzed by capillary GC-MS and elucidated based on the standard mass spectral data. 42 and 37 kinds of volatile components were identified respectively. Relative mass fractions of the constituents were determined by area normalization method. The identified relative contents of essential oils were 94.09% and 94.13%, respectively. There were differences among some chemical constituents of two kinds of essential oils. But their main constituents were safrole, ( )-4-carene, ?-myrcene, eugenol methyl ether, 2,6-dimethoxy toluene, limonene and estragole.

Abstract:Oil-dispersible β-NaLuF4:Yb3+, Er3+ colloid particles were synthesized via a facile hydrothermal method in the liquid-phase system containing ethanol-water-oleic acid-sodium oleic acid. The hexagonal phase structure of the sample was characterized by the X-ray diffraction technique. Transmission electron microscopy and high resolution transmission electron microscopy indicated that the β-NaLuF4:Yb3+, Er3+ colloid particle was crystallized in the hexagonal morphology with the size of 10nm×10nm×40nm. Upon 980 nm near-infrared irradiation, the as-prepared particles showed strong emission peak at 543nm, which corresponded to the 4S3/2-4I15/2 transition of the Er3+ ions. The double-photon emission was assigned to the emitting mechanism.

Abstract:Abstract: aminoguanidinium 1-methyl-5-nitriminotetrazolate have been prepared by reacting aminoguanidine bicarbonate with 1-methyl-5-nitriminotetrazole which is obtained from 5-aminotetrazole through methylation and nitration.Reaction temperature, time, material ratio, alkali concentration and the amount of solvent were studied about effects on the methylation reaction, and the optimized yield was 44% which was 3% higher than literature values.Then,Nitration dosage, reaction temperature and time were also investigated into nitrification yield,and the optimized yield was 81%. the products were characterized by 1HNMR,IR,MS,etc.

Abstract:Triglycol benzo[5,6]coumarin-3-carboxylate (D) was prepared and characterized by 1H NMR, 13C NMR, FT-IR, MS and elemental analysis. Compound D and triglycol dibenzo[5,6]coumarin-3-carboxylate (E) emit blue fluorescence. The maximum emission wavelength λem of D and E was little influenced by solvent polarity. The fluorescence intensity of E was increased in methanol and ethanol, and dimethyl sulfoxide is its fluorescence quenching agent. In acetonitrile, upon the addition of Ca2+, the fluorescence intensity of D reduced by 30 %, while that of E increased by 40 %.

Abstract:Three acenaphthopyrazine derivatives were designed and synthesized，where pyrazine groups were used as the electron acceptor connected by carboxyl acids to aromatic groups used as electron donor, applied for dye-sensitized solar cells (DSSC). A higher total solar energy conversion efficiency (η) of 3.06 % was obtained for the 3-(diphenylamino) acenaphtho [1,2] pyrazine-8-carboxylic acid (Va), compared with the conventional N719 dye which gives 7.05% under the same conditions. The range of absorption of the dye Va is concentrated upon 400 to 500 nm and the votage of LUMO is -1.10 eV, which indicated that the process of electron injected into CB of TiO2 to form the excited dyes is feasible in thermodynamics. The data of EHOMO 1.31eV, more positive than I-/I3- redox couple 0.4eV, also indicated that the oxidized dyes could be reduced effectively by electrolyte and then regenerated.

Abstract:The Star macro-initiator of octakis(2-bromo-2-methylpropionoxypropyl dimethyl- siloxysilsesquioxane(OBPS) was synthesized via hydrosilylation and esterification with octakis(dimethylsiloxy)silsesquioxane(Q8M8H), allyl alcohol, and 2-bromo-2-methylpropionyl bromide. The structure of OBPS was characterized by FTIR, 1H-NMR, 29Si-NMR and GPC methods. The influence of solvent, temperature and reaction time on the product structure and yields was discussed. The optimal experiment conditions were: solvent THF, 0℃ for 3h and then room temperature for 20h. The yield was 85.0%. OBPS can be used as the macro-initiator in atom transfer radical polymerization to synthesize star polymers.

Abstract:An asymmetric Gemini surfactant, comprising two nonidentical hydrocarbon chain lengths and two different anionic hydrophilic groups, abbreviated as C12CO2Na-p-C10SO3Na has been synthesized through Williamson etherification, sulfonation and saponification. Ethyl 2-bromomyristate and 4-decylphenol were used as the starting material. The structures of main intermediate products and the title product were characterized by FT-IR and 1H NMR. The optimum conditions for etherification were n (ethyl 2-bromomyristate) : n (4-decylphenol) = 1.05:1, K2CO3 as acid binding agent, DMF and toluene as solvent, and refluxing for 3 h. The yield of ethyl -(4-decyl) phenoxytetradecanoate was 77.2% (basing on 4-decylphenol). The surface activity of C12CO2Na-p-C10SO3Na was measured by Wilhelmy method. The surface tension could decrease to about 26 mN/m, and the critical micelle concentration (CMC) was found to be 3.28×10-6 mol/L. The CMC value was nearly 3 orders of magnitude lower than that of the corresponding traditional surfactants, such as sodium myristate and sodium m-decylbenzene sulfonate. The results illustrated that the asymmetric anionic Gemini surfactant show high surface activity.

Abstract:Three surfactant monomers of maleic hemiester were synthesized in two steps ,and the structures of the products and intermediates were identified by IR and 1HNMR. The surface activity and emulsification properties of the products were measured. The results showed that the lowest surface tension of SHE12 was 27.5mN/m,SHE16 was 30.5mN/m and SHE18 was 37.2mN/m. Compared with normal surfactant SDS, the cmc values were decreased at great degree (1~2 orders of magnitude).Furthermore, the lg(cmc) of surfactants decreased nearly linearly along with the growth of alkyl chain.The emulsification properties of SHE16 and SHE18 were superior to that of SDS and SHE12. The results of viscosity measures showed that the copolymers of acrylamide/sodium acrylate/SHE12 existed critical association concentration(CAC) and had the better tackify performance than HPAM.

Abstract:An extensive study of the foaming properties of APG influenced by APG’s concentration，N2 flow rate and salt concentration were investigated using the Foam Scan. The results showed that all the APGs had good foam stabilities in 1000s. In addition of c(APG) = 0.25cmc of foaming time was 149s,the remaining concentration of foaming time were at the range of 144 ?2s.The foam relative conductivity, foam maximum density and foam stability index continu-ally increased with increasing the surfactant concentration. N2 flow rate had comparatively effect and there was an op-timal N2 flow rate of 40mL/min. Foaming time slightly reduced but foam stability index increased with the increase of salt concentration.During the foaming stability investigation, the number of foams were fewer and fewer while single foam area changed more larger with increasing time and N2 flow rate. More the number of foam had been found in high salt concentration than low salt concentration. With the increase of surfactant concentration, the quantity of foam in-creased but the total area and average size of the bubble decreased.

Abstract:The water solubilization of the microemulsion system composed of TritonX100, different co-surfactant and oil are investigated. The effect of temperature, pH value on the stability of the systems are studied. The pseudo-ternary phase diagrams in quaternary microemulsion systems of TritonX100 are measured. The results showed that when the mass ratio of TritonX100 to isoamyl alcohol is 1:1, and the mass ratio of both TritonX100 and isoamyl alcohol to n-heptane is 4:1, the most water solubilizing capacity in the TritonX100/isoamyl alcohol/n-heptane/water system is 50%. Its stability region has increases along with the temperature increment below 80℃. The influence of pH value for stability of the system is less.

Abstract:The three different Ni-Cu/γ-Al2O3 bimetallic catalysts were prepared by co-precipitation method, impregnation method and co-precipitation - impregnation method. Under different conditions, the three Ni-Cu/ γ-Al2O3 catalysts for dehydrogenation of the hydrogen carrier catalytic performance were investigated by using a continuous tubular micro-reactor. XRD, SEM, BET and BJH were used to characterize the catalysts. The results showed that: Using Ni-Cu/γ-Al2O3 catalyst prepared by co-precipitation - impregnation method is better than the others (the Ni-Cu loading of the three catalysts were 26% and the proportion of nickel and copper was 8 to 1). Under the conditions of the reaction temperature 673K, reaction pressure 0.6Mpa, MCH/N2 = 19/27 and the volume of gas space velocity 240 h-1 , MCH dehydrogenation conversion rate reached 98.5% and the product selectivity was close to 100% .Besides, it is feasible that using the Ni-Cu/γ-Al2O3 bimetallic catalyst is better than the platinum or other noble metal catalysts and nickel catalysts in this reaction system.

Abstract:Palygorskite（PGS）supported TiO2 is prepared by dipping method of acid activated palygorskite, and then it is modified by H2SO4 to achieve the SO42- / TiO2-PGS solid super acid. The catalyst is characterized by FT-IR, XRD spectroscopy, SEM and BET. It is applied in trioctyl trimellitate synthesis．The orthogonal experiment shows that the esterification yield is 94.15% under the conditions： the molar ratio of trimellitic anhydride to 2-ethylhexyl alcohol is 1∶4.5, the weight of catalyst is 3.7％of total weight, the reaction time is 6 h and the oil bath temperature is at 210℃．

Abstract:Abstract: Hβ zeolites were modified by different metal ions (Al3+,Tl4+,Fe3+）under microwave radiation, and used to catalyze the synthesis of anthraquinone with benzene and phthalic anhydride. The modified zeolites were characterized by means of XRD, NH3-TPD and Pyridine-IR. The results showed that the microwave radiation was more effective for the modification of zeolite, and the catalytic performance of modified zeolites were improved. Microwave radiation did not destroy the crystal structure of β zeolite.There was great difference in catalytic activity among the zeolites modified by different metal ions. The zeolite modified with 0.5 mol•L-1 Al2(SO4)3 showed the best catalytic activity for the reaction, and the yield of anthraquinone was 38.87 %; selectivity reached 92.78 %. The surface acidity of zeolite had a significant influence on the catalytic performance in the synthesis of anthraquinone, and the medium strong acid sites were the active sites. The ratio of L acidity to B acidity played the important role in the catalysis reaction.

Abstract:Benzalhydantoin sulfonic mesoporous (SBM) was gotted by MCM-41 graftting with benzyl chloride and chlorosulfonic respectively. The composition ,structure and surface physical and chemical properties of the samples were characterized by surface of elemental analysis (EDS), fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption, X-ray diffraction (XRD), Transmission electron microscopy (TEM) and so on. The results of EDS and organic elemental analysis shows that the grafting yield was 5.84% of C（w%） for BM (sample, MCM-41 Si-OH graftting with benzyl chloride) . Further sulfonation, S grafting ratio (w%) was up to 7.46% for SBM. The results show that, after a two-step grafting reaction, SBM still has a mesoporous structure. The BET surface area is 366.9 m2•g-1and the pore volume is 0.349 cm3•g-1． The process for synthesis of tri-n-butyl citrate using SBM as catalyst was studied. The results show that when n (acid): n (alcohol) = 1.0:9.0, w (cat) = 3%, the reaction temperature is 110 ℃, reflux time 7 h, yield was 93.22%. And the catalyst can be reused, repeated five times, the esterification rate remains at 76.33 %.

Abstract:The catalyst of ZrOCl2 8H2O supported on molecular sieves USY was prepared using impregnation method and characterized by XRD and SEM. The catalytic properties were examined by the catalytic esterificaton of lauric acid and lauryl alocohol. Used the conversion of lauric acid as an index, the effects of catalyst activity and others conditions such as reaction solvent, catalyst loadings, and reaction time on the conversion of lauric acid were investigated. The results showed that the conversion of lauric acid was up to 95.2 % in the esterification of lauric acid and lauryl alocohol under the optimum conditions of 5.0 % quantity of catalysts, eflux temperature of solvent and reaction time of 16 h by used the 30 % ZrOCl2•8H2O/USY as catalyst and chlorobenzene as solvent.

Abstract:A new type of sweetening catalyst was explored for removing high molecular weight mercaptan in hydrogenated gasoline. The effects of reaction temperature，catalyst concentration and mercaptan structure on mercaptan conversion were studied. The results showed that in a certain range, the catalytic activity can be increased by rising the reaction temperature and the concentration of catalyst. The lower molecular weight mercaptans and n-thiols could be easily oxidated than the contrary mercaptans. The novel catalyst could effectively oxidize the mercaptans to disulfides. The mercaptan concentration in gasoline could be reduced from 100ug/g to less than 5ug/g , and the Doctor Test became negative.

Abstract:Ultrasound assisted extraction of proanthocyanidin from rapeseed hull using ethanol as the extraction solvent was studied. Based on the single factor tests of ethanol volume fraction, extraction time, liquid-solid ratio and ultrasound power, the optimum process were evaluated by Box-Behnken central composite experimental design and response surface methodology analysis. The results indicated that ethanol volume fraction 62.9%, extraction time of 20.8min and liquid-solid ratio of 25mL/g were found optimum. Under these optimized conditions, the experimental value of proanthocyanidin extraction yield 5.05mg/g, in good agreement with the predictive value 5.02mg/g. Therefore, the ultrasound-assisted extraction of proanthocyanidin from rapeseed hull using response surface methodology is very reliable.

Abstract:With vanillin, decanoic acid and sulfinyl chloride as initial material, capsaicinoid of N-( 4-hydroxy-3-methoxybenzyl )-decanoylamide was synthesized successfully by three synthesis procedures only. According to IR, 1HNMR, 13CNMR and elemental analysis data, its molecular structure was confirmed. Comparative research on physiological activity for natural capsaicinoid and target compound was made.And the experiment results on physiological activity were as follows: N-( 4-hydroxy-3-methoxybenzyl )-decanoylamide was similar to natural capsaicinoid in potency of pungency and the former was 0.4% smaller than the latter in pungency; the antinociceptive effect of target compound was stronger 30% than natural capsaicin; they were almost same and stronger than sodium benzoate in antibacterial activity; they were also similar as a repellent for mice. The target compound and natural capsaicinoid were both in the toxicity grade of 3 (low toxicity) As a conclusion, the synthetic capsaicinoid of N-( 4-hydroxy-3-methoxybenzyl )-decanoylamide had the value of replacing natural capsaicin in the above biological activity.

Abstract:Abstract: In the synthetic route towards tetrasulfonic acid dereivative of hypericin, self-condensation reaction of emodin anthrone was prompted by means of the microwave assisted organic synthesis. Three influencing factors of this step such as the microwave heating temperature, irradiation time and catalyst were studied and the resulting optimal conditions were determined as follows: 150°C, 1 h and no catalyst used. The yield of this step was increased by 82.2% with microwave assisted synthesis, and the total yield of the scaled-up synthesis of hypericin tetrasulfonic acid was achieved 65.3%. In comparison with conventional heating method, it is demonstrated that the use of the microwave method has enhanced the reaction efficiency and yield, reduced side-reactions and made the synthetic procedure more beneficial to low-carbon and environmental protection.

Abstract:A modified synthesis of alfuzosin hydrochloride (1) is proposed. The 2-chloro-4-amino-6,7 -dimethoxyquinazolin(4) was prepared from 6,7-dimethoxyquinazolindione (2) through chlorination and amination, and the synthesis of 2 was cyclocondensed by 2-amino- 4,5-dimethoxybenzonitrile with DMF in the catalyst of ZnCl2 in sealed tube. Compound 4 was condensed with tetrahydro-N-[3-(methylamino)-propyl]-2-furancarboxamide (5) and then treated with hydrogen chloride to give the target compound 1. The total yield is 41.3%. This method avoids highly toxic sodium cyanate, and shortens the synthetic route. The effects of catalyst, temperature and time to the yield of key intermediate 2 were investigated. The results show that the optimal yield of 2 reaches 98% with the catalyst of zinc chloride in the presence of hydrochloric acid at 170℃ for 5 h. The target products were characterized with IR, ESI-MS and 1HNMR.

Abstract:The hydroxyl polyacrylate emulsions (HPAE) for waterborne two-component polyurethane coatings (WB 2K-PUR) were synthesized by semi-continuous seeded emulsion polymerizations with trihydroxymethyl propane triacrylate (TMPTA) used as an inner cross-linking agent added by multi-stage. The effects of the TMPTA amounts and distributions in core/shell parts of latexes on the emulsion polymerization stability and the film properties were studied. The results indicated that the WB 2K-PUR film with 2 wt% TMPTA displays excellent physical-chemical properties including 0.78 of hardness, 96.4% of cross-linkage degree and 92% of gloss, besides good emulsion polymerization stability with 0.26% of coagulation contents. TGA curves indicated that WB 2K-PUR film with 3:7 of the TMPTA distribution ratio in the core and shell parts exhibits good thermal stability.

Abstract:The polycarboxylate superplasticizer(PC) was synthesized with methoxy polyethylene glycol methacrylate, methacrylic acid, sodium methyl acryl sulfonate as monomers, using ammonium persulfate (APS) as initiator. The effect of the mole ratio of different monomers on dispersing properties was analyzed. Results show that dosage of monomers and initiator impact molecular weight and dispersing properties of PC greatly; When mole ratio of MAS, MAA and PMA45 is 0.5:3.75:1, dosage of APS is 0.4%, the product of PC has best properties, with 45.09 ml?g-1 of inherent viscosity; when used in cement system with W/C ratio of 0.25 and dosage of 0.2%, the initial fluidity is 269 mm and 281 mm 30 min later.

Abstract:The Iridium catalytic systems composed of the [IrHCl2(COD)]2 and the chiral diaminodiphosphine ligand was applied for the asymmetric transfer hydrogenation of propionphenone in synthesis of (S)-(-)-1-phenyl-1-propanol. Influence of temperature, substrate/catalyst molar ratio, metal complex/chiral ligand molar ratio was tested. The 94.5% of conversion and 96.0% ee was achieved when propionphenone was reduced 6 hour in this catalytic system.

Abstract:Trimethylolpropane (TMP) tricaprylate was prepared by using trimethylolpropaneand octanoic acid as raw materials and acidic ionic liquid as catalyst．The effect of the reactants feed ratio，reaction time and amount of catalyst on reaction was studied. The results showed that the optimum reaction conditions were as follows：molar ratio of acid to T-MP is 4.2:1 and catalyst amount is 9 percent of the reactants，the reaction temperature is 140℃，and reflux for 2h．Under this condition，the yield of trimethylolpropane tricapryla-te is up to 98％.The reaction system exhibited good biphasic behavior when the reaction was completed．There is no appreciable decrease of catalyst activity for both the systems after 5 cycle catalyst repetition. The product Was analysed by IR, LCMS, HPLC, NMR.