Abstract:Reported in this paper is a practical method to synthesize quaternary ammonium salt of chitosan (HACC) in high substitution rate by reacting chitosan with 2,3-epoxypropyltrimethyl ammonium chloride. Reaction conditions were screened and the main factors were analyzed independently. Optimized condition factors were determined as follow: mole ratio of the reactants nc:ng = 1:4; molecular weight of Chitosan MWc = 320000g/mol; alkaline pretreatment time ta = 14h; moisture content of the pretreated chitosan Wi = 20%; reaction pH = 7; reaction temperature T = 75℃; reaction time tr =8h. The substituted product was analyzed by IR, SEM and TG/DTG. The analysis results indicate that the substitution occurred mainly on the amino groups of chitosan. Compared to unsubstituted chitosan, the substituted product has a smaller particle size and slightly lower thermostability.

Abstract:The synthesis of cinnamate catalyzed by phosphotungstic acid supported on strong acid cationic resin D001 was studied with cinnamic acid and n-butyl alcohol as beginning materials.The factors effected on the reaction yields, such as the reactants ratios, reaction time, temperature, the amount of catalyst and the reusability of catalyst, were investigated. The result showed that the optimized conditions were as follows: the reaction temperature was 100° C, the reaction time was 3 hours, the ratio of acid and alcohol was 1:3, and the catalyst dosage was 15% (based on total mass of cinnamic acid). Under the optimum conditions, the percentage of esterifation achieves 92.4% and the yield was above 83% after the catalyst was used for 4 times without any treatment. The synthesis of several other cinnamates were also studied in the optimum conditions, and the percentages of esterifation were all over 85%.It was showed that the catalyst of phosphotungstic acid supported on resin D001 has a good catalytic effect.

Abstract:A series of KF / ૪ -Al2O3 catalysts were prepared and used for glycerol polymerization. The effect of the calcination temperature and KF loading on the degree of polymerization of the polyglycerin were investigated. The structure and performance of catalysts were characterized by XRD ,Hammett indicator method, TG-DTA，CO2-TPD，BET methods. The results showed that under the conditions: the calcination temperature was 600°C, the KF content was 40%, the degree of polymerization of the polyglycerin was up to 6.21. Catalytic activity depended on the amount of K3AlF6 existed on the surface of catalyst.

Abstract:A new sulfation technique was developed using DMF-katastaltic chlorosulfonic acid as sulfation/sulfonation agent which showed higher selectivity of sulfation against sulfonation for the feedstocks containing both aromatic ring and hydroxyl intramolecularly. Nonylphenol polyproxylene ether sulfate (NPPS), one of the extended surfactant was highly selectively synthesized from nonylphenol polyproxylene ether (NPP) by using the aforementioned technique. The influential factors such as dosages of sulfation agent, ageing temperatures and ageing times were systematically investigated. The selectivity of sulfation could reach to 100 % and the maximum yield was as high as 98.4 % under the optimal conditions of 1.3:1 molar ration of HSO3Cl to NPP at 35 oC reacting 15 min. And fortunately DMF could be simply recovered and reused. The experimental results showed that it was difficult to obtain high sulfation selectivity by only using chlorosulfonic acid as sulfation agent. And it is also showed that compared with sulfamic acid as sulfation agent, this technique was much simple, more efficient and more inexpensive. It is expected that the novel technique is a hopeful sulfation method with high sulfation selectivity for the other feedstocks containing both aromatic ring and hydroxyl intramolecularly.

Abstract:Copper-containing hexagonal mesoporous molecular sieve Cu-HMS were synthesized by adjusting ethanol/water ratio of synthetic system. The effects of micelle behaviors on structure and surface morphology on structure and surface morphology were characterized by infrared resonance (IR) spectroscopy, X-ray powder diffraction(XRD), scanning electron microscopy (SEM) and N2 adsorption–desorption. All the PdCl2/Cu-HMS catalysts exhibited high selectivity for diethyl carbonate (over 99.0%) by oxidative carbonylation of ethanol in the gas-phase reaction. An optimized ethanol/water molar ratio existed for catalytic performance, which was about 1. The PdCl2/Cu-HMS catalyst exhibited higher catalytic performance, which is attributed to the fact that the larger surface area would facilitate the dispersion of the active component Pd, as well as the electron transfer of catalytic active sites Cu and Pd.

Abstract:In this paper, two novel organic dyes with 4-nitrobenzene in electron acceptor were designed and synthesized as sensitizers for dye sensitized solar cells (DSSCs). The dyes were characterized by mass spectrometry (MS), proton nuclear magnetic resonance spectrometry (1H–NMR), and carbon nuclear magnetic resonance spectrometry (13C–NMR). The photophysical and electrochemical properties of the dyes were studied. Dye L-TPNC achieved a higher light to electricity conversion efficiency (η) of 1.59% (open-circuit photovoltage Voc = 0.65 V, short-circuit photocurrent density Jsc = 3.49 mA/cm2 and fill factor FF= 0.70) under 100 mW/cm2 (AM 1.5G), and the efficiency of DSSCs based on S-TPNC reached 1.23%.

Abstract:Due to its sustained secondary structure and plenty of thiols, Keratin obtained via reduction system could be used to prepare Protein-polymer hybrids(PPHs) bio-materials. In the paper, pig hair was dissolved in reduction mixture under optimized conditions (pH 6.5, NaS2O5 1.0 mol/L, Urea 14 mol/L, SDS 0.2mol/L, 8h, 65℃) to extract keratin, it gave conversion of 55-60%. The FT-IR spectra and TGA curves of result keratin, when compared with the original hair, showed that its secondary structure was maintained. Polyacrylamide Gel Electrophoresis (SDS-PAGE) analysis indicated that the keratin had molecular weight distribution of three bands (13kDa-15kDa、45kDa-50kDa and 52kDa-55kDa). The result of Ellman test indicated that free thiols of keratin covered about 38.9% of total sulfur in keratin.

Abstract:According to the experimental design principle of response surface methodology, four factors and three levels of response surface experiment was designed to optimize the preparation process of the tilapia scales collagen peptide iron chelate. A mathematical model was established to describe peptide iron chelate rate as a function of pH, peptide iron mass ratio, time and temperature. The results show that pH, peptide iron mass ratio and time have a significantly effect on the peptide iron chelate rate. The optimal preparation conditions is pH 5.4, temperature 40 ℃, the peptide iron mass ratio 3:1, and time 41 min. Under the optimal preparation process, the practical value of peptide iron chelate rate is 90.49%, which has no significant difference with the predicted value.

Abstract:The hydrophobic bifunctional mesoporous of palygorskite solid acid was prepared by using H2O2 to oxidize the chemical palygoriskite, which is modified by grafting 3- mercaptopropyl trimethoxysilane and four kinds of silane coupling agent different carbon number. The samples were characterized by IR, XRD, SEM, BET, NH3-TPDand elemental analysis. The catalytic activity of solid acid was tested for the esterification of trimellitic anhydride with 2-ethyl hexanol. The experimental results showed that the catalytic activity of palygorskite solid acid was increased and amount of catalysts was decrased by hydrophobic hydrocarbon chain leading into. The esterification yield is 94.81% under the conditions： the molar ratio of trimellitic anhydride to 2-ethylhexyl alcohol is 1:4.5, the weight of catalyst is 1.2％ of total weight(0.12 g), the reaction time is 6 h and the oil bath temperature is at 210℃．

Abstract:With the raw material maleic anhydride, mixed alcohols and styrene, the copolymer maleic anhydride mixed alcohols ester- styrene(PMST) is synthetized, the reaction conditions are investigated and the pour point depressant effect is tested. The suitable esterifications are, molar ratio of mixed alcohols and material maleic anhydride is 2:1, esterification time is 3h, amount of catalyst is 1.5%, amount of esterification solvent is 20%; and the suitable polymerizations are, molar ratio of styrene and maleic anhydride mixed alcohols is 1:1, amount of polymerization solvent is 50%, polymerization temperature is 80℃, amount of initiator is 1.5%, polymerization time is 3h. IR and 1H-NMR spectra confirm the structure of products. When the addition dose of PMST is 0.4%(based on the mass of wax oil), and the heat treatment temperature is 70℃, PMST can make the pour point of wax oil used in experiment decline 26℃,this pour point point can make high freezing point wax oil have an ideal fluidity in room temperature even lower temperature.

Abstract:By post-crosslinking reaction with piperazine , New poly(styreneiviny benzene) hypercrosslinked adsorption resins of NDA-201 were successfully prepared by chemical modification of macroporous resin of XDA-200. The static adsorption and desorption characteristics for norfloxacinin aqueous solution onto above adsorption resins were studied. A batch sorption experiments showed that NDA-201 resin had high adsorption capacities for norfloxacinin．Equilibrium adsorption data fitted to both Langmuir and Freundlich isotherms in the studied concentration range．Adsorption was exothermic arid basically of physical character．Kinetic analysis showed that the adsorption reaction could be approximated by a Lagergren pseudo-second-order-rate equation for which intraparticle diffusion was the essential rate-controlling step．

Abstract:The Cu/Ni ultrafine mixed catalyst were prepared by sol-gel technique, the catalysts were applied for liquid phase hydrogenation of furfural to 2-methyltetrahydrofuran. The effects of Cu/Ni molar ratio, concentration of Na2CO3 solution on the properties of the catalyst were investigated, and the effects of reaction pressure, reaction time, reaction temperature on the conversion of furfural and selectivity to 2-methyltetrahydrofuran were studied in detail. The results indicated that catalyst preparation conditions under Cu/Ni molar ratio 5/5, concentration of Na2CO3 solution 1.0mol/l, liquid phase hydrogenation under reaction pressure 8MPa, reaction time 3.5h, reaction temperature 180℃, The conversion of furfural and the selectivity of 2-methyltetrahydrofuran were 100% and 64.52% respectively by GC analysis.

Abstract:Polyaline(PANI) films doped with dodecyl benzene sulfonic acid (DBSA) were polymerized by cyclic voltammetry on gold-plated PET films. To research the effect of acid concentration and polymerization cycle on PANI, infrared spectra, micro morphology, cyclic voltammetry curves, X-ray diffraction patterns and UV-vis-NIR reflection spectra were measured respectively. Results show that DBSA- could incorporate into PANI molecular chains, which lead to form PANI fibers by compatibilization of long-chain alkyl in DBSA-. In polymerization progress, the polymerization rate increased as DBSA concentration increasing, which lead to flaky dense structure, high degree of crystallinity, large ion steric hindrance and low spectral reflectance. With the increase of polymerization time, surface morphology of PANI becomes worse and appears clusters phenomenon, nucleation rate gradually increase and fibers grow laterally into bands.

Abstract:The 4-fluorobenzoylhydrazide (2) was prepared by esterification and hydrazinolysis of 4-fluorobenzoic acid (1). 4-Fluorobenzoylhydrazide (2) reacted with aromatic formaldehydes to give 4-fluorobenzoylhydrazones (3a-3h). The cyclization dehydration of 4-fluorobenzoylhydrazones with mercaptoacetic acid afforded 2-aryl-3-(4-fluorobenzoylamino)-4-thiazolidinones (4a-4h). The structures of 4a-4hwere confirmed by elementary analyses, IR, 1H NMR, 13C NMR, and MS spectra，and their in vitro anticancer activity against the three cancer cell lines of HepG-2, A549-1 and 231-2 was evaluated. The bioactive assay showed that 4b and 4f exhibited a significant anticancer activity.

Abstract:Oxidized starch-aminothiazole Schiff-base (OSAT) was synthesized based on the reaction of aminothiazole (AT) and water soluble oxidized starch with high carbonyl content which was prepared by the oxidation of sodium hypochlorite. The synthesis conditions of OSAT were studied and the optimum conditions were as follows: nitrogen protection, water as solvent, adjusting the pH value of solution by acetic acid, pH = 5, T = 70 ℃, t = 16h. The substitution degrees of AT chould be adjusted by controlling the molar ratio of AT to carbonyl groups and the aldehyde groups utilization rate of 100% was achieved. The structure of OSAT was characterized by FT-IR, NMR and UV. The adsorption performance of OSAT to Cu2+ and Ag+ was also studied. The result showed that the adsorption capacity of OSAT (degree of substitution is 0.14) to Cu2+ and Ag+ was 0.82, 1.48 mmol/g, respectively.

Abstract:The cleaning production technology for N,N-Dibenzyl hydroxylamine(Referred to as DBHA)was studied. Using benzyl chloride and hydroxylamine hydrochloride as raw material，triethylamine as proton acceptor，DBHA was synthesized in organic solvents after the two-phase reaction. The optimal conditions of synthesis were as following：the molar ratio of hydroxylamine hydrochloride and benzyl chloride was 1：2.3，the first-phase reaction was carried at 50 ℃ for 80 min，while the second-phase reaction at 80 ℃ for 220 min. Under the above optimum conditions，the yield of the product was 81.3％ with the melting point of 123.6～125.3 ℃. The structure of product was confirmed by IR、1H RMR、13C NMR、MS. This technology was adopted to resolve the problem of sewage including salt and organic solvents which were generated by traditional technology. Compared with traditional technology，this new one was suitable for industrial production.

Abstract:Guanosine (1) as the starting material was protected by acetic anhydride to get 2′,3′,5′-tri-O-acetyl-guanosine(2) , then chlorinated with phosphorus oxychloride to obtain 2-amino-6-chloro-9-(2′,3′,5′-tri-O-acetyl-β-D-ribofuranosyl)purine(3). Further diazotization-sulfenylation processes gave rise to 2-alkylthio-6-chloro-9-(2′,3′,5′-tri-O-acetyl-β-D-ribofuranosyl)purines(4). 6-Alkoxy-2-alkylthio adenosine (5) were acquired by aromatic nucleophilic substitution and deprotection reaction. The structures of the compounds were identified by 1H NMR、13C NMR、IR and HRMS. What is more, platelet aggregation rate(PAR) for the compounds were measured. The results show that, these compounds have a certain anti-platelet aggregation activity under 10μmol/L, wherein 6-(2-furanylmethyl)oxy-2-propylthio adenosine presents the most significant activity.

Abstract:A kind of anionic polymerizable lipids sodium conjugated linoleates was prepared from high purity natural linoleic acid through alkali catalytic isomerization reaction. The sodium conjugated linoleates molecularly self-assembled into spherical micelles in aqueous phase, and the intramicellar self-crosslinking reaction among the sodium conjugated linoleates were induced by some free radical initiators to result in formation of spherical self-crosslinking micelles of sodium conjugated linoleates. The influence such as type and amount of initiators, reaction times and temperatures were investigated on the self-crosslinking degree of the sodium conjugated linoleates and the morphologies of the self-crosslinking assemblies were intuitively imaged by TEM. Experimental results indicated that the self-crosslinking spherical micelles of 20 nm in average diameter were obtained when self-crosslinking was induced by using ammonium persulfate as initiator at pH 13 and 80 oC for 10 h, which is a potential stable drug nanocarrier or microreactor.

Abstract:C/NiFe2O4 composite material was prepared by sol-gel method using glutinous rice as raw material of carbon. The structure, micro-morphology and adsorptive properties of acid fuchsin were studied. The nanoparitilce C/NiFe2O4 synthesized under the condition 450℃, 6h is 20nm and disperse homogeneously. It was found that the best adsorption condition was pH 5 and the remove rate can reach 88% in 10min. The remove rate of composite material was higher than sigle phase carbon and NiFe2O4, this mean that composition material can imporve removal rate effectively.

Abstract:Synthesis and polymization of acrylate containing perfluoronineyl were investigated. N-methyl-N-p-perfluorononenoxybenzenesulfamidethyl acrylate (III) was synthesized from p- perfluorononenyloxybenzenesulfonyl chloride by amidation and esterification. The optimum conditions of esterification was n(II):n(Acryloyl chloride)=1:3, react at room temperature for 6h, The yield of III was 75.0 %. The fluorinated copolymer emulsion with blue-fluorescence was synthesized by semicontinuous emulsion polymerization of III initiated by K2S2O8 with butyl acrylate (BA), methyl methacrylate (MMA). Acrylate (III) and copolymer film were characterized by FT-IR,1HNMR and ESI-MS respectively. The copolymers emulsion stability and content of III in copolymer on the water contact angle on the copolymer film were studied. When the film contains 20 % III in weight, the water contact angle on the film is 88.2?

Abstract:A series of post cross-linked acrylic emulsion adhesives were synthesized by pre-emulsion technology and semi-continuous emulsion polymerization. Butyl acrylate (BA), vinyl acetate (VAc) and acrylic acid (AA) were used as main monomers and diacetone-acryloamide (DAAM) /adipic dihydrazide (ADH) as post cross-linker. Emulsion polymer was characterized by means of fourier transform infrared (FTIR) analysis, transmission electron microscopy(TEM) and thermo-gravimetric analysis (TGA). Polymer structures and the cross-linked between emulsion particles have been characterized by FTIR spectroscopy and TEM photographs, respectively. TGA indicated its potential use in the environment of high temperature. Corresponding pressure sensitive adhesive（PSA）tapes were prepared at a thickness of 50 μm, their properties including tack, 180o peel strength, and shear strength at room temperature and 100 oC and their influence by BA:VAc ratio, AA content and DAAM/ADH content were studied. The results showed best properties were obtained when BA:VAc was 85:15 and AA content was 3%. The tack ball size was 17, 180o peel strength was 504 N/m, room temperature shear strength was more than 1 month, and 100 oC shear strength was 140 min. Further introducing of DAAM/ADH significantly improved 100 oC shear strength of the PSA tapes to 540 min at little sacrifice of their tack property and 180o peel strength, which could be explained by the mechanism of post cross-linking.

Abstract:Abstract：More than 99% purity of liquid crystal intermediate of 4-ethoxy-2,3-difluorophenyl acetic acid was synthesized via alkaline hydrolysis and acidification after Willgerodt-Kindler reaction with 4-ethoxy-2,3-difluoroacetophenone as the starting material. The target compound was characterized by 1HNMR、IR and GC-MS. The results of condition experiments showed the effect of Willgerodt-Kindler reaction was best when the molar ratio of 4-ethoxy-2,3-difluoroacetophenone/sulfur/morpholine was 1:2:4, the reaction temperature was 105～115 ℃ and the reaction time was 2 h.The mass ratio of the main product was 71.54%,the mass ratio of the by-product of 4-ethoxy-2-morpholine-3-fluoro-phenyl thiomorpholine amide was 14.60%.The generation reason of the by-product during Willgerodt-Kindler reaction was proposed according to the results of experiments,and its structure was confirmed by 1HNMR and GC-MS.

Abstract:The [Bmim]OAc，[Bmim]2CO3 and [Bmim]OH ionic liquid were synthesized and their structure were confirmed by IR、1HNMR and elemental analysis. First, Chitosan was alkalized by ionic liquid. Then the alkalized chitosan reacted with bromododecane. And thus N-dodecyl chitosan with high degree of substitution (DS) was produced. The structure of alkylation product was characterized by IR、1HNMR and XRD. It studied the effects of time, temperature and the ratio of reactant on the DS of N-dodecyl chitosan. The suitable reaction conditions were found as follows：n([Bmim]OH):n(chitosan)=3:1，the chitosan was alkalized for 1h with alkalization temperature 45℃，n(bromododecane): n(alkalized chitosan)=2:1，the alkalized chitosan reacted for 3h with alkylation reaction temperature 80℃. Under above conditions，the DS of N-dodecyl chitosan can be over 81％. The reusability of the ionic liquid was also investigated，and it was found that the DS still could be kept above 80％ after the [Bmim]OH ionic liquid was reused for 3 times without any retreatment.

Abstract:The reaction rules of selective hydrogenation p-chloronitrobenzene(p-CNB) to p-chloroaniline(p-CAN) over skeletal copper（S-Cu） catalyst were studied. The microstructure of S-Cu was characterized by XRD, BET and SEM. The effects of solvent, reaction temperature, reaction pressure and concentration of substrate on the conversion of the reaction and the selectivity of target product have been investigated. Under the optimized reaction conditions of n(p-CNB) = 7 mmol, m(S-Cu) = 0.5 g (wet weight), V(CH3OH) = 20 mL, 60 ℃, and P（H2）= 1.0 MPa, the conversion of p-CNB was up to 100% and the selectivity of p-CAN was 97.9% in 120 minutes.

Abstract:Thiophene was refluxed with carbon tetrachloride and methanol or ethanol to give dimethyl thiophene-2, 5-dicarboxylate (1a) or diethyl thiophene-2, 5-dicarboxylate (1b) using Ferrous acetate as catalyst. The optimum conditions were n (thiophene)：n (carbon tetrachloride)：n (ferrous acetate)＝1: 2.5: 0.01 and reflux time 6 h in excess alcohol. Yields of thiophene-2, 5-dicarboxylate were 91.5%~95.2%. Compound 1a or 1b was hydrated in base condition and then acidified to give thiophene-2, 5-dicarboxylic acid (2). The optimal reaction conditions were n (thiophene-2, 5-dicarboxylate): n (sodium hydroxide)=1: 2.5 and reflux time 5 h in methanol and water (1: 2). Yields of thiophene-2, 5-dicarboxylic acid were 90.5%~92.0%.

Abstract:An efficient one-pot method is used to prepare a series of N-aryl substituted piperazine hydrochloride from substituted aniline and N,N'-bis(2-chloroethyl)amine hydrochloride in 2-(2-methyloxyethoxy)ethanol under microwave irradiation. The reactions were completed in 3～4 min with 36.9%～75.4% yields. It is confirmed from the experimental results that substituents on the benzene rings of the substituted aniline exerted consistent influences in the ongoing N-aryl piperazination with that of plausible prediction. Compared with conventional heating method, the method of microwave irradiation possesses advantages including short time, hige yield, easy working out and environmental benignity. Their molecular structures were characterized by IR, 1H NMR and MS spectroscopy.