2014, 31(11).
Abstract:2,3,5,6-tertraaminopyridine-2,5-dihydroxy terephthalic acid was synthesized through neutralization reaction by using 2,3,5,6-tetraaminopyridine(TAP) hydrochloride and 2,5-dihydroxy terephthalic (DHTA) as raw materials. PIPD was polymerized from TD salt by condensation polymerization. The effect of various reaction parameters on polymerization, including the type of monomer, reaction time, additional amount of monomer and molar ratio of reactants was investigated in detail. The optimal reaction conditions were confirmed: the molar ratio of DHTA and TAP hydrochloride was 1.05:1. Additional amount of TAP hydrochloride was 0.5%wt of TD salt and added at 140 ℃, and then the reaction proceeded at 180℃ for 3.5 h. Compared with existing processes,the relative viscosity for characterizing the molecular weight of PIPD by this way increased approximately twice.
XU Mu-ru , SUN Kan , WU Han-bing , NIE Hua-li , QUAN Jing , ZHU Li-min
2014, 31(11).
Abstract:Poly(DEGMA-co-OVNG) with narrow polydispersity (PDI) and obvious thermosensitivity was effectively prepared via enzymatic synthesis combined with Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization. The structure and molecular weight of the synthesized glycopolymer were characterized by 1H NMR, FTIR and gel permeation chromatography (GPC), respectively. Measurement by Dynamic Light Scattering (DLS) and transmission electron microscopy (TEM) revealed that Poly(DEGMA-co-OVNG) was able to self-assemble into nano-micelles with well-defined structure and uniform size in aqueous solution. UV-visible spectroscopy tests showed that the low critical solution temperature (LSCT) of the polymer can be controlled by the molar ratio of monomers. Especially, as the molar ratio of DEGMA and OVNG was 8:1, the LCST of Poly(DEGMA-co-OVNG) could be 36oC in aqueous solution. The results demonstrate that Poly(DEGMA-co-OVNG) can form nano-micelles in the human body environments, which may have potential as functional drug carriers.
2014, 31(11):0-0.
Abstract:The precursor Sm(OH)3 of Sm2O3 was synthesized by homogeneous precipitation hydrothermal method using hexamethylenetetramine(C6H12N4) and hydrated samarium nitrate[Sm(NO3)3·6H2O] as raw materials. The optimum calcination temperature (800 °C)was derived from thermogravimetry (TG) analysis and X-ray powder diffraction (XRD). The Sm2O3 mirco/nano particles were then prepared by calcining the precursors at 800 °C. The structures, morphologies and size of the Sm2O3 mirco/nano particles were characterized by XRD, scanning electron microscope (SEM). The influences of reaction temperature and time on the size and shape of the products were investigated. The results showed that Sm2O3 micro/nano particles and its precursor Sm(OH)3 were cubic and hexagonal crystalline, respectively. With the increase of the reaction time, mirco/nano Sm2O3 sheet structure gradually self-assembled into three-dimensional spherical flowers. The size of the Sm2O3 micro/nano particles decreased as the temperature increased, and the Sm2O3 nano-sheet structure become thicker and more closer.
ZHANG Lin-ya , YU Han-jiang , LIU Fang-fang , ZHAO Xiu-yuan
2014, 31(11):0-0.
Abstract:The quaternary ammonium hemicellulose was prepared by which the hemicelluloses isolated from production waste liquid of viscose fiber was used as raw materials and the 2, 3-epoxypropyl trimethyl ammonium chloride was used as etherifying agent. The optimal conditions for the synthesis of quaternary ammonium hemicellulose were determined by orthogonal experiment, in which the mass ratio of the hemicellulose and 2, 3-epoxy propyl trimethyl ammonium chloride was 1:2, the dosage of NaOH was 5% of total mass of raw materials, the reaction temperature was 70℃, the reaction time was 4h, and the substitution degree of quaternary ammonium hemicellulose could be up to 53.1%. The quaternary ammonium hemicellulose as dispersant was used in titanium dioxide slurry. The dispersion property of quaternary ammonium hemicellulose dispersant were studied. The test showed that the best deosage of quaternary ammonium hemicellulose dispersant was 0.4% of total mass of slurry,and the deosage on flowpoint was 0.0215g。
NI Mao-jun , Liu Si-yang , Bao Wen-ting , Peng Chao-rong
2014, 31(11):0-0.
Abstract:N-vinyl pyrrolidone grafted polylactic acid (M-PLA) scaffold for tissue engineering was fabricated by thermal induced phase separation technique. The effect of polymer concentration, water/ dioxane ratio and coarsening temperature on the scaffold porosity and structure were studied with grafting ratio of 36%. And the effect of grafting ratio on the scaffold structure was also studied with the same preparation condition. The hydrophilisity and protein adhesion of M-PLA scaffold was tested. The results showed that, the porosity of the M-PLA scaffold with grafting ratio of 36% decreased with the increase of polymer concentration, water was helpful to form a regular porous structure, the pore size and the porosity of the scaffold increased with the decrease of coarsening temperature. With increasing grafting ratio, there were no significant changes of the porosity and pore size of the scaffold, but better pore regularity and connectivity compared with PLA scaffold. The hydrophilisity and protein adhesion test showed that the M-PLA scaffold had higher hydration, protein adhesion ratio and better biocompatibility.
2014, 31(11).
Abstract:The performance of carboxymethylated lignin (CML) dispersant prepared from black liquor by carboxymethylation was studied and the optimal formulation of 40% Myclobutanil wettable powder was confirmed. The results showed that carboxyl groups were largely introduced into alkali lignin by carboxymethylated modification therefore the solubility and dispersibility of alkali lignin were greatly improved. The suspensibility before and after heat storage of 40% Myclobutanil optimal formulation were respectively 91.9% and 88.1% and the wetting time was less than 90 seconds those met the requirements of WP.
2014, 31(11):0-0.
Abstract:Using industrial monomer solution of methacrylatoethyltrimethyl ammonium chloride(DMC) as raw material, ammonium persulphate(APS) as initiator and tetrasodium EDTA(Na4EDTA) as chelating agent, the preparation of poly(methacrylatoethyltrimethyl ammonium chloride) (PDMC) was researched, based on the method of adding initiator all at once, two-step increasing of temperature for aqueous polymerization. The optimal process conditions were w(DMC)=72.5%, m(APS):m(DMC)=0.20:100, m(Na4EDTA):m(DMC)=0.018:100, and polymerization carried out at 35℃ and then 50℃, each for 3h via the orthogonal experimental method. The intrinsic viscosity of PDMC product and monomer conversion rate under optimal process conditions reached 10.38 dL•g-1 and 98.40% respectively. Structure of the product was characterized via FTIR and 1HNMR spectra. Thus, this results made a foundation to the further research on the preparation of optimization and serialization PDMC products.
JING Jian-ge , LIU Hui-e , DING Chuan-qin , CHEN Shuang , QI Xuan-liang
2014, 31(11):0-0.
Abstract:Abstract:The Winsor phase diagram and the optimum solubilization parameter curves are used to compare the oil solubilization property among microemulsion systems of four kinds of common anionic surfactants, including sodium dodecyl sulfate (SDS), sodium lauryl sulfonate (SLS), sodium dodecyl benzene sulfonate(SDBS) and sodium alcohol ether sulphate (AES). The order of their solubilization ability is SDBS>AES>SDS>SLS. Mixed surfactants of SDS-octadecyl trimethyl ammonium chloride (OTAC) and SLS-OTAC were used to forming microemulsion systems, respectively. When the optimal mixing ratio was reached, the optimum solubilization parameter(SP*) of SDS/OTAC and SLS/OTAC systems increased by 150% and 170% and the optimum salinity decreased by 91% and 95% respectively when compared with the single SDS and SLS microemulsion systems. It was also found that, when the temperature changes from 20℃ to 50℃, the optimum solubilization parameter of the SDS-OTAC microemulsion system reduced slightly and the optimum salinity only increased slightly. However, when the temperature exceeded 50℃, the optimum solubilization parameter decreased and the optimum salinity increased rapidly.
ZHANG Wen-qi , WEI Jia-qian , CHEN Juan , JI Bin
2014, 31(11):0-0.
Abstract:Through adding cross-linking agent into water-in-oil (W/O) emulsion system of Lipase solution, Lipase spherezymes is formed after emulsifying cross-linked by centrifugation. This paper studies different cross-linking agents, different cross-linking time and different enzyme mass concentration to the affect of spherezymes activity. This paper concludes that the suitable condition of making Lipase spherezymes is: 25% glutaraldehyde solution and 3% polyethyleneimine solution are allowed to react for 5min in a 1︰1 volumetric ratio at room temperature, then the Glu-PEI copolymer is formed and used for cross-linking agent of Lipase spherezymes, and cross-linking time is 2 hour and enzyme concentration is 50g/L, the residual ratio of the Lipase spherezymes activity is up to 86.3%.
CHENG Liang , xu li , HOU Cui-hong , LUO Ting-liang , ZHANG Bao-lin , LIU Guo-ji
2014, 31(11).
Abstract:Abstract:The ordered mesoporous materials V/SBA-15 was prepared by hydro-thermal method under the acidic conditions using P123(tri-block copolymer) as template, tetraethoxysilane(TEOS) as silicon source, citric acid vanadyl complexes as precursors. The influence factors of preparation mesoporous molecular sieves V/SBA-15 including the different crystallization time and the dosage of template agent were systematically investigated. The experimental results showed that under the optimum condition such as the crystallization time 96h and dosage of template agent n=1.0, V/SBA-15 remains a highly ordered two-dimensional hexagonal pore structure of SBA-15, and the load of active ingredient metal vanadium oxide uniformly distributed on the surface of mesoporous. The structure of V/SBA-15 was characterized by the XRD, BET, FT-IR, meanwhile, the catalytic performances were verified by the selectivity and yield of acetophenone in the oxidation of ethyl-benzene to acetophenone reaction. The results displayed under the optimum condition of catalyzation oxidation ethyl-benzene to acetophenone, the selectivity and yield of acetophenone are 82.65% and 38.96%, respectively.
SUN Jiang-bo , YE Yun-ting , ZHU Jiang , WANG Yu , CUI Miao , MENG Chang-gong
2014, 31(11).
Abstract:The supports with secondary building units (SBUs) for zeolite membrane was prepared by MOR zeolite powder using the cold isostatic pressing-solid state sintering method. The propertities of the porous suppport were examined by N2 permeance, open porosity, cross-bending strength, mean pore size and distribution of pore size, the coefficient of thermal expansion, X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The results were that with the rising of sintered temperature and the extending of calcination holding time, N2 permeance and open porosity decreased, but the cross-bending strength increased. The mean pore size became big with the sintered temperature increasing and the distribution of pore size was narrow with a narrow distribution of starting material particle size. The SBUs of 4, 5 and 8 membrane ring of MOR were kept in the supports. The MOR membrane prepared on the support had good thermostability because of the SBUs and low coefficient of thermal expansion (at the level of 10-6 ℃-1).
YUAN Zhen-zhen , Lou Hong-ming , Zhou Ming-song , Huang Jin-hao
2014, 31(11).
Abstract:A softwood Kraft black liquor was acidified with carbon dioxide at different temperatures. The effect of temperature on the recovery yield, the content of inorganics and carbohydrates was investigated. The chemical structure of lignin was determined by GPC, IC, elemental analyzer and TG analyzer. The results showed that a higher temperature was negative to lignin precipitation. The recovery yield of lignin decreased with the temperature increase. However, the lignin, obtained at the higher temperature, had lower ash and carbohydrate contents, and a higher purity. With the increase of temperature, the molecular weight and methoxyl group content of lignin increased, while the phenolic hydroxyl group decreased. TG and DTG curves indicated that the higher acidification temperature resulted in the larger weight loss rate and smaller solid residue mass.
ZHANG Xiao-juan , XIONG Shuang-li
2014, 31(11):0-0.
Abstract:In order to separate and prepare the antioxidant peptide, this article used central composite design and response surface to optimize the extraction process of antioxidant peptide.Taking DPPH radical scavenging rate as response, analyzed the influence of solid-liquid ratio, hydrolysis time and enzyme concentration on the preparation of antioxidant peptides. Got the peptide with antioxidant activity after Sephadex G-50、G-25and G-10 used to separate and purify it, and then measured the DPPH radical scavenging, Superoxide anion radical scavenging activity, ABTS radical scavenging, hydroxyl radical scavenging activity and metal ion chelating activity. The optimum extraction conditions as follows: Solid-liquid ratio was 1:3, extraction time 6h and enzyme concentration 6500U/g at the same time the DPPH radical scavenging was 66.89%. The IC50 of the DPPH radical scavenging, Superoxide anion radical scavenging activity, ABTS radical scavenging, hydroxyl radical scavenging activity were 0.073g/L、0.989 g/L、0.192 g/L and 1.261 g/L, respectively. The IC50 of metal ion chelating activity was 6.505 g/L, the molecular weight was 175.00 Da.
2014, 31(11):0-0.
Abstract:The catalysts of supported potassium iodide were produced using dip method. The catalytic activity were evaluated by the reaction of carbon dioxide, propylene epoxide and glycerol to synthesize glycerol carbonate and KI/γ-Al2O3 was found to be the best one, where the conversion of glycerol was 58.5% and the yield of glycerol carbonate was 54.6%. Different specific surface area of γ-Al2O3 had some effect on KI loading of active component. KI/γ-Al2O3 catalysts were characterized by BET and XRD, which showed that γ-Al2O3 supporter with high specific surface was beneficial to dispersion of KI. At the same time, the effects of reaction temperature, molar ratio of reactants and KI loading on the reaction were investigated and the optimal experimental parameters were obtained. Through repeated using tests, the result showed that the catalysts of KI/γ-Al2O3 had good stability.
2014, 31(11).
Abstract:Mandelic acid was oxidized into vanillin by utilizing a soluble Cu(II) complex. When the molar ratio of CuSO4.5H2O to mandelic acid was 2.5, pH value was 13.5, reaction temperature was 95℃ and reaction time was 8 h, the oxidation yield reached 95.6%. The copper (II) salt can be efficiently recovered in H2SO4 solution by the oxidation of Cu2O in the presence of H2O2, and the activity of the regenerated copper (II) salt has no significant decrease. The yield of vanillin had almost no change each time, and kept at about 95.4% after ten cycles.
GONG Wei , YANG Shao-xiang , SUN Bao-guo , CHEN Kai , LIU Yong-guo , TIAN Hong-yu
2014, 31(11):0-0.
Abstract:The preparation of (R)-gamma-lactones was studied. The racemic homoallylic alcohols underwent kinetic resolution catalyzed by lipase CAL-B to give (R)-homoallylic alcohols and the corresponding acetates with S configuration. After 3 repeated resolutions, the ee values of the products exceeded 95% and the yields were about 40%. (S)-Acetates of homoallylic alcohols were converted to the opposite configuration in about 66% yield after hydrolysis and Mitsunobu reaction. (R)-Homoallylic alcohols reacted with acetic anhydride to produce the corresponding acetates in about 91% yield. (R)-Acetates of homoallylic alcohols were treated with borane in THF and CrO3 in acetic acid aqueous solution to give the intermediates, which were hydrolyzed and cyclized directly without purification to give (R)-gamma-lactones in about 72% yield with >94% ee.
2014, 31(11):0-0.
Abstract:L-pentofuranose derivative(4a) and D-pentofuranose derivative(4b) were synthesized via mesylation, removing isopropylidene group and acetylation with L-ribofuranose (3a) and D-ribofuranose((3b) as starting materials, respectively. Subsequent Vorbruggen coupling with 3-oxo-5,6-dihydropyrazine-2-carboxamide, cyclization, demesylation and debenzylation afforded 7-Hydroxy-1-(hydroxymethyl)-3-[4-(3-oxo-3,4-dihydropyrazine-2-carboxamide)-yl]-2,5-dioxabicyclo[2.2.1] heptane with two different configurations (2a, 2b) in yields 24.6% and 31.5% , respectively. The reaction conditions of ring-closing, demesylation and debenzylation were optimized with yields 83.5%, 62.5% and 86.9%. The chemical structures of target compounds were finely identified by IR, 1H NMR, MS and elementary analysis.
2014, 31(11):0-0.
Abstract:Bis(p-hydroxybenzaldehyde) Schiff base containing piperazine ring,N,N'-bis(4- hydroxybenzyl)-1,4-bis(3-iminopropyl)piperazine, was synthesized with 1,4-bis(3-amino- propyl)piperazine (BAPP) and p-hydroxybenzaldehyde (PHBA) as raw materials. The structure of the product was characterized by means of elemental analysis, IR, 1HNMR and UV-vis spectra. The interaction of the title compound with CT-DNA was investigated by UV-vis absorption spectroscopy and viscosimetry. The hypochromic effect and red shift were observed in the UV-vis absorption spectra, and the relative viscosity of CT-DNA increased with the addition of the title compound. The results indicated that the bis-Schiff base binds to CT-DNA by intercalation mode.
2014, 31(11).
Abstract:In this work, pH/thermo dual responsive tertiary amine starch ether was prepared using N,N-di-n-propyl/butyl-2,3-epoxylpropylamind as tertiary ammoniation reagent. Influences of the reaction conditions to the molecular degree of substitution of the product (MS) were investigated, which including reaction temperature, reaction time, quantity of solvent and catalyst NaOH. As the ratio of AGU to tertiary ammoniation reagent was 1:1, MS could be 0.59, under the optimum condition, at that time, the reaction condition was temperature 90oC, n(NaOH):n(AGU)=0.5, m(H2O):m(AGU)=4, reaction time12h. The result of transmittance of the aqueous solution on different pH showed that this kind of tertiary amine starch has excellent pH/thermo dual responsive property. The cloud points(TC) decreased with the increasing of pH or the length of the carbon chains of alkyl group, which could be adjusted critically in the range of 14.9-77.7oC.
2014, 31(11).
Abstract:Flame charring agent caged dimethicone double cage phosphate were synthesized from 1-oxy phospha-4- (hydroxymethyl)-2, 6, 7- trioxabicyclo [2. 2. 2] octane (PEPA) and dimethyldichlorosilane, it was dimethyl silicate di{1-oxy phospha- 2, 6, 7-trioxabicyclo[2. 2. 2]octane -(4)- methyl} ester (DSDE). The effects of different solvent, eaction temperature and amount ratio of substance on product yield was discussed, the optimal conditions were selected as follows PEPA and dimethyldichlorosilane in molar ratios 2.16:1, the yield was 92.6%. The structure and properties of flame retardant products was characterized by using FTIR, 1H-NMR, elemental analysis, TG-DTA analysis and limiting oxygen index techniques. Experiments showed the product had a good char and thermal stability.
yannan , Xiong Yun-kui , Lin Chun-hua , Lei Zhi-wei , LIAO Wei-lin , XIA Jian-hui
2014, 31(11).
Abstract:In this paper, ten kinds of 5-[(Indol-3-yl)-arylmethyl]-2,2-pentamethylene -1,3-dioxane-4,6-dione derivatives (3-indole derivatives)were synthesized by the three component condensation reactions of indole with aromatic aldehydes and 2,2-pentamethylene -1,3-dioxane-4,6-dione using succinimide-N-sulfonic acid lanthanum as catalyst, without solvent under ultrasonic irradiation. The results indicate that the yield ranged from 82.4% to 98.5%,when using 3%( the mole fraction of indole) succinimide-N-sulfonic acid lanthanum and reacting at 30℃ for 20-60min. In addition, the possible catalytic mechanism for the reaction catalyzed by succinimide-N-sulfonic acid lanthanum was proposed. The advantages of this protocol were mild reacions conditions, short reaction time, wide substrate scope, excellent yields and benign to environment, Furthermore, the catalyst could be recovered four times conveniently and reused efficiently.
ZHANG Ping-hui , ZHAO Zhen-dong
2014, 31(11).
Abstract:Dibornyl oxalate was synthesized from esterification reaction between borneol and oxalic acid catalyzed by metatitanic acid or boron anhydrous. The effect of reaction conditions such as selectivity and dosage of catalyst, material ratio, reaction temperature and reaction time on the conversion of borneol and product selectivity of dibornyl oxalate were explored. The results showed that the optimal synthetic conditions of this reaction were: mass ratio of borneol with anhydrous oxalic acid and catalyst 5.0∶12.0∶3.0, reaction temperature 55℃ and reaction time 96 h. Under the reaction conditions, the conversion rate of borneol and the selectivity of dibornyl oxalate were 95.8% and 99.4%, respectively. The structure of dibornyl oxalate was identified and characterized by HRMS, IR, 1H NMR and 13C NMR.
LIU Ya-ling , LI-Kang-wu , WANG Hai-bin
2014, 31(11).
Abstract:Deoxyarbutin is synthesized by deacetylation of 2-[(4-acetyloxy)]tetrahydropyran, with the sodium borate, which is an intermediate obtained by condensation of 3,4-dihydropyran and monoacetyhydroquinone. Meanwhile, optimisations have been made with yields of 83.4%, 83.9% and 80.4% for each step , and a total yield of 56.3%, which is about 2.5 times of previous result. The procedure of the recent route is performed easily at room temperature, under the presence of common salts(sodium hydrogen sulfate,PPTs,and sodium borate for each step) used as catalysts.
ZHU Cai-yan , ZHANG Qiang , YUE Xia-dan , MA Huimin , MA Jun-jun , ZHANG Tianlin
2014, 31(11).
Abstract:Three kinds of novel unsaturated quaternary ammonium were synthesized with the starting material of 5-chloromethylsalicylaldehyde and unsaturated tertiary amines including dimethylaminoethyl methacrylate(DMAEA), N,N-dimethyl allyl amine(DMAA) and N-methyl-diallylamine(DAMA), and optimized conditions of the model reaction. Through optimizing the reaction conditions, we concluded the ideal conditions:dichloromethane as a solvent, the reaction molar ratio of 5-chloromethylsalicylaldehyde and unsaturated tertiary amines is n(1):n(2a)= 1:1, the reaction temperature is 0℃, and the reaction time is 10 h. Under optimal conditions, the yield of the compounds is all above 90%. The obtained products have been characterized by melting point, IR, 1HNMR, 13CNMR and ESI-MS spectra. Antibacterial activity of the compounds using Oxford Cup were tested. The results showed that three kinds of quaternary ammonium (3a, 3b, 3c) all have good antibacterial activity against Staphylococcus aureus, while there is no significant antibacterial activity against E. coli.
LV Kun-zhi , LIU Yuan-yuan , Li Jie , Gao Shang , HU Lai-feng , Jiang Lu-lu , LI Fang-shi
2014, 31(11):0-0.
Abstract:The pivotal intermediate (E)-methyl 2-(2-(bromomethyl)phenyl)-2-(methoxyimino)acetate of Trifoxystrobin was synthesized from 2-methylacetophenone via a serial of reactions included alkaline oxidation with potassium permanganate in the presence of the phase-transfer catalyst, esterification with methanol, oximation with methoxyamine hydrochloride, bromination with N-bromosuccinimide (NBS). The structure was characterized by melting point and 1H-NMR. Under the optimized reaction conditions, the total yield was 52%.