Synthesis of Polyketone STCO Promoted by Rare Earth Catalyst

To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copoiymerization of carbon monoxide (CO) and styrene (ST) to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2'-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectrosco py respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copoiymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copoiymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/(mol·h).     

Synthesis of polyketone by copolymerization of styrene and CO using carbon nanotube-complex Pd2+ catalyst

The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst(Pd/CNT) for the copolymerization of carbon monoxide(CO) and styrene(ST) towards the formation of polyketone(PK).The Pd/CNT was characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM).The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy(FTIR),13C-nuclear magnetic resonance(NMR) and XRD,respectively.The catalyst showed excellent activity and reusability in promoting the fabrication of PK.It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%.The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.     

Ionic Liquid-Complex Pd/C System as Catalyst for Copolymerization of CO and Styrene简

The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance(13C-NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and gel permeation chromatography(GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid / 1 g active carbon carrier) and the theoretical content of Pd2+ is 5wt%(0.05 g Pd2+/ 1 g active carbon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw /Mn=1.389.     

Strong influences of polymerization temperature on ethylene/1-hexene copolymerization catalyzed by (2-PhInd)_2ZrCl_2/methyl aluminoxane

Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)2ZrCl2/MAO (methyl aluminoxane) at 0 ℃ and 50 ℃ respectively. High copolymerization activity and 1-hexene incorporation were observed at 0 ℃, with the copolymer formed having random sequence distribution and narrow molecular weight distribution. Ethylene polymerization at 50 ℃showed high activity, but copolymerization at 50 ℃ showed much lower activity, which decreased sharply with increasing 1-hexene concentration in the monomer feed. Copolymer formed at 50 ℃ showed blocky sequence distribution and broad molecular weight distribution. A mechanism model based on ligand rotation hindered by the propagation chain has been proposed to qualitatively explain the observed phenomena.     

Effects of fish protein hydrolysate on growth performance and humoral immune response in large yellow croaker (Pseudosciaena crocea R.)

We investigated the effects of fish protein hydrolysate (FPH) on growth performance and humoral immune response of the large yellow croaker (Pseudosciaena crocea R.). One thousand and two hundred large yellow croakers [initial average weight: (162.75±23.85) g] were divided into four groups and reared in floating sea cages (3 m×3 m×3 m). The animals were fed with 4 diets: basal diet only (control) or diets supplemented with 5%, 10% and 15% (w/w) FPH. The results show that dietary FPH levels significantly influenced the growth and immunity of the large yellow croaker. Compared with the control group, total weight gain (TWG) in all treatment groups, relative weight gain (RWG) and specific growth rate (SGR) in fish fed with diets supplemerited with 10% and 15% FPH were significantly increased (P＜0.05). Similar results were observed in immune parameters [lysozyme activity, serum complements, immunoglobulin M (IgM)]. Lysozyme activity, complement C4 and IgM were also significantly increased (P＜0.05) in fish fed with diets supplemented with 10% and 15% FPH, while complement C3 level was significantly increased (P＜0.05) in all treatment groups. In general, with the supplementation of FPH, particularly at dose of 10%,the growth performance and immunity of the large yellow croaker can be improved effectively.     

Synthesis of Novel Ionic Liquid （[C4CNmim]^＋PF6^-） and Application to Preparation of Polyketone

N-valeronitrile-N’-methylimidazolium hexafluorophosphate ([C 4 CNmim]+ PF 6),as a novel ionic liquid with polar nitrile functional group,was prepared.The structure of the ionic liquid was characterized by using IR and 1 H NMR.As a medium,the ionic liquid plays an important role in copolymerization of carbon monoxide (CO) with styrene (St).Some synthetic conditions were determined,including the usage of ionic liquid,palladium composite catalyst and methanol,CO pressure,reaction time and reaction temperature.The influence of these factors on catalytic activity was analyzed.The results show that the catalytic activity has reached 1 724.1 gStCO/(gPd·h) and the catalyst could be reused 5 times under the optimal condition:composite catalyst 0.015 mmol,ionic liquid 3 mL,methanol 0.75 mL,CO pressure 2MPa,reaction time 2 h and reaction temperature 70℃.This CO/St copolymerization within [C 4 CNmim]+ PF 6 system could facilitate ionic liquids with efficient and economical applications to polymeric materials.     

Ni/ZrO_2 Catalysts Synthesized via Urea Combustion Method for CO_2 Methanation

A series of Ni/ZrO_2 catalysts were synthesized by urea combustion method for CO_2 methanation.The effects of zirconium precursors and urea dosage on the structure and catalytic performance of the catalysts were tested.Results showed that the Ni/ZrO_2–O catalyst derived from zirconium oxynitrate hydrate exhibited better catalytic activity than the Ni/ZrO_2 catalyst because of its higher Ni dispersion and smaller Ni particle size.In addition,the urea dosage significantly influenced the low-temperature activity of the catalysts by affecting the metal–support interaction,Ni dispersion,and Ni particle size.The Ni/ZrO_2–O-0.4 catalyst with a urea-to-nitrate molar ratio of 0.4 exhibited the best catalytic activity owing to its moderate metal–support interaction,highest Ni dispersion,and smallest Ni particle size,achieving 69.2% CO_2 conversion and 100% CH_4 selectivity at 300℃,0.1 MPa,and a weight hour space velocity(WHSV)of 50,000 mL/(g·h).Moreover,the urea combustion method can lead to the entire phase transformation from monoclinic ZrO_2 to tetragonal ZrO_2 accompanied by the incorporation of oxygen vacancies in the ZrO_2 lattice.This phenomenon can also be related to the high catalytic activity of the as-prepared catalysts.     

Synthesis of novel electron donors and their application to propylene polymerization

A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.     

Bulk Polymerization of Styrene Using Benzyl Dithiobenzoate as a Chain Transfer

Bulk polymerization of styrene was carried out in the presence of a reversible addition-fragmentation chain transfer (RAFT) of benzyl dithiobenzoate (BDB). The comparison between reaction systems with and without BDB indicates that there is significant retardation in the reaction rate when BDB is used. The molecular weight of styrene polymer prepared with BDB shows linear relationship with the conversion of monomer, polydispersity is as narrow as 1.2, and no gel effects are observed during the polymerization with BDB, which are characteristics of a living radical polymerization. It has been found that the concentrations of BDB and azobis(isobutyronitrile) (AIBN) have opposite effects on the polymerization kinetics, and the AIBN dominates.     

Optimization of Co-precipitation Condition for Preparing Molybdenum-Based Sulfur-Resistant Methanation Catalysts

In this study, the effects of ZrO_2 carrier precursors, MoO_3 loading, and washing treatment on the catalytic performance of Mo O_3/ZrO_2 toward sulfur-resistant methanation were investigated. All the catalysts were prepared by co-precipitation method and further characterized by N_2 adsorption–desorption, H_2-temperature-programmed reduction, X-ray diffraction, Raman spectroscopy and transmission electron microscopy. The prepared MoO_3/ZrO_2 catalysts were tested in a continuous-flow pressurized fixed bed reactor for CO methanation. The results revealed that the carrier precursors, MoO_3 loading, and washing treatment affected not only the crystalline phase of Mo species but also the grain size of ZrO_2 carrier and consequently influenced the MoO_3/ZrO_2 activity toward sulfur-resistant methanation. The 25 wt% MoO_3/ZrO_2 catalyst prepared using Zr(NO_3) 4 ·5 H_2O as the precursor and treated by water washing displayed the best activity for sulfur-resistant methanation due to its greater number of octahedral Mo species and smaller ZrO_2 grain size.     

Graft Copolymerization of Ethyl Acrylate onto Hydroxypropyl Methylcellulose Using Potassium Persulfate as Initiator

Cellulose is one of the mostabundantnatural pol-ymers that have received much attention in research tomodify its physical and chemical structures to improveits properties and broaden its applications. A lot ofwork[1—5]has been reported on the modification viagraft copolymerization of vinyl monomers onto cellu-lose, often using different initiator systems. Variousvinyl monomers such as methyl methacrylate[6,7], 4-vinylpyridine[8], acrylonitrile[9,10], and styrene[11]have been used for cellulos…     

Cloning, expression, purification, and characterization of LC-1 ScFv with GFP tag

INTRODUCTION Because of its low molecular weight and ability to fluoresce independently (George, 1997), the new molecular tag, green fluorescent protein (GFP), has become more and more popular after Prasher et al.(1992) cloned its cDNA in 1992. There are many reports describing the co-expression of GFP and a specific antibody or cytokine gene, with the fusion protein expressing the fluorescent activity and bio-logical activity of the complement protein (Haraguchi et al., 1999; Mclean…     

强碱性介质中锡酸钠与邻羟基苯酚对铝阳极的协同抑氢作用

The performance of Al-alloy anode in 4 mol/L KOH with and without stannate and o-aminophenol at 25℃and 55℃was studied by hydrogen collection,potentiodynamic polarization and electrochemical impedance spectrum,o-amino- phenol acts as a perfect inhibitor because of its adsorbability and forming chelate complex at its optimum concentration of 0.4 mol/L.Stannate enhances the inhibition of o-aminophenol and improves the activity of Al-alloy because of its reduction to tin.There is synergetic effect of stannate with o-aminophenol on the behavior of Al-alloy,and the inhibitive efficiency at 55℃is better than that at 25℃.     

Catalytic effects of V_2O_5 on oxidative pyrolysis of spent cation exchange resin

Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins. In this work, the catalytic effects of V_2O_5 on the pyrolysis of cation exchange resin are investigated for the first time. The results show that it is a better catalyst than others so far studied and achieves a lowering of final pyrolysis temperature and residual rate simultaneously when aided by physical blending. The maximum reductions of the final pyrolysis temperature and the residual rate are 173 ℃ and 11.9%(in weight), respectively. Under the action of V_2O_5, low-temperature(445℃) removal of partial sulfonic acid groups occurs and the pyrolysis of the resin copolymer matrix is promoted. This is demonstrated by the analysis of pyrolysis residues at different temperatures by X-ray photoelectron spectroscopy(XPS) and element analysis. The catalytic activity of V_2O_5 is determined by effects both at acid sites and oxidation-reduction centers via H_2-TPR(temperature programmed reduction), O_2-TPD(temperature programmed desorption), CO_2-TPD, and NH_3-TPD. The catalytic effect of oxidation-reduction centers in V_2O_5 is achieved by close contact with the sulfur bond through chemisorption under the effect of acid sites. V_2O_5 is also believed to be the reason for the removal of partial sulfonic acid groups at lower temperatures(445℃). V_2O_5 is an effective catalyst for spent resin pyrolysis and can be further applied in industry.     

Purification and Biochemical Characterization of D-hydantoinase and D-N-carbamoylase from Burkholderia cepecia, njut01

Hydantoinase and N-carbamoylase play important roles in the production of optically pure amino acids from racemic 5-monosubstituted hydantoins. In this report, hydantoinase and the N-carbamoylase from Burkholderia cepecia, njut01 were purified to homogeneity by chromatography (Pharmacia Explorer 100 system). The substrate specificity, enantioselectivity, pH dependence of activity and temperature stability of the activity were characterized. The results show that the hydantoinase and N-carbamoylase induced from Burkholderia cepecia, njut01 are both strict D-stereo selective enzymes. They both hydrolyze substrates with side chains containing aliphatic and aromatic residues with higher activity and affinity toward aromatic than aliphatic substituted substrates. The hydantoinase is a homotetramer with subtmit molecular weight near 52,000 and is active between pH 6.5 and 10 with an optimum near pH 9.0. The enzyme is active at temperatures up to 60~C, however, it appears instable at higher temperatures. The subunit molecular weight of N-carbamoylase is about 35KD. The N-carbamoylase is active in the pH range from 6.0 to 9.5. The optira-pH is 7.2 and the optinfizing bioconversion temperature of the N-carbamyolase is 52℃.     

Performance of Methanol-to-Olefins Catalytic Reactions by the Addition of PEG in the Synthesis of SAPO-34

SAPO-34, a silicoaluminophosphate zeolite, has been synthesized by the hydrothermal method with the addition of different molecular weights of polyethylene glycol(PEG), and has been characterized with XRD, SEM,N_2 adsorption–desorption, FT-IR, and NH_3 temperatureprogrammed desorption(NH_3-TPD). We studied SAPO-34 as a catalyst in the methanol-to-olefins(MTO) reaction, in a fixed-bed reactor. The results show that the chain length of PEG has a great influence on the particle size and morphology of SAPO-34. PEG acts as inhibitor in the crystallization process. With the increase of the chain length of PEG used in the synthesis, from a relative molecular weight of 400-6000, the morphology of SAPO-34 changes gradually from cubic to nanoplate-like and then changes to cubic again. The particle size decreases markedly at first and then increases to some extent. The catalytic stability in the MTO reaction also increases first and then decreases, with all the catalysts having almost the same selectivity to olefins. When the sample is synthesized with PEG800, the particles become nanoplate-like with a thickness of 46 nm on average, and the catalytic stability is appreciably prolonged, which is attributed to the shorter diffusion paths of the reactants in the zeolite.     

Microwave-assisted synthesis, anticonvulsant activity and quantum mechanical modelling of N-（4-bromo-3-methylphenyl） semicarbazones

Objective： To study the effect of halo substitution on disubstituted aryl semicarbazones on the anticonvulsant potential and model the activity based on quantum mechanics. Methods： A series of twenty-six compounds of N^4-（4-bromo-3-methylphenyl） semicarbazones were synthesized and evaluated for the anticonvulsant activity in the maximal electroshock seizure （MES） and subcutaneous pentylenetetrazole （scPTZ） seizure threshold tests. Some potential compounds were also tested in the subcutaneous strychnine （scSTY） and subcutaneous picrotoxin （scPIC） seizure threshold tests. The synthesized compounds were tested for behavioral impairment and CNS （central nervous system） depression in mice. Quantum mechanical modelling was carried out on these compounds to gain understanding on the structural features essential for activity. Results： Some compounds possessed broad spectrum anticonvulsant activity as indicated by their effect in pentylenetetrazole, strychnine, picrotoxin and maximal electroshock seizures models in resemblance to other aryl semicarbazone derivatives reported earlier. The higher the difference in HOMO （highest occupied molecular orbital） and LUMO （lowest unoccupied molecular orbital） energy levels was, the greater was the activity profile. Conclusion： The pharmacophoric requirements for compounds to exhibit anticonvulsant activity that includes one aryl unit in proximity to a hydrogen donor-acceptor domain and an electron donor have been justified with the molecular orbital surface analysis of the synthesized compounds.     

Preparation and application of supported amorphous alloy catalyst CoP/TiO2

A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC Its application in decomposing PH3 to high purity phosphor and its catalytic activity were studied. The decomposition rate is over 95% at 450 ℃. For comparison, unsupported CoP amorphous catalyst was prepared by the same method. The result suggests that CoP/TiO2 exhibits higher thermal stability and catalytic activity than CoP, which is attributed to the high dispersion of CoP alloy particles on the support-TiO2.     

Molecular dynamics simulation and microscopic observation of compatibility and interphase of composited polymer modified asphalt with carbon nanotubes

Interfacing and compatibility are the most challenging issues that affect the performance of polymer modified asphalt. Mechanisms of interfacial enhancement among four base asphalt components(asphaltenes, resins, aromatics, and saturate), styrene-butadiene-styrene(SBS), and carbon nanotubes(CNTs) were investigated by molecular dynamics simulation, with the aim of understanding the key parameters that control the compatibility of CNTs and interphase behavior on the molecular scale. The compatibility of SBS-modified asphalt(SBSMA) was simulated based on self-assembly theory using indexes of binding energy, mean square displacement, diffusion coefficient, and relative concentration distribution. The interphase behavior and microstructure were observed by fluorescence microscopy and scanning electron microscopy. In addition, a rutting experiment was used to verify the molecular dynamics simulation based on macroscopic performance. The results showed that after adding CNTs, the binding energy of the SBS and aromatics increased from 301.8343 to 327.1102 kcal/mol. The diffusion coefficient of the SBS and asphaltenes decreased more than 3.2×10-11 m2/s, and the correlation coefficients between the diffusion coefficient and the molecular weight, surface area and volume were all lower than 0.3. Relative concentration distribution curves indicated that CNTs promote the ability of SBS to swell. Microscopic observations demonstrated that the swelling ability of SBS was increased by CNTs. Overall, the interphase of SBSMA was improved by the additional reinforcement, swelling, and diffusion provided by CNTs. Finally, the rutting experiment found that no matter what the temperature, the rutting factor of CNT/SBSMA is higher than that of SBSMA, which corroborates the findings from the molecular dynamics simulations.