增强型离子交换树脂催化醚化汽油TAME的合成

在高压釜式反应器中,以甲醇和异戊烯为原料,增强型离子交换树脂Amberlyst为催化剂,制备了高辛烷值醚化汽油组分TAME。改变反应温度、催化剂用量等单一实验变量,探索得到了最佳工艺条件:反应温度70℃,催化剂用量为20%,醇/烯比为2。在最优条件下,该催化反应只需进行4.5h,TAME的摩尔产率就达到70%。

Synthesis and Characterization of Novel Hydrolytically Degradable Polyesters

Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.

Preparation of Nitrogen-doped Carbon Dots from Coke Powder as a Fluorescent Chemosensor for Selective and Sensitive Detection of Cr (Ⅵ)

The nitrogen-doped carbon dots(N-CDs)were prepared by using coke powder as carbon source and one-step hydrothermal method.The N-CDs were studied as a fluorescent chemosensor for determining Cr(Ⅵ)in water.The selective,sensitive,reproducibility and stability of as-prepared N-CDs were investigated.The morphology,composition and properties of N-CDs were characterized by a series of methods.The fluorescence quenching of N-CDs by Cr(Ⅵ)was explored.The experimental results reveal that the obtained N-CDs have great hydrophilicity and strong luminescence properties,which demonstrates the successful doping of nitrogen into the CDs.The surface-active groups and emission wavelength range of CDs increase due to the electronegativity and electron donor effect of doping N atom.Furthermore,the N-CDs exhibit good photochemical properties for the detection of Cr(Ⅵ),including a wide linear range from 0.3 to 200μM(R^(2)=0.9935)and a low detection limit of 0.10μM at the signal-to-noise ratio of 3(S/N=3).Moreover,the N-CDs as a sensor was used successfully for Cr(Ⅵ)detection in real water samples with recovery rates of 99.9%-110.6%.This sensor also shows highly reproducibility and stability.The N-CDs fluorescent chemical sensor may be a potential candidate for applying in the field of other fluorescent chemical sensing,catalysis,photoelectric devices and other fields.

基于CFD模拟的聚丙烯环管反应器非稳态分析

聚丙烯环管反应器中颗粒的非均匀流动现象是引发轴流泵功率波动的重要原因。基于CFD非稳态模拟,研究了环管反应器管内液固两相流体在时间尺度上的非均匀流动特性,并对比了颗粒粒径对非均匀流动的影响。模拟发现,颗粒粒径越大,环管出口处颗粒浓度及非均匀度的波动幅度和波动频率越大,越不利于轴流泵的稳定操作。此外,液固两相流体在经过环管反应器的弯头后,颗粒团聚物等结构会导致固相体积分数出现新的周期行为(脉动频率约为10 Hz),这使得流场的湍动程度加剧、颗粒-颗粒及颗粒-壁面间的摩擦碰撞加剧以及能量耗散加快。

乙醛酸的氧气-硝酸联合氧化制备及快速分析

在氧气辅助下,硝酸选择性氧化乙二醛制备了乙醛酸。在单因素试验基础上,通过高效液相色谱法,考察了通氧速率、保温反应温度、硝酸用量等因素对乙二醛转化率和乙醛酸收率的影响。研究结果表明:制备乙醛酸的最佳反应条件为通氧速率50 m L/min,保温反应温度60℃,硝酸与乙二醛物质的量比0. 59。在此条件下,乙二醛转化率为99. 00%,乙醛酸收率为84. 00%。与传统的硝酸氧化生产工艺相比,硝酸物质的量降低近10%,乙醛酸收率提高了5%以上。

Preparation of Different Lights Irradiated ZnSe/GSH QDs and Their Interaction with BSA

Using L-glutathione(GSH) as a capping agent,Zn Se/GSH quantum dots(QDs) were prepared under microwave irradiation and irradiated under dark, ultraviolet light and incandescent light, respectively. The properties and interaction of different lights irradiated ZnSe/GSH QDs and bovine serum albumin(BSA) were studied systematically. The fluorescence(FL) spectra results reveal that the quenching mechanism are all the static quenching in nature. The quenching constant(Ksv) and binding constant(K) value of different irradiated Zn Se/GSH QDs and BSA all increased with the change of light types from dark to incandescent light and UV light. The number of binding site(n) is close to 1 at different temperatures. The lighting types influence the enthalpy and entropy changes. The Fourier transform infrared(FTIR) spectra indicate that the light induced GSH ligand will facilitate photocatalytic oxidation on the surface of ZnSe/GSH QDs. The circular dichroism(CD)results show that the α-helicity content of BSA decreases from 60.34%, 59.31%, to 58.79% under UV lighting,incandescent lighting and dark conditions. The interaction results of different lights illuminated ZnSe/GSH QDs with BSA by CD spectra method matches well with that by FL and FTIR spectra. That is, the interaction of ZnSe/GSH QDs and BSA from strong to weak is UV light, incandescent light and dark in sequence.

Lewis酸催化三组分合成喹啉-2,4-二羧酸酯类化合物

采用价廉易得的无水三氯化铝、三氯化铁、氯化铜等Lewis酸催化取代芳胺、乙醛酸乙酯和丙酮酸甲酯三组分一步反应,高效合成了4个喹啉-2,4-二羧酸酯类化合物.产物通过柱层析分离纯化,并采用FT-IR、~1H NMR、^(13)C NMR和元素分析等手段进行了结构表征.探讨了反应机理和取代芳胺的分子结构对反应的影响规律,为该类新颖化合物的分子设计与合成方法提供参考.该方法具有原料廉价易得、反应条件温和、原子经济性高、产率高等优点.

Synthesis and Characterization of Poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) Copolyester

Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.

Synthesis of Magnetically Modified Fe-Al Pillared Bentonite and Heterogeneous Fenton-like Degradation of Orange II

Magnetically modified Fe-Al pillared bentonite（Fe3O4/ Fe-Al-Bent） was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction（XRD）, Brunauer-EmmettTeller（BET）, Fourier transform infrared spectroscopy（FTIR） and scanning electron microscopy（SEM）. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous catalysts in the presence of H2O2. The experimental result indicated that the synthetic materials had a high catalytic activity and good reusability.

Microwave Synthesis of CdTe/TGA Quantum Dots and Their Thermodynamic Interaction with Bovine Serum Albumin

The thioglycollic acid（TGA） as a capping agent, CdTe/TGA quantum dots（QDs） with excellent properties were synthesized under microwave irradiation. The TGA/Cd/Te molar ratios, reaction time, temperature and p H are the crucial factors for properties of QDs. The QDs were characterized by UVvis absorption and fluorescence spectra, transmission electron microscopy and Fourier transform infrared spectroscopy. The experimental results show that when the p H value is 11.5 and molar ratio of TGA：Cd：Te is 1.2：1：0.4 at 100 ℃ heating for 15 min, the resulted QDs exhibit a high fluorescence quantum yield of 78%. The fluorescence full width at half maximum（FHMW） of QDs is around 23 nm. The products are spherical with average size of 3-5 nm. There is a strong coordination effect between TGA and Cd2＋. Moreover, the results of interaction between as-made QDs and bovine serum albumin（BSA） suggest that the QDs-BSA binding reaction is a static quenching. The negative values of free energy（△G〈0） suggest that the binding process is spontaneous, △H〈0 and △S〈0 show that hydrogen bonds and van der Waals interactions play a major role in the binding reaction between QDs and BSA.

Synthesis of Agomelatine by One-pot Catalytic Hydrogenation and Acetylation with NiO

Nano-NiO and bulk NiO were prepared from Ni(AC)_2·4 H_2O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Diffraction(XRD) and scanning electron microscopy(SEM). The results indicate that nano-sized NiO has a crystal phase with a standard face-centered cubic lattice structure, with a mean particle diameter of about 10 nm. The evaluation of the activity of nickel oxide nanoparticles in the catalytic hydrogenation of 7-methoxy-1-naphthylacetonitrile was carried out. The results demonstrate the efficient synthesis of the title compound by a one-pot catalytic hydrogenation and acetylation with NiO. The NiO nanoparticles displayed superior catalytic activity in the synthesis of agomelatine in the one-pot reaction.The total yield of agomelatine is over 81.8% with a purity of 99.2%, as determined by HPLC. The structure of agomelatine was confirmed by IR, MS, and 1 H NMR analysis.

Degradable Polyesters based on Oxygenated Fatty Acid Monomer

A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.

基于含硫单体的可降解聚酯的表征与性能

以硫代二丙酸和间苯二酚二(2-羟乙基)醚为主要原料,Sb2O3为催化剂,通过熔融缩聚法合成了聚(硫代二丙酸-间苯二酚二(2-羟乙基)醚)酯。采用FT-IR、1H NMR,对聚酯的结构进行了表征;采用GPC、DSC、TGA测试其相对分子质量和热性能;并采用自然掩埋法,对其在土壤中的降解性能进行了考察。结果表明:该新型含硫聚酯数均相对分子质量和重均相对分子质量分别为12634 g/mol和19708 g/mol、热分解5%温度为351.7℃,热分解50%温度为401.5℃,熔点为99.12℃,ΔHm为90.12 J/g,且在自然土壤环境下经过24个月的降解,聚酯P的失重率达到9.3%,具有较好的降解性能。

可降解含氮聚酯的合成与性能

以N-(羧甲基)甘氨酸和对苯二酚二(2-羟乙基)醚为主要原料,三氧化二锑为催化剂,采用熔融聚合法,合成聚[N-(羧甲基)甘氨酸-对苯二酚二(2-羟乙基)醚]酯(P1)。采用FT-IR、1H-NMR对聚酯P1结构进行了表征;采用GPC、DSC、TGA测试其分子量和热性能;并采用自然掩埋法,对其在土壤中的降解性能进行了研究。GPC测试结果表明,该聚酯具有较高的分子量,Mn为41500g/mol。TG结果显示,该聚酯有良好的热稳定性,起始热分解温度高于333℃。在自然土壤环境下,聚酯P1经过两年的降解,分子量下降20%,降解性能好,具有良好发展前景。

Properties of Magnetite Nanoparticles Produced by Magnetotactic Bacteria

The magnetic nanoparticles（magnetite） were prepared through the fermentation of the Magnetospirillum strain WM-1 newly isolated by our group. The samples were characterized by TEM, SAED, XRD, rock magnetic analysis, and Mossbauer spectroscopy. TEM and SAED measurements showed that the magnetosomes formed by strain WM-1 were single crystallites of high perfection with a cubic spinel structure of magnetite. X-ray measurements also fitted very well with standard Fe3O4 reflections with an inverse spinel structure of the magnetite core. The size of crystal as calculated by the Debye-Scherrer’s equation was approximately 55 nm. Rock magnetic analysis showed WM-1 synthesized single-domain magnetite magnetosomes, which were arranged in the form of linear chain. The high delta ratio（（δFC / δZFC = 4） supported the criteria of Moskowitz test that there were intact magnetosomes chains in cells. The Verwey transition occurred at 105 K that closed to stoochiometric magnetite in composition. These observations provided useful insights into the biomineralization of magnetosomes and properties of M. WM-1 and potential application of biogenic magnetite in biomaterials and biomagnetism.