含有三氟乙烯基芳基醚侧基的聚丙烯酸酯的合成与表征

研究了聚丙烯酸酯侧基上引入三氟乙烯基芳基醚结构单元的方法. 首先, 合成了含有三氟乙烯基芳基醚侧基的丙烯酸酯单体, 然后通过原子转移自由基聚合实现了该单体的均聚和无规共聚, 得到了含有三氟乙烯基芳基醚侧基的聚丙烯酸酯聚合物, 聚合物的分子量分布较窄. 通过控制共聚投料比, 可以得到具有不同含量三氟乙烯基芳基醚侧基的无规共聚物.     

Controlled adsorption of cellulase onto pretreated corncob by pH adjustment

The effective recycling of cellulase requires an in-depth understanding of cellulase adsorption and desorption. In the present study, we examined the adsorption behaviors and stabilities of cellulase at different pH values. Acidic pH (<4.8) was found to favor adsorption, whereas neutral and alkaline pH (especially pH 7 and 10) favored desorption. The influence of pH on cellulase activity was temperature dependent. Under mild conditions (e.g., pH 7 and 25 °C), the effect of pH on cellulase activity was reversible, and the cellulase activity can return to almost 100% by adjusting the pH value to 4.8. However, under severe conditions (e.g. pH 10 and 50 °C), irreversible inactivation may take place. We also explored the roles of pH and temperature in cellulase adsorption kinetics and isotherms. At pH 4.8, temperature had no remarkable effect on the adsorption capacity of the cellulases onto substrate. However, at pH 7 and 10, high temperatures lead to more cellulase desorption. Only at pH 4.8 does cellulase adsorption well fit (R ² > 0.96) the pseudo-first-order kinetic and Langmuir adsorption isotherm (R ² > 0.99) models.     

基于5-甲基-3-吡唑甲酸为配体的钴(Ⅱ)、镍(Ⅱ)配合物的合成、晶体结构和电化学性质

利用5-甲基-3-吡唑甲酸、咪唑和相应醋酸盐在乙醇和水混合溶剂中反应,得到了配合物[M(MPA)2(Im)2].2H2O(1:M=Co;2:M=Ni)(HMPA=5-甲基-3-吡唑甲酸,Im=咪唑)。用元素分析、红外光谱、X-单晶衍射结构分析、热重分析、循环伏安等对其进行了表征。配合物1和2的晶体结构参数如下:配合物1和2的晶体都属于单斜晶系,空间群为P21/n。配合物1的晶胞参数为a=0.847 02(16)nm,b=1.461 5(3)nm,c=0.899 67(17)nm,β=101.759(6)°,V=1.090 3(4)nm3,Z=2;配合物2的晶胞参数为a=0.853 59(6)nm,b=1.451 77(9)nm,c=0.889 83(6)nm,β=102.382 0(10)°,V=1.077 04(12)nm3,Z=2。金属离子与来自2个5-甲基-3-吡唑甲酸配体中的2个氮原子及2个氧原子,2个咪唑分子中的2个氮原子配位,形成八面体配位构型。配合物中的独立结构单元[M(MPA)2(Im)2].2H2O通过2种分子间氢键(N-H…O和C-H…O)形成三维超分子。循环伏安性质测试表明配合物1和2的电解过程均为准可逆过程。     

Brφnsted酸性离子液体催化合成长链脂肪酸甲酯

本文合成了以1-丁基-3-甲基咪唑为阳离子,HSO4-、H2PO4-和BF4-为阴离子的Brφnsted酸性离子液体,并以长链脂肪酸与甲醇的酯化反应考察了这些Brφnsted酸性离子液体的催化性能。实验结果表明,1-丁基-3-甲基咪唑硫酸氢根鎓盐([bmim][HSO4])离子液体具有很高的催化活性,当n(醇)∶n(酸)∶n(离子液体)=6∶1∶0.25,反应温度为70℃,不分水酯化反应2h,长链脂肪酸甲酯的产率可达到93.4%以上,选择性达到100%;且产物酯与离子液体分离容易;离子液体经干燥处理后可以循环使用5次以上,催化活性没有明显降低。     

Flexible Magnetic Nanoparticles–Reduced Graphene Oxide Composite Membranes Formed by Self‐Assembly in Solution

A facile and robust route for the pre‐synthesized Fe₃O₄ nanoparticles (NPs) exclusively assembled on both sides of reduced graphene oxide (RGO) sheets with tunable density forming two‐dimensional NPs composite membranes is developed in solution. The assembly is driven by electrostatic attraction, and the nanocomposite sheets display considerable mechanical robustness, such as it can sustain supersonic and solvothermal treatments without NPs falling off, also, can freely float in solution and curl into a tube. The obtained two‐dimensional composite grain membranes exhibit superparamagnetic behavior at room temperature but responds astutely to an external magnetic field. In addition, these magnetic composite membranes show an enhanced absorption capability for microwaves. The grain sheets are attractive for biomedical, sensors, environmental applications and electric‐magnetic devices benefited from large surfaces, high magnetization moment, and superparamagnetic properties. The effective integration of oxide nanocrystals on RGO sheets provides a new way to design semiconductor–carbon nanocomposites for nanodevices or catalytic applications.     

氢化物发生-原子荧光光谱法测定海产品中总砷

采用氢化物发生-原子荧光光谱法测定海产品中总砷的含量。样品经硝酸-高氯酸(4+1)混合酸消解,样品溶液中加入硫脲和抗坏血酸混合溶液作为预还原剂。于盐酸(5+95)溶液中加入10g.L-1硼氢化钾-5g.L-1氢氧化钾溶液使与溶液中砷离子反应生成氢化物。分析时采用载气流量为400mL.min-1,屏蔽气流量为800mL.min-1。砷的质量浓度在20μg.L-1以内与荧光强度呈线性关系,方法的检出限(3s/k)为0.015μg.L-1。应用此法对3种海产品进行分析,测定值的相对标准偏差(n=6)在3.4%～4.2%之间,回收率在98.5%～101.0%之间。     

含能配合物[Zn(CHZ)3](C1O4)2的晶体结构、热行为及感度性能研究

通过碳酰肼水溶液与高氯酸锌水溶液反应制得含能配合物[zn(cHZ)3](CIO4)2.培养获得了配合物的单晶,用x射线单晶衍射法测定了晶体结构,该晶体属于单斜晶系、P2(1)/n空间群,晶胞参数a=1.0005(2)nm,b=0.8428(1)nm,c=2.1218(4)nm,β=100.948(3)°,y=1.756...     

液相色谱-三重串联四极杆质谱测定粮油中的黄曲霉毒素

建立了超声提取-液相色谱-电喷雾三重串联四极杆质谱测定玉米、大米、大豆等粮油固体样品中黄曲霉毒素B1、B2、G1和G2(AFB1、AFB2、AFG1和AFG2)的方法。分析前对样品进行超声提取,优化得到最佳超声提取条件: 溶剂为甲醇-水(含40 g/L NaCl) (80:20, v/v)溶液、料液比为1:3(g:mL)、温度为50 ℃、时间为3 min。然后对提取的样品进行免疫亲和特异性净化。最后与液相色谱-电喷雾三重串联四极杆质谱联用,使用C18反相色谱柱,流动相为甲醇-10 mmol/L乙酸铵水溶液梯度洗脱,以黄曲霉毒素M1(AFM1)作为内标进行定量测定。结果表明,AFB1、AFB2、AFG1和AFG2的检出限分别为0.002、0.004、0.004和0.012 μg/kg。方法的加标回收率为87%～111%,日内相对标准偏差(RSD)和日间RSD分别不大于6.7%和5.6%。实验结果表明该方法可以有效地降低基质效应的影响,相比于外标法能极大地提高方法的准确度。     

SCR脱硝催化剂失活及其原因研究

以运行后的蜂窝型SCR（Selective catalytic reduction）催化剂和新鲜催化剂为研究对象。应用红外光谱、氮气吸脱附、X射线衍射、电镜扫描等手段对新鲜催化剂及运行后催化剂进行表征。结果表明,运行后催化剂表面官能团发生了变化,比表面积严重降低,载体（TiO₂）产生了型变,并且催化剂表面微粒出现了团聚现象。对运行后催化剂活性降低的原因进行了研究,结果表明,脱硝催化剂在运行过程中遭遇了突发性高温(如t> 650℃),导致活性出现劣化。此外,催化剂表面沉积物中水溶性离子及砷、磷等物质也对催化活性产生了影响。     

溶剂诱导聚合物结晶的研究进展

溶剂诱导结晶(SINC)又称为液体诱导结晶,它是结晶性高聚物在溶剂(或包括其蒸汽)作用下,在低于通常Tg下诱导结晶,而在高于通常Tg时能加速结晶的现象。本文主要对溶剂诱导结晶的机理、动力学和形态学进行了讨论。