Separation and analysis of trace volatile formaldehyde in aquatic products by a MoO3/polypyrrole intercalative sampling adsorbent with thermal desorption gas chromatography and mass spectrometry

An in situ embedded synthesis strategy was developed for the preparation of a MoO₃/polypyrrole intercalative sampling adsorbent for the separation and analysis of trace volatile formaldehyde in aquatic products. Structural and morphological characteristics of the MoO₃/polypyrrole intercalative adsorbent were investigated by a series of characterization methods. The MoO₃/polypyrrole sampling adsorbent possessed a higher sampling capacity and selectivity for polar formaldehyde than commonly used commercial adsorbent Tenax TA. Finally, the MoO₃/polypyrrole adsorbent was packed in the thermal desorption tube that was directly coupled to gas chromatography with mass spectrometry for the analysis of trace volatile formaldehyde in aquatic products. Trace volatile formaldehyde from real aquatic products could be selectively sampled and quantified to be 0.43–6.6 mg/kg. The detection limit was achieved as 0.004 μg/L by this method. Good recoveries for spiked aquatic products were achieved in range of 75.0–108% with relative standard deviations of 1.2–9.0%.     

PAN-based activated carbon nanofiber/metal oxide composites for CO2 and CH4 adsorption: influence of metal oxide

In the present study, we successfully prepared two different electrospun polyacrylonitrile (PAN) based-activated carbon nanofiber (ACNF) composites by incorporation of well-distributed Fe₂O₃ and Co₃O₄ nanoparticles (NPs). The influence of metal oxide on the structural, morphological, and textural properties of final composites was thoroughly investigated. The results showed that the morphological and textural properties could be easily tuned by changing the metal oxide NPs. Even though, the ACNF composites were not chemically activated by any activation agent, they presented relatively high surface areas (S_BET) calculated by Brunauer–Emmett–Teller (BET) equation as 212.21 and 185.12 m²/g for ACNF/Fe₂O₃ and ACNF/Co₃O₄ composites, respectively. Furthermore, the ACNF composites were utilized as candidate adsorbents for CO₂ and CH₄ adsorption. The ACNF/Fe₂O₃ and ACNF/Co₃O₄ composites resulted the highest CO₂ adsorption capacities of 1.502 and 2.166 mmol/g at 0 °C, respectively, whereas the highest CH₄ adsorption capacities were obtained to be 0.516 and 0.661 mmol/g at 0 °C by ACNF/Fe₂O₃ and ACNF/Co₃O₄ composites, respectively. The isosteric heats calculated lower than 80 kJ/mol showed that the adsorption processes of CO₂ and CH₄ were mainly dominated by physical adsorption for both ACNF composites. Our findings indicated that ACNF-metal oxide composites are useful materials for designing of CO₂ and CH₄ adsorption systems.     

A new catalytic mode of the modularly designed organocatalysts (MDOs): enantioselective synthesis of dihydropyrano[2,3-c]pyrazoles

The enantioselective tandem Michael addition-cyclization reaction between 3-methyl-2-pyrazolin-5-one and benzylidenemalononitriles was studied with modularly designed organocatalysts (MDOs) to yield 6-amino-5-cyanodihydropyrano[2,3-c]pyrazoles in high yields and moderate to good enantioselectivities. Most importantly, a new catalytic mode of the MDOs was established. Instead of being used as a nucleophile to form an enamine intermediate, the reaction center modules (amino acids) of the MDOs are now used as a Lewis base in this base-catalyzed reaction. Since there are more reactions catalyzed by Lewis bases than by the enamine mechanism, this finding greatly expands the scope of the MDOs in organic reactions. On the other hand, because the stereocontrolling modules (cinchona alkaloid derivatives) themselves may be used as Lewis base catalysts, this new method may also be viewed as an expeditious way for the modification of the reaction center of the cinchona alkaloid catalysts.     

Synthesis of a Cationic Polymer-Bentonite Composite Utilizing a Simple and Green Process for the Adsorption of Acid Orange 7 from Aqueous Solution

A one-step, green process is reported for synthesis of poly([2-(methacryloyloxy)ethyl] trimethylammonium chloride) (PMETAC) modified bentonite (Bent-PMETAC). The Bent-PMETAC was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Zeta potential, scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA). The results indicated that large amounts of PMETAC were successfully grafted on the surface and interlayers of bentonite, and changed the Zeta potential of the sample from negative to positive. Acid Orange 7 (AO 7), as adsorbate, was used to test the anionic dye adsorption of the samples. The batch adsorption results implied that this novel Bent-PMETAC adsorbent exhibited a much higher removal (95%) of AO 7 than bentonite (10%). In addition, the adsorption process was hardly influenced by pH, which is in good agreement with the results of the Zeta potential analysis. The equilibrium adsorption isotherms and the adsorption kinetics of AO 7 fitted well to the Langmuir model and pseudo-second-order kinetic model, respectively. The maximum adsorption capacity of AO 7 onto Bent-PMETAC was 208.6?mg·g^?1 at 298?K, which is much higher than for most other materials. Overall, the results indicated the Bent-PMETAC is a low-cost, simple synthesis and highly efficient adsorbent for anionic dye removal from aqueous solutions.     

带电聚合电介质表面吸附理论研究

应用聚合电介质吸附的定标理论,根据介质和表面电介质常数的比率,考虑多化合价吸附电介质之间强相关性作用,我们提出一种表面排斥电荷的近似定标理论方法,根据这种方法把电介质表面吸附层的相图分为本质上不同的两大类。从相图可知：当表面电荷密度低（或体带相反电荷离子密度高）,这时表面和体带相反电荷离子密度几乎相同;一旦表面电荷密度足够高,就使带相反电荷的离子在表面上浓缩。据此,可确定在这个区域内,低化合价聚合电介质形成一个相关的多链状态,当化合价足够高时,由于近邻链之间的更强排斥增强,使状态转变成单链。     

Selective removal of caffeine from tea extracts using macroporous crosslinked polyvinyl alcohol adsorbents

The hydrolysis reaction of ester groups in vinyl acetate (VAc) was used to introduce hydroxyl groups into the matrix of a macroporous adsorbent, which was itself prepared by free radical suspension copolymerization of triallyl isocyanurate (TAIC) and VAc. Therefore, the copolymerization incompatibility between the hydrophilic and the hydrophobic monomer was overcome successfully and the hydrophobic matrix of the polymeric adsorbent containing a polyvinyl alcohol (PVA) segment was obtained. Introduction of the PVA segment decreased the hydrophobic adsorption affinity of the adsorbent while producing the hydrogen-bonding interaction. When isolating the two active components, polyphenols (TPh) and caffeine (CAF), from green tea extracts, this polymeric adsorbent, namely poly(TAIC-co-VA), exhibited good adsorption selectivity towards TPh over CAF. The adsorption mechanism leading to this selectivity involved a hydrophobic interaction mechanism for CAF and multiple weak hydrophobic and hydrogen-bonding interactions for TPh. The adsorption thermodynamics for TPh on poly(TAIC-co-VA) were studied. The effects of adsorbent structure and gradient desorption conditions on isolation were investigated. The result showed that adsorbent, with 20% TAIC content, was able to efficiently remove CAF from different tea extracts with different ratios of TPh and CAF. Finally, almost no CAF was detected in the TPh fraction and the recovery of TPh was greater than 95%.     

基于QuEChERS-HPLC法检测油炸食品中丙烯酰胺的含量

建立了基于QuEChERS(quick,easy,cheap,effective,rugged and safe)-HPLC测定油炸食品中丙烯酰胺含量的方法。 该方法的优势在于：改进的QuEChERS前处理方法中没有引入有机溶剂而直接采用纯水消除样品基底的影响。 研究中,使用纯水超声提取丙烯酰胺,丙基乙二胺(PSA)吸附剂分散净化提取液,乙腈和水(体积比1∶99)作为流动相,水系C18色谱柱分离,208 nm紫外波长条件下检测丙烯酰胺的含量。 结果表明,丙烯酰胺在0.020~0.800 μg/g浓度范围内与出峰面积呈线性关系,相关系数r=0.9994;检测限为0.005 μg/g;加标回收率为83.96%~89.43%,相对标准偏差(RSD)为2.13%~5.87%。 该方法具有操作简单、快速、可靠和灵敏度高等特点,成功应用于方便面等油炸食品中丙烯酰胺含量的测定。     

氨基功能化纳米复合材料对磷酸盐的吸附研究

合成了4种氨基(乙二胺(EDA), 二乙烯三胺(DETA), 三乙烯四胺(TETA)和四乙烯五胺(TEPA))功能化纳米复合材料(NH₂-NCMs, 分别命名为EDA-NCMs, DETA-NCMs, TETA-NCMs和TEPA-NCMs). 采用FTIR(傅立叶变换红外光谱分析), TG/DTG(热重差热分析), XPS(X-射线光电子能谱分析)等手段对其进行了表征, 并考察了其对水中磷酸盐的吸附性能. 结果表明: 溶液pH对其吸附性能影响较大, 在pH为2.5的条件下, 4种吸附剂对磷酸盐的吸附效果最佳; 在5 min内即可达到平衡吸附量的90%; 4种吸附剂对磷酸盐的吸附均符合Langmuir等温吸附模型; 吸附行为均符合准二级速率模型; 吸附反应为自发进行的放热反应和熵减的过程; 推测其吸附机理以静电作用力为主. 4种吸附剂用于磷酸盐含量为50 mg/L的废水处理的吸附率均大于97%, 均达到一级A出水的排放标准(≤1.53 mg/L, 以PO₄^3-计).     

吸附制冷用复合吸附剂的吸附热

本文推导出由一条吸附等温线和同一吸附质的汽化潜热,计算吸附热的简化模型。对水和乙醇在自制复合吸附剂、13X分子筛、硅胶和活性炭上的吸附热进行了计算;对吸附热与吸附量的关系进行了关联,给出了拟合方程。结果表明:在相同的吸附量条件下,水在复合吸附剂上的积分吸附热比在13X分子筛上低11％～17％;乙醇在复合吸附剂上的积分吸附热较在活性炭上低23％～27％。该研究为吸附制冷系统结构设计提供了计算吸附热的简便算法。     

红外光谱法测定固相微萃取新型吸附质中单体的摩尔比

以丙烯酸丁酯和苯乙烯为单体 ,过氧化苯甲酰为引发剂 (用量为wt 0 3% ) ,醋酸丁酯和甲苯作混合溶剂 ,溶剂用量与单体混合物的体积相同 ,采用溶液聚合的方法合成了一种新型固相微萃取吸附质 (苯乙烯 丙烯酸丁酯共聚物 )。以朗伯 比耳定律为依据 ,通过一系列的推导过程 ,得出了共聚物中两种官能团的吸收值比与共聚物中两种单体摩尔比的线性关系式A1 /A2 =kn1 /n2 。采用红外光谱法测定聚合物中两种官能团的吸收值比 ,再通过外标曲线法确定了共聚物中两种官能团的吸收值比 (y)与共聚物中两种单体的摩尔比 (x)的线性回归方程 y =0 136 2 0 0 84 1x。方法的精密度RSD(% ) =2 4 6 4 ,方法的回收率为 92 89%～10 3 94 %。红外光谱法测定作为固相微萃取新型吸附质的苯乙烯与丙烯酸丁酯共聚物中单体的摩尔比是一种快速准确的分析方法