溴代-1-甲基-3-己基咪唑离子液体表面分子印迹聚合物的制备及选择性吸附

以聚苯乙烯-二乙烯基苯颗粒为载体,制备溴代-1-甲基-3-己基咪唑离子液体表面印迹聚合物;通过扫描电镜、红外光谱、紫外光谱、比表面积及热分析等手段,对聚合物进行表征;静态实验结果显示,聚合物对模板底物有较强的吸附能力,印迹和非印迹聚合物对模板底物的饱和吸附量分别为667和322μmol g~(-1);动力学实验表明,印迹聚合物在1.0 h内能够达到吸附平衡,其吸附特征符合假二级动力学方程;选择性实验表明,印迹聚合物能够从结构类似物中选择性吸附模板分子。     

β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能

以N,N-二甲基甲酰胺(DMF)为溶剂, 利用静电纺丝法制备了聚丙烯腈(PAN)/β-环糊精(β-CD)纳米纤维. 通过场发射扫描电镜、红外光谱和粉末XRD对纳米纤维进行了表征, 并检测了纺丝溶液的电导率和黏度. 结果表明, β-CD的添加量可以改善纳米纤维的形貌, 固定在纤维上的β-CD保留了空腔结构, 为其在纳米纤维中发挥超分子特性提供了可能. 通过紫外-可见光谱法研究了PAN/β-CD纤维对亚甲基蓝(MB)溶液的吸附性能. 结果表明, 纳米纤维中的β-CD显著提高了PAN/β-CD纤维对MB的吸附能力, 使其在吸附分离、电化学传感器及药物控制释放等领域具有潜在的应用价值.     

分子印迹球状β-环糊精聚合物的合成及性能研究

利用分子印迹技术,以β-环糊精为功能单体,甲苯-2,4-二异氰酸酯为交联剂,茶碱为模板分子,合成了分子印迹β-环糊精聚合物。采用反相悬浮聚合的方法,以戊二醛为交联剂,用聚乙烯醇(PVA)包埋环糊精聚合物合成了分子印迹球状β-环糊精聚合物(MI-CDPs)吸附剂,对聚合物的合成条件进行了考察,并利用静态吸附方法对球状MI-CDPs的吸附性能进行研究,结果表明,球状MI-CDPs对水溶液中的茶碱分子表现出良好的分子识别能力,实现了对水溶液中茶碱的分子识别,证实在pH=9时,球状MI-CDPs的吸附性能最佳。     

β-环糊精修饰的壳聚糖对氯酚吸附的动力学和热力学

制备了β-环糊精(β-CD)修饰的壳聚糖(CS)—β-环糊精-6-壳聚糖(CS-CD), 并用傅里叶变换红外(FT-IR)光谱仪, 扫描电镜(SEM), X 射线衍射(XRD)仪和比表面分析仪(BET)进行了表征. 详细研究了其对2-氯酚(2-CP)、2,4-二氯酚(DCP)和2,4,6-三氯酚(TCP)的吸附行为和机理. 研究表明其吸附较好地满足Langmuir 和Freundlich 吸附模型, β-环糊精的引入能够较大地提高吸附效率, 2-CP、DCP和TCP在CS-CD上吸附的最大吸附量分别为14.51、50.68和74.29 mg·g^-1. 动力学研究表明其吸附速率快, 在1 h内能达到吸附平衡, 并符合假二级动力学模型. 计算出了热力学参数ΔG⁰、ΔH⁰和ΔS⁰的值, ΔG⁰为负值表明吸附剂对氯酚的吸附是一个自发的过程. 电解质和溶液pH值对吸附的影响说明在吸附过程中主要是氯酚与吸附剂之间形成了氢键, 并进一步讨论了可能的吸附机理. 改性吸附剂易重复利用, 重复使用六次后的质量和吸附效率与初次相比分别保持在90%和82%以上, 然而CS的质量有较大的损失, 吸附效率也明显降低.     

反式白藜芦醇双功能单体印迹固相萃取柱的制备及应用

采用自组装技术,分别以β-环糊精和甲基丙烯酸为功能单体,反式白藜芦醇为模板分子,乙二醇二甲基丙烯酸酯为交联剂,制备了一种双功能单体印迹聚合物。 并将其作为固相萃取材料萃取红酒和白酒酒样中的反式白藜芦醇。 结果表明,与单功能印迹材料和非印迹材料相比,这种双功能单体印迹材料具有更高的吸附容量和选择性;结合高效液相色谱,建立了酒样中反式白藜芦醇浓度的检测方法。 该方法的线性范围在0.003~2 mg/L,红酒的回收率在87.9%~93.2%,白酒的回收率在89.3%~91.2%,检测限为0.001 mg/L。     

邻苯二甲酸二甲酯印迹吸附材料的水相合成及固相萃取应用

在硅胶表面以邻苯二甲酸二甲酯(DMP)为模板分子,甲基丙烯酰胺(MAM)为功能单体,N,N-亚甲基双丙烯酰胺(MBAA)为交联剂在甲醇/水体系中制备了DMP印迹聚合物。采用紫外光谱法(UV)研究单体与模板间的相互作用,红外光谱分析印迹聚合物的结构特征。用平衡吸附实验方法研究聚合物对DMP的结合性能,Scatchard法分析聚合物的吸附解离常数(Kd)和最大表观吸附容量(Qmax)。对不同底物的选择性实验表明聚合物对模板分子具有良好的亲和性和选择性。将MIP用作固相萃取(SPE)柱填料,对环境水样中的DMP进行富集试验,回收率为90.28-95.25%,相对标准偏差(RSD)为3.52-7.61%。     

胆酸印迹聚合物的制备及在含水介质中的结合性能

为了在含水介质中进行有效印迹,本研究中以双甲基丙烯酰-β-环糊精（BMA-β-CD）和2-(二乙基胺基)乙基甲基丙烯酸酯(DEAEM)为功能单体制备了胆酸印迹聚合物MIP1,并用平衡结合实验研究了MIP1在含水介质中对模板分子的识别能力。结果表明,MIP1比单独以BMA-β-CD或DEAEM为功能单体制备的印迹聚合物MIP2和MIP3,显示出对模板分子更好的选择性结合能力。MIP1的特异性吸附量ΔCP为38.81μmol/g,印迹因子IF为2.46。研究表明,在含水介质中,利用模板分子与功能单体之间的疏水作用和离子作用是提高印迹聚合物分子识别能力的关键。研究还表明,在识别过程中,疏水作用在驱动分子进入印迹孔穴时起重要作用。     

氧化石墨烯表面坐果安分子印迹聚合物的合成及其表征

以氧化石墨烯为载体,坐果安为模板分子,α-甲基丙烯酸(MAA)为功能单体,采用表面分子印迹技术制备了坐果安分子印迹聚合物微球。利用紫外光谱和扫描电镜等对聚合物进行表征,研究聚合物的结合和识别特性。通过静态平衡结合法研究了吸附时间、温度、pH和底物初始浓度对其吸附性能的影响,并考察了其重复利用性。通过Scatchard分析研究了聚合物的结合特征,最大表现结合量(Q_(max))为114.902μg/mg,其表明聚合物对坐果安分子具有优良的选择吸附性能和较高的吸附容量。     

L-肉碱分子表面印迹聚合物的制备及其识别性能研究

以L-肉碱(L-carnitine)作为印迹模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,采用硅胶表面分子印迹技术合成了L-肉碱分子印迹聚合物(MIP)和非印迹聚合物(NMIP).通过紫外光谱研究了MAA与L-肉碱之间的结合作用.利用IR和SEM测试分别对产物进行了结构表征和表面形貌观察,说明分子印迹聚合物成功接枝到了硅胶表面.吸附动力学实验结果表明,MIP对L-肉碱有较好的识别性和吸附性;Scatchard分析表明该印迹聚合物中存在着一类等价的结合位点,最大表观结合量为71.00μmol/g,离解常数Kd=2.76×10-4mol/L;选择性吸附实验结果表明,MIP对L-肉碱的吸附结合量高于其D型异构体和其他类似物;拆分实验结果表明,MIP对DL-肉碱的拆分有一定作用.     

咪唑基取代β-环糊精聚合物固相萃取剂制备及分析应用

合成了单-6-脱氧-6-咪唑-β-环糊精聚合物（β-CDIMCP）,建立了以β-CDIMCP为固相萃取剂分离分析碱性桃红T的新方法。 结果表明,与β-环糊精聚合物(β-CDCP)相比,β-CDIMCP具有更好的吸附能力。 室温下、pH=11.0时,β-CDIMCP能快速定量吸附碱性桃红T（吸附率95%）;以3.0 mL无水乙醇在8 min内可脱附碱性桃红T（脱附率90.0%）。 在最佳条件下,β-CDIMCP对碱性桃红T富集倍数为10,检出限为4.9 μg/L,相对标准偏差3.4%(n=3,ρ=3.00 mg/L),线性范围为0.09~6.00 mg/L,相关系数R为0.9972。 通过包合常数测定探讨了β-CDIMCP对碱性桃红T的吸附机理。 采用该方法对实际样品中碱性桃红T含量测定,结果令人满意。     

分子印迹固相萃取检测罐装食品中双酚A

以双酚A为模板分子,3-氨基丙基乙氧基硅烷为功能单体,通过溶胶-凝胶反应合成双酚A分子印迹纳米硅胶微球。以印迹微球为固相萃取吸附剂,优化固相萃取条件,确定二氯甲烷为上样溶剂。固相萃取选择性实验表明,在双酚A及其结构类似物四溴双酚A、双酚C、壬基酚的混合物溶液中,印迹萃取柱对双酚A具有良好的选择性能,回收率达到90.7%。浓度为2.5和5μmol/L的加标罐装食品样品,经印迹萃取柱预处理,液相色谱检测得到回收率72%～84%,相对标准偏差2.9%～4.4%。     

A novel sol-gel-material prepared by a surface imprinting technique for the selective solid-phase extraction of bisphenol A

A novel and simple imprinted amino-functionalized silica gel material was synthesized by combining a surface molecular imprinting technique with a sol-gel process on the supporter of activated silica gel for solid-phase extraction-high performance liquid chromatography (SPE-HPLC) determination of bisphenol A (BPA). Non-imprinted silica sorbent was synthesized without the addition of BPA using the same procedure as that of BPA-imprinted silica sorbent. The BPA-imprinted silica sorbent and non-imprinted silica sorbent were characterized by FT-IR and the static adsorption experiments. The prepared BPA-imprinted silica sorbent showed high adsorption capacity, significant selectivity and good site accessibility for BPA. The maximum static adsorption capacity of the BPA-imprinted and non-imprinted silica sorbent for BPA was 68.9 and 34.0 mg g⁻¹, respectively. The relatively selective factor value of this BPA-imprinted silica sorbent was 4.5. Furthermore, the difference of the retention characteristics of BPA on the C₈ SPE column and BPA-imprinted silica SPE (MIP-SPE) was compared. The MIP-SPE-HPLC method showed higher selectivity to BPA than the traditional SPE-HPLC method. At last, the BPA-imprinted polymers were used as the sorbent in solid-phase extraction to determine BPA in water samples with satisfactory recovery higher than 99% (R.S.D. 3.7%).     

β-环糊精功能化聚丙烯腈纳米纤维的制备及对亚甲基蓝的吸附性能

以N,N-二甲基甲酰胺(DMF)为溶剂,利用静电纺丝法制备了聚丙烯腈(PAN)/β-环糊精(β-CD)纳米纤维.通过场发射扫描电镜、红外光谱和粉末XRD对纳米纤维进行了表征,并检测了纺丝溶液的电导率和黏度.结果表明,β-CD的添加量可以改善纳米纤维的形貌,固定在纤维上的β-CD保留了空腔结构,为其在纳米纤维中发挥超分子...     

Decontamination of bisphenol A from aqueous solution by graphene adsorption

The decontamination of bisphenol A (BPA) from aqueous solution by graphene adsorption was investigated. The maximum adsorption capacity (q(m)) of graphene for BPA obtained from a Langmuir isotherm was 182 mg/g at 302.15 K, which was among the highest values of BPA adsorption compared with other carbonaceous adsorbents according to the literature. Both π-π interactions and hydrogen bonds might be responsible for the adsorption of BPA on graphene, and the excellent adsorption capacity of graphene was due to its unique sp(2)-hybridized single-atom-layer structure. Therefore, graphene could be regarded as a promising adsorbent for BPA removal in water treatment. The kinetics and isotherm data can be well described by the pseudo-second-order kinetic model and the Langmuir isotherm, respectively. The thermodynamic studies indicated that the adsorption reaction was a spontaneous and exothermic process. Besides, the presence of NaCl in the solution could facilitate the adsorption process, whereas the alkaline pH range and higher temperature of the solution were unfavorable.     

金-石墨烯修饰电极电化学检测塑料瓶中双酚A

在离子液体碳糊电极(CILE)表面上采用一步电还原法制备了纳米金(nAu)-石墨烯(GR)复合膜修饰电极(nAu-GR/CILE)。研究了双酚A(BPA)在nAu-GR/CILE上的电化学行为,BPA的电极反应过程为受吸附控制的不可逆过程;采用示差脉冲伏安法研究了BPA氧化峰电流和浓度之间的关系,在0.08~400.0μmol/L范围内,检出限为0.021μmol/L(3σ)。将nAu-GR/CILE用于塑料瓶中BPA的检测,与采用高效液相色谱法(HPLC)进行对比,结果表明两种方法对BPA的检测结果相吻合。     

Hydrothermal synthesis of MoS2 with controllable morphologies and its adsorption properties for bisphenol A

The effect of preparation conditions (molar ratio of S/Mo, hydrothermal temperature and time) on the morphologies of MoS₂ was investigated. The as-synthesized materials were characterized by X-ray diffraction (XRD), field emission scanning microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectra and Brunauer–Emmett–Teller’s (BET) surface area measurement. Results showed that the three kinds of morphologies of MoS₂ were obtained. Morphologies varied gradually from the coral-like aggregated particles to flower-like spheres to wrapped nano-sheet structure with increasing hydrothermal temperature and time. It is meaningful for specific morphology demand in different fields. Moreover, the prepared materials were used as tentative adsorbents for the removal of bisphenol A (BPA) as a representative of endocrine disruptors. The results showed that the prepared MoS₂ materials with wrapped nano-sheet structure had good adsorption capacity (39.03 mg/g) and fast adsorption rate (0.0053 g/(mg/min). The adsorption process was thermodynamically exothermic and spontaneous. The study indicated that electrostatic interaction is strong and π-π interaction between BPA and the MoS₂ materials play an important role for BPA adsorption.     

Novel sponge-like molecularly imprinted mesoporous silica material for selective isolation of bisphenol A and its analogues from sediment extracts

Bisphenol A (BPA) imprinted sponge mesoporous silica was synthesized using a combination of semi-covalent molecular imprinting and simple self-assembly process. The molecularly imprinted sponge mesoporous silica (MISMS) material obtained was characterized by FT-IR, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption measurements. The results show that the MISMS possessed a large specific surface area (850.55 m² g⁻¹) and a highly interconnected 3-D porous network. As a result, the MISMS demonstrated a superior specific adsorption capacity of 169.22 μmol g⁻¹ and fast adsorption kinetics (reaching equilibrium within 3 min) for BPA. Good class selectivity for BPA and its analogues (bisphenol F, bisphenol B, bisphenol E and bisphenol AF) was also demonstrated by the sorption experiment. The MISMS as solid-phase extraction (SPE) material was then evaluated for isolation and clean-up of these bisphenols (BPs) from sediment samples. An accurate and sensitive analytical method based on the MISMS–SPE coupled with HPLC–DAD has been successfully established for simultaneous determination of five BPs in river sediments with detection limits of 0.43–0.71 ng g⁻¹ dry weight (dw). The recoveries of BPs for lyophilizated sediment samples at two spiking levels (50 and 500 ng g⁻¹ dw for each BP) were in the range of 75.5–105.5% with RSD values below 7.5%.     

Study on the Joint Toxicity of BPZ,BPS, BPC and BPF to Zebrafish

Bisphenol Z (BPZ), bisphenol S (BPS), bisphenol C (BPC), and bisphenol F (BPF) had been widely used as alternatives to bisphenol A (BPA), but the toxicity data of these bisphenol analogues were very limited. In this study, the joint toxicity of BPZ, BPS, BPC, and BPF to zebrafish (Danio rerio) was investigated. The median half lethal concentrations (LC50) of BPZ, BPS, BPC, and BPF to zebrafish for 96 h were 6.9 × 10⁵ µM, 3.9 × 10⁷ µM, 7.1 × 10⁵ µM, and1.6 × 10⁶ µM, respectively. The joint toxicity effect of BPF–BPC (7.7 × 10⁵–3.4 × 10⁵µM) and BPZ–BPC (3.4 × 10⁵–3.5 × 10⁵µM) with the same toxic ratio showed a synergistic effect, which may be attributed to enzyme inhibition or induction theory. While the toxicity effect of the other two bisphenol analogue combined groups and multi-joint pairs showed an antagonistic effect due to the competition site, other causes need to be further explored. Meanwhile, the expression levels of the estrogen receptor genes (ERα, ERβ1) and antioxidant enzyme genes (SOD, CAT, GPX) were analyzed using a quantitative real-time polymerase chain reaction in zebrafish exposure to LC₅₀ of BPZ, BPS, BPC, and BPF collected at 24, 48, 72, and 96 h. Relative expression of CAT, GPX, and ERβ1 mRNA declined significantly compared to the blank control, which might be a major cause of oxidant injury of antioxidant systems and the disruption of the endocrine systems in zebrafish.