Construction and application of an electrochemical sensor based on graphene-MXene nanocomposites for baicalin detectionEI北大核心CSCD

Redox graphene-MXene(rGO-MXene) nanocomposites were prepared by ion polymerization and used to construct a highly sensitive electrochemical sensor for baicalin(BA) detection. The synergistic effect of rGO and MXene increased the specific surface area and electron transport capacity of the electrode, and significantly enhanced the electrochemical response of BA. The cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of BA on the sensor. Under the optimal conditions, the peak current exhibited a good linear relationship with BA concentration in the range of 0. 05-10 μmol / L, and the limit of detection was as low as 28 nmol / L. The method was applied to analyze traditional Chinese medicine preparations containing baicalin, such as Qingkailing Capsule and Sanhuang Tablets with good accuracy and spiked recovery. The results were highly consistent with those of high performance liquid chromatography, providing a technical means for the rapid and sensitive detection of traditional Chinese medicine preparations. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

基于镍基纳米材料电化学传感器的α-糖苷酶抑制剂筛选方法研究

采用多周期的电化学循环伏安(CV)法在泡沫镍(NF)上一步制备了镍基纳米材料修饰电极(Ni(OH)₂/NF)用于α-糖苷酶抑制剂的酶抑制活性评价,并基于此建立了一种简便的中药糖苷酶抑制剂筛选方法。采用X射线粉末衍射仪和扫描电镜表征修饰电极表面的结构和形貌;采用CV法和计时电流法测试电极的电化学性能。结果表明,Ni(OH)₂/NF传感器检测复杂酶体系中的葡萄糖具有良好的电化学响应,灵敏度高达3222μA·mmol/(L·cm²),线性范围为3.0～6000μmol/L,检出限低至0.9μmol/L (S/N=3)。采用临床降糖药物阿卡波糖验证了此传感器用于α-糖苷酶活性检测的可行性;并将传感器应用于莲须提取液的酶抑制效果评价,发现莲须具有一定的α-糖苷酶抑制活性,其半数抑制浓度(IC₅₀)为3.31 g/L。本研究结果表明,研制的传感器适用于α-糖苷酶抑制活性分析,为天然降糖药物筛选提供了一种新方法。     

Lewis酸催化纤维素制乳酸机理研究

Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y³⁺, Sc³⁺, and Al³⁺) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y³⁺ > Al³⁺ > Sc³⁺. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y³⁺ > Al³⁺, Y³⁺ > Sc³⁺), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc³⁺ > Y³⁺ > Al³⁺), and the conversion of DHA or GLY to the final product lactic acid (Al³⁺ > Y³⁺ > Sc³⁺). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.      

Construction and application of carbon nanotube/polypyrrole-based bacterial surface imprinted sensorEI北大核心CSCD

A simple and fast "non-hole" bacteria surface imprinted (SPBIP) impedance sensor was constructed for ultrasensitive detection of Salmonella. The SPBIP sensor was prepared by one step electropolymerization of pyrrole (functional monomer), single-walled carbon nanotube (SWNT, nano-modulator), and Salmonella(template) onto a glassy carbon electrode. After removing the bacterial template, "non-hole" imprinted sites were formed on the surface of the polymer matrix, allowing the target bacteria to be specifically recognized. The resulting changes in the electrode surface impedance could be used to detect the target bacteria. The effects of the amount of SWNT, polymerization cycles, eluents, elution time and recognition time on the recognition ability of the sensor were investigated. Under the optimal conditions, the sensor could be used to detect 10~1×107 CFU/mLSalmonella with the limit of detection of 3.5 CFU/mL. The sensor could be used for the detection of salmonella in drinking water and orange juice samples with the recoveries ranging from 95.4% to 109.5%. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

基于咔唑的分子内电荷转移分子聚集体对Ag+的比率荧光检测

以吡啶套索醚银离子络合基团为电荷受体,N-苯基咔唑为电荷给体,构筑分子内电荷转移共轭体系。咔唑基团的亲脂性可以增强分子在水介质中的疏水作用而形成分子聚集体。随着混合溶剂中水比例的上升,该分子呈现明显的丁达尔现象,荧光发射峰呈现先红移后蓝移的现象。在四氢呋喃-水(THF-H₂O,φ_H2O=87%)介质中,分子聚集体于428 nm处呈现较弱的荧光发射峰,随着溶液中Ag⁺浓度的增加,Ag⁺配合物在498 nm处的发射峰逐渐增强,该传感器分子聚集体可以对Ag⁺实现比率荧光检测,检出限0.337μmol/L。该传感器比率信号在0～0.7μmol/L范围内对Ag⁺具有较好的线性关系。     

基于荧光共振能量转移的核酸适配体传感器检测环丙沙星

建立了一种基于荧光共振能量转移（FRET）的核酸适配体传感器,并用于检测实际水体和牛奶中的环丙沙星（CIP）。为了防止羧基荧光素（FAM）被CIP猝灭,FAM和四甲基罗丹明（TAMRA）分别标记在互补单链DNA(FAM-cDNA)和适配体（TAMRA-APT）,通过DNA杂交发生FRET, TAMRA有效猝灭FAM的荧光。CIP加入后,其与FAM-cDNA发生亲和力竞争反应,CIP与TAMRA-APT形成结构更稳定的CIP/TAMRA-APT复合物,使体系FAM的荧光恢复。在优化条件下,本方法对CIP表现出高灵敏度和高选择性,检测浓度线性范围为0.01～1μmol/L,检出限为6 nmol/L;对实际水样和牛奶的加标回收率为90.4%～113.2%,相对标准偏差为1.8%～11%。该荧光适配体传感器具有成本低、灵敏度高、特异性好等优点,在环境中CIP残留快速检测方面具有良好的应用潜力。     

基于g-C_(3)N_(4)-UiO-66复合物修饰电极的电化学发光传感器用于测定水中邻苯二酚的含量北大核心CSCD

利用锆金属有机骨架(UiO-66)与半导体石墨相氮化碳(g-C_(3)N_(4))复合可形成异质结结构,构建了一种基于g-C_(3)N_(4)-UiO-66复合物修饰电极的电化学发光传感器用于水中污染物邻苯二酚的检测。分别合成g-C_(3)N_(4)和UiO-66,将二者充分研磨、煅烧后,得到g-C_(3)N_(4)-UiO-66复合物。以N,N-二甲基甲酰胺为溶剂配制1.0 g·L^(-1)的g-C_(3)N_(4)-UiO-66分散液,分取3.0μL,用滴涂的方式修饰到处理好的玻碳电极(GCE)表面,自然晾干后,得到g-C_(3)N_(4)-UiO-66修饰的GCE(g-C_(3)N_(4)-UiO-66@GCE)。以g-C_(3)N_(4)-UiO-66@GCE为工作电极,铂丝为辅助电极,Ag/AgCl为参比电极,将该三电极系统置于含有50 mmol·L^(-1) K_(2)S_(2)O_(8)的磷酸盐缓冲溶液(pH 7.5)中,采用循环伏安法在-1.6~0 V内,以0.1 V·s^(-1)速率进行扫描,记录加入邻苯二酚前后体系的电化学发光强度差值,即猝灭值。结果表明:体系电化学发光强度猝灭值与邻苯二酚浓度的对数呈线性关系,线性范围为1.0×10^(-5)~5.0×10^(-2)μmol·L^(-1),检出限为9.0×10^(-12)mol·L^(-1);用6根g-C_(3)N_(4)-UiO-66@GCE进行重现性试验,6次测定值的相对标准偏差(RSD)为3.3%;按照测试条件在-1.6~0 V内连续循环扫描31次,结果显示,加入邻苯二酚前后,测定值的RSD均小于4.0%;并且该传感器对对苯二酚、间苯二酚、葡萄糖、Na^(+)、K^(+)等干扰物质具有较好的抗干扰能力;用此电化学发光传感器分析自来水样品并进行加标回收试验,结果未检出邻苯二酚,回收率为98.4%,测定值的RSD(n=5)为3.8%。     

基于羧基化聚吡咯-氯化血红素和点触发链置换反应信号放大的电化学生物传感器检测转基因作物中CaMV35S序列

为适应快速增长的转基因生物(GMOs)安全评价与管理的需求,高效、可靠的转基因检测技术研究与应用的重要性日益凸显。该文采用一步法合成了羧基化聚吡咯(cPPy)与氯化血红素(Hemin)的纳米复合物(cPPy-hemin),并以其为信号标签合成了一种DNA双链结构功能化的纳米信标(DNA-cPPy-hemin)。利用cPPy-hemin增强的模拟酶催化活性,结合点触发链置换反应(TSDR)信号放大策略,制备了一种新型电化学基因传感器用于转基因成分的灵敏检测。通过信号探针(Ps)与模板链(Ts)、辅助链(As)结合形成DNA双链体结构中的-NH2功能化cPPy-hemin,制备Ts/As/Ps-cPPy-hemin双链DNA结构的纳米信标。在目标花椰菜花叶病毒35S启动子(CaMV35S)序列和燃料链(Fs)存在下,TSDR过程释放出的Ps-cPPy-hemin与固定在电化学沉积金纳米粒子修饰GCE表面上巯基化的DNA捕获探针(Cs)相结合,利用cPPy-hemin对H₂O₂的模拟酶催化产生的电信号,可实现对CaMV35S的定量检测。在最优条件下...     

抗坏血酸电化学传感研究进展

抗坏血酸是维持人体正常功能的必需生物小分子物质,间接或直接地参与众多人体关键的生物反应过程。电化学检测抗坏血酸具有响应时间快、灵敏度高和操作简单等众多优势,是近些年传感研究的热点。本文系统介绍了安培型电化学传感器的工作原理,综述了近年来抗坏血酸电化学传感的研究进展。基于不同材料构建的抗坏血酸传感器的性能,结合各传感材料的性质,对其传感优缺点进行了分析与总结,最后对抗坏血酸电化学传感的发展方向和趋势进行了展望。     

过硫酸铵氧化多孔碳/聚十六烷基三甲基溴化铵修饰电极灵敏检测铜离子

以壳聚糖为原料,通过高温热解法制备了多孔碳(PC),再用过硫酸铵(APS)氧化后得到APS氧化PC(APS-PC)。经APS氧化后的PC表面含氧官能团增多,既提高了其表面润湿性又增强了其对重金属离子的吸附能力。基于APS-PC及聚十六烷基三甲基溴化铵(p-CTAB)的高导电性、大比表面积和良好的吸附性能,构建了一种灵敏检测Cu²⁺的电化学传感器。采用差分脉冲阳极溶出伏安法(DPASV)和电化学交流阻抗法(EIS)表征了传感器的电化学性能,并考察了电聚合十六烷基三甲基溴化铵(CTAB)圈数、APS-PC的修饰量、缓冲溶液种类、溶液pH、搅拌速率、沉积电位及沉积时间等条件对传感器响应的影响。在最优条件下,该传感器对Cu²⁺的检测线性范围为0.25～25μg·L^-1,检出限为0.04μg·L^-1。该传感器具有良好的抗干扰性能、重现性和稳定性,应用于检测实际样品中的Cu²⁺含量,与石墨炉原子吸收光谱法(GFAAS)测定结果接近,加标回收率为86.0～96.4%。