“鳄鱼皮状”荧光纳米纤维对苦味酸的检测方法
【技术领域】
[0001]本发明涉及到爆炸物的检测技术与静电纺丝技术领域，尤其涉及到“鳄鱼皮状”荧光纳米纤维对苦味酸的检测方法。
【背景技术】
[0002]2，4，6-三硝基苯酸(俗称苦味酸，picric acid，PA)是一种重要的有机化工原料，被广泛用于皮革、制药、黄色染料和防腐剂生产等(Niu Q, Gao K1Lin Z, etal.Amine-capped carbon dots as a nanosensor for sensitive and selectivedetect1n of picric acid in aqueous solut1n via electrostatic interact1n[J].Analytical Methods，2013，5 (21): 6228-6233.)。但与此同时，苦味酸也是一种常见的爆炸物和典型的污染物，具有突出的公共安全威胁性和生态破坏性，也是潜在的致癌物质(Kumar S，Venkatramaiah N，Patil S.Fluoranthene Based Derivatives forDetect1n of Trace Explosive Nitroaromatics[J].Journal of Physical ChemistryC，2013，117(14):7236-7245.) 0因此，研究痕量苦味酸的检测方法，对预防恐怖犯罪和环境污染监测等至关重要。
[0003]在目前的爆炸物检测方法中，荧光化学传感器因其具有较高的灵敏度和检测的简便性得到广泛关注。然而，研制一种高效的荧光化学传感器用于如PA、2，4-二硝基甲苯(DNT)和2，4，6-三硝基甲苯(TNT)等爆炸物的检测仍然是一个挑战。近年来，将一维纳米纤维作为传感器用于爆炸物的检测报道相对较少。因此，利用纤维的独特性质研发新颖材料在科学界和工业界意义重大D (Sun X，Liu Y，Shaw Gj et al.Fundamental Studyof Electrospun Pyrene-Polyethersulfone Nanofibers Using Mixed Solvents forSensitive and Selective Explosives Detect1n in Aqueous Solut1n[J].ACS AppliedMaterials&Interfaces, 2015，7(24):13189-13197.)
[0004]采用静电纺丝制备直径为几十纳米到微米量级的纳米纤维材料，是一种非常简便而有效的方法(Xing C，Guan Jj Li Y，et al.Effect of aRoom-Temperature 1nic Liquid on the Structure and Properties of ElectrospunPoly (vinylidene fluoride)Nanofibers[J].ACS Applied Materials&Interfaces, 2014,6(6):4447-4457.h静电纺丝通过对黏性溶液施加高电压，从而连续产生大量的纳米纤维(Park S Mj Kim D S.Electrolyte-Assisted Electrospinning for aSelf-Assembled, Free-Standing Nanofiber Membrane on a Curved Surface[J].Advanced Materials, 2015，27 (10): 1682-+) o所得到的纳米纤维因具有可控形貌，比表面积大(约I至10m2.g x)以及多孔结构等众多优点，而被广泛应用于组织工程(Trinca RB，Abraham G A, Felisberti M 1.Electrospun nanofibrous scaffolds of segmentedpolyurethanes based on PEG, PLLA and PTMC blocks:Physico-chemical propertiesand morphology[J].Materials science&engineering.C，Materials for b1logicalapplicat1ns，2015，56:511-7.)，过滤(Liu B，Zhang S，Wang X，et al.Efficient andreusable polyamide-56 nanofiber/nets membrane with bimodal structures for airfiltrat1n [J].Journal of colloid and interface science，2015，457:203-11)，电子器件(Zhu H，Du Mj Zhang M，et al.The design and construct1n of 3D rose-petal-shapedMoS2 hierarchical nanostructures with structure-sensitive properties [J].Journal of Materials Chemistry A，2014，2 (21): 7680-7685.)，催化剂载体(Ghouri ZKj Barakat N A M，Obaid M，et al.Co/Ce02_decorated carbon nanofibers as effectivenon-prec1us electro-catalyst for fuel cells applicat1n in alkaline medium[J].Ceramics Internat1nal，2015，41 (2): 2271-2278.)，增强复合材料(Tian M，Wang YN，Wang R.Synthesis and characterizat1n of novel high-performance thin filmnanocomposite (TFN)FO membranes with nanof ibrous substrate reinforced byfunct1nalized carbon nanotubes [J].Desalinat1n, 2015，370:79-86.)和传感器件(Wang L，Deng J，Lou Zj et al.Cross-linked p-type Co304 octahedral nanoparticlesin ID n-type Ti02 nanofibers for high-performance sensing devices [J].Journal of Materials Chemistry A，2014，2 (26): 10022-10028.)等方面。由于焚光传感器的高灵敏度和快速响应，电纺纳米纤维材料在荧光传感方面已发展为具有良好前景的纳米材料。目前，已报道了几种电纺纤维膜的化学传感器用于在水相中一些分析物的检测，主要包括金属离子(Min Mj Wang X，Chen Y，et al.Highly sensitive andselective Cu2+sensor based on electrospun rhodamine dye doped poly (ethersulfones)nanofibers[J].Sensors and Actuators B-Chemicalj 2013,188:365-371.)，亚硝酉爱盐(Ding Y，Wang Y，Li B，et al.Electrospun hemoglobin microbelts basedb1sensor for sensitive detect1n of hydrogen peroxide and nitrite [J].Biosensors&B1electronics，2010，25 (9):2009-2015.)，挥发性气体(Liang X，Kim TH，Yoon J Wj et al.Ultrasensitive and ultraselective detect1n of H2S usingelectrospun CuO-1oaded In203 nanofiber sensors assisted by pulse heating[J].Sensors and Actuators B-Chemical，2015，209:934-942.)等。然而，这些薄膜一般是通过覆盖，染料掺杂，或通过其它物理方法进行制备，而这些制备法都存在的各种问题，如荧光团的聚集而导致荧光猝灭，荧光泄漏，以及内层分析物扩散等(Long Y, ChenH，Yang Y，et al.Electrospun nanofibrous film doped with a conjugated polymerfor DNT fluorescence sensor[J].Macromolecules, 2009，42(17):6501-6509.)。 一种更为直接、简单的方法是对聚合物纳米纤维的表面进行修饰，这种处理法不会影响纳米纤维的整体性质。表面修饰的方法在很大程度上取决于形成纤维聚合物的性质，到目前为止，表面修饰法主要有等离子体处理法(Padil V T, Nguyen N HA,Rozek Zj et al.Synthesis,fabricat1n and antibacterial properties of aplasma modified electrospun membrane consisting of gum Kondagogujdodecenylsuccinic anhydride and poly (vinyl alcohol) [J].Surface&CoatingsTechnology，2015，271:32-38.)，物理吸附法(Polini A, Pagliara S，Stabile R，etal.Collagen-funct1nalised electrospun polymer fibers for b1engineeringapplicat1ns[J].Soft Matter，2010，6 (8):1668-1674.)，自组装法(Duan G，JiangSj Jerome V，et al.Ultralight,Soft Polymer Sponges by Self-Assembly of ShortElectrospun Fibers in Colloidal Dispers1ns[J].Advanced Funct1nal MateriaIs, 2015, 25 (19): 2850-2856.)以及共价嫁接法(Mangeon C, Mahouche-Chergui S, VersaceD L, et al.Poly(3-hydroxyalkanoate) -grafted carbon nanotube nanofillers asreinforcing agent for PHAs-based electrospun mats[J].Reactive&Funct1nalPolymers, 2015, 89:18-23.)等。
[0005]本发明通过充分利用静电纺丝技术的简便性和具有聚集诱导发光效应(aggregat1n-1nduced emiss1n, AIE)小分子焚光探针(TPE_2pTPA，结构如图1 所示)的简单掺杂，研制一种便携式“鳄鱼皮状”的纳米纤