“鱷魚(yú)皮狀”熒光納米纖維對(duì)苦味酸的檢測(cè)方法
【技術(shù)領(lǐng)域】
[0001]本發(fā)明涉及到爆炸物的檢測(cè)技術(shù)與靜電紡絲技術(shù)領(lǐng)域，尤其涉及到“鱷魚(yú)皮狀”熒光納米纖維對(duì)苦味酸的檢測(cè)方法。
【背景技術(shù)】
[0002]2，4，6-三硝基苯酸(俗稱(chēng)苦味酸，picric acid，PA)是一種重要的有機(jī)化工原料，被廣泛用于皮革、制藥、黃色染料和防腐劑生產(chǎn)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.)。但與此同時(shí)，苦味酸也是一種常見(jiàn)的爆炸物和典型的污染物，具有突出的公共安全威脅性和生態(tài)破壞性，也是潛在的致癌物質(zhì)(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，研究痕量苦味酸的檢測(cè)方法，對(duì)預(yù)防恐怖犯罪和環(huán)境污染監(jiān)測(cè)等至關(guān)重要。
[0003]在目前的爆炸物檢測(cè)方法中，熒光化學(xué)傳感器因其具有較高的靈敏度和檢測(cè)的簡(jiǎn)便性得到廣泛關(guān)注。然而，研制一種高效的熒光化學(xué)傳感器用于如PA、2，4-二硝基甲苯(DNT)和2，4，6-三硝基甲苯(TNT)等爆炸物的檢測(cè)仍然是一個(gè)挑戰(zhàn)。近年來(lái)，將一維納米纖維作為傳感器用于爆炸物的檢測(cè)報(bào)道相對(duì)較少。因此，利用纖維的獨(dú)特性質(zhì)研發(fā)新穎材料在科學(xué)界和工業(yè)界意義重大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]采用靜電紡絲制備直徑為幾十納米到微米量級(jí)的納米纖維材料，是一種非常簡(jiǎn)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靜電紡絲通過(guò)對(duì)黏性溶液施加高電壓，從而連續(xù)產(chǎn)生大量的納米纖維(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所得到的納米纖維因具有可控形貌，比表面積大(約I至10m2.g x)以及多孔結(jié)構(gòu)等眾多優(yōu)點(diǎn)，而被廣泛應(yīng)用于組織工程(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.)，過(guò)濾(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)，電子器件(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.)，催化劑載體(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.)，增強(qiáng)復(fù)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.)和傳感器件(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。由于焚光傳感器的高靈敏度和快速響應(yīng)，電紡納米纖維材料在熒光傳感方面已發(fā)展為具有良好前景的納米材料。目前，已報(bào)道了幾種電紡纖維膜的化學(xué)傳感器用于在水相中一些分析物的檢測(cè)，主要包括金屬離子(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.)，亞硝酉愛(ài)鹽(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.)，揮發(fā)性氣體(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，這些薄膜一般是通過(guò)覆蓋，染料摻雜，或通過(guò)其它物理方法進(jìn)行制備，而這些制備法都存在的各種問(wèn)題，如熒光團(tuán)的聚集而導(dǎo)致熒光猝滅，熒光泄漏，以及內(nèi)層分析物擴(kuò)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.)。 一種更為直接、簡(jiǎn)單的方法是對(duì)聚合物納米纖維的表面進(jìn)行修飾，這種處理法不會(huì)影響納米纖維的整體性質(zhì)。表面修飾的方法在很大程度上取決于形成纖維聚合物的性質(zhì)，到目前為止，表面修飾法主要有等離子體處理法(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.)，自組裝法(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.)以及共價(jià)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]本發(fā)明通過(guò)充分利用靜電紡絲技術(shù)的簡(jiǎn)便性和具有聚集誘導(dǎo)發(fā)光效應(yīng)(aggregat1n-1nduced emiss1n, AIE)小分子焚光探針(TPE_2pTPA，結(jié)構(gòu)如圖1 所示)的簡(jiǎn)單摻雜，研制一種便攜式“鱷魚(yú)皮狀”的納米纖