用智能手机读数检测柴油掺假的荧光纸片
Summary
在这里, 我们提出了一个协议, 以检测柴油与煤油的掺假使用测试条涂层荧光粘度探头与智能手机的分析系统。
Abstract
研究了三种荧光分子转子的 4-二甲基氨基-4-硝基雌二 (4-dns) 作为粘度探针的潜在用途, 以表明在二丝/煤油共混物中煤油的含量, 这是一种广泛的掺假燃料活性。在低粘度溶剂中, 染料通过所谓的扭曲分子内电荷转移状态迅速失活, 有效地淬火荧光。对柴油/煤油共混物的测定表明, 在柴油/煤油共混物中, 荧光的减少与黏性较低的煤油分数的增加有很好的线性关系。纤维素纸中羟基衍生物4-dns-oh 的固定化产生了保持荧光指示器行为的试纸。结合基于智能手机和控制应用程序的读卡器的条带, 可以创建一个简单的现场测试。该方法能可靠地检测柴油中煤油的含量在 7% ~ 100% 之间, 优于现有的柴油掺假标准方法。
Introduction
燃料掺假在世界许多不同地区是一个严重的问题, 这仅仅是因为燃料作为一种能源具有巨大的相关性。在掺假燃料上运行发动机会降低其性能, 导致较早的发动机故障, 并造成环境污染1。如果柴油掺入通常含有较高含量的硫 2, 3 的煤油,则会产生更多的 sox 排放。虽然这个问题存在了几十年, 但在其来源地发现这种犯罪活动的可持续燃料管理仍然很少, 因为对燃料掺假的简单和可靠的检测基本上缺乏4。尽管在过去几十年中在实验室矿物油分析方面取得了重大进展, 但现场测量的方法仍然很少。最近设计了在实验室外使用的各种方法, 使用光纤8、场效应晶体管9或机械变色材料10。虽然它们克服了传统方法的一些缺点, 但仍然严重缺乏可靠、方便用户和可移植的方法。基于分子转子的荧光粘度探针是一个有趣的替代品11,12, 因为矿物油是由各种碳氢化合物组成的, 这些碳氢化合物在链长和旋回性上各不相同, 而且通常反映在不同的粘度。由于燃料是复杂的混合物, 没有特定的铅化合物作为示踪剂, 测量的宏观性质的变化, 如粘度或极性似乎是非常有希望的。后者可以通过荧光分子转子来解决, 荧光量子产量取决于环境粘度。光激发后, 失活通常涉及扭曲的分子内电荷转移 (tiict) 状态, 其种群是由其周围微环境的粘度决定的 13.高粘度溶剂阻碍分子转子采用 tict 状态, 从而产生明亮的排放。在低粘性溶剂中, 转子可以更好地进入 tict 状态, 加速非辐射衰变, 从而抑制荧光。在27°c 时, 将粘度为 1.64 mm 2 s*-1的煤油添加到柴油中, 在1d、24.0、en 950 级的温度下, 其粘度分别为1.0-2.4、1.9-4.1、2.0-4.5 或 5.5-24-44.0 毫米 *-1 4d14、15、16降低了混合物的运动粘度, 并有可能导致分子转子探针荧光的比例淬火。4-二甲基氨基-4-硝基雌二苯醚 (4-dns) 的家族似乎对我们最有希望, 因为它们在 0.74-70.6 mm2的运动粘度范围内具有很强的荧光变化。这个范围与煤油和柴油的已知值很匹配。
因此, 我们探索了4dns 的能力, 2-[ethyl[4-[4-硝基苯) 苯] 氨基] 乙醇 (4dnsoh) 和 (e)-4-(2-(ethyl(4-(4—–(4-亚硝基苯乙烯) 苯基) 氨基)-4-氧丁烷酸 (4dsooh) 表明其粘度柴油煤油混合物通过其荧光, 取决于分子内的旋转, 并最终产生了一个快速测试柴油掺假与煤油。一次性测试易于使用, 精确、可靠、经济高效且尺寸小。研究了探针作为固体载体对滤纸的吸附, 并利用嵌入式智能手机荧光读取器进行了分析。如今, 无处不在的智能手机配备了高质量的摄像机, 使颜色和荧光等光学变化的检测变得简单, 并为强大的现场分析铺平了道路。我们在这里证明, 测量用智能手机吸附在纸带上的荧光探针的排放, 可以用可靠的方式检测燃烧燃料上的欺诈行为17。
Protocol
Representative Results
Discussion
以分子转子染料为基础, 在柴油及其不同与煤油共混物的范围内, 对粘度敏感, 利用荧光探针获得了检测柴油掺假的简单有效的试纸。不同柴油/煤油共混物中的 4-dns 在550纳米的排放强度与煤油比例增加时粘度降低有关。在24°c 的温度下, 观察到高达55% 的非线性荧光淬火, 可用于100% 与煤油一起掺假, 从而能够可靠地定量掺假, 标准偏差较低, 为1.70。
然而, 由于疏水性染料与疏水?…
Disclosures
The authors have nothing to disclose.
Acknowledgements
作者希望通过重点领域的分析科学: https://www.bam.de/Navigation/EN/Topics/Analytical-Sciences/Rapid-Oil-Test/rapid-oil-test.html, 感谢 bam 提供资金。
Materials
| 4-dimethylamino-4-nitrostilbene (CAS Number: 2844-15-7) | Sigma-Aldrich | 39255 | 4-DNS Dye |
| 2-[ethyl[4-[2-(4-nitrophenyl)ethenyl]phenyl]amino]ethanol (CAS Number: 122258-56-4) | Sigma-Aldrich | 518565 | 4-DNS-OH Dye |
| Whatman qualitative filter paper, Grade 1 | Sigma-Aldrich | Z274852 | Test strips support |
| Whatman application specific filter, activated carbon loaded paper, Grade 72 | Sigma-Aldrich | WHA1872047 | Fuel pre-treatment filters |
| Pall reusable in-line filter holders stainless steel, diam. 47 mm | Sigma-Aldrich | Z268453 | Holder pre-treatment filters |
| (3-Aminopropyl)triethoxysilane | Sigma-Aldrich | 919-30-2 | APTES |
| 4-(Dimethylamino)pyridine | Sigma-Aldrich | 1122-58-3 | DMAP |
| Succinic anhydride | Sigma-Aldrich | 108-30-5 | |
| Triethylamine | Sigma-Aldrich | 121-44-8 | Et3N |
| N,N'-dicyclohexylcarbodiimide | Sigma-Aldrich | 538-75-0 | DCC |
| Stuart Tube Rotators | Cole-Parmer | SB3 | Rotator |
| FreeCAD | freecadweb.org | – | Freeware – 3D design |
| Ultimaker Cura | Ultimaker | – | Freeware – 3D printing |
| Android Studio | – | Freeware – App programming | |
| Renkforce SuperSoft OTG-Mirror Micro-USB Cable 0,15 m | Conrad.de | 1359890 - 62 | Smartphone setup electronic part |
| Black Cord Switch 1 x Off / On | Conrad.de | 1371835 - 62 | Smartphone setup electronic part |
| Carbon Film Resistor 100 Ω | Conrad.de | 1417639 - 62 | Smartphone setup electronic part |
| 492 nm blocking edge BrightLine short-pass filter | Semrock | FF01-492/SP-25 | Filter excitation |
| 550/49 nm BrightLine single-band bandpass filter | Semrock | FF01-550/49-25 | Filter emission |
| Ø1/2" Unmounted N-BK7 Ground Glass Diffuser, 220 Grit | Thorlabs | DG05-220 | Diffuser excitation |
| LED 465 nm, 9 cd, 20 mA, ±15°, 5 mm clear epoxy | Roithner | RLS-B465 | LED excitation |
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