Sensing application and mechanism of organic-inorganic nanocomposites
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摘要: 有机-无机杂化复合纳米材料可以在微观尺寸上将有机和无机组分相结合,使复合材料兼具两种组分的优点,实现所需的性能或功能,因此成为材料学的研究热点之一。本文以有机荧光染料罗丹明、三苯胺和金属配合物发光材料为母体,制备出一系列对汞离子、铜离子、铁离子等常见金属离子具有明显光谱响应的探针类材料并选取合适的支撑基质组装成有机-无机复合材料,实现了对金属离子和一些阴离子的目视比色传感。不同离子的加入及加入顺序都会对探针类材料的吸收及发光光谱造成明显的变化。以不同的金属离子或氧气作为输入值,以吸收强度/发光强度作为输出值,模拟了分子水平的逻辑门,拓展了这些材料的应用。为了解决背景荧光干扰,我们利用六角相的β-NaYF4纳米晶为激发源,采用二氧化硅进行包覆,然后将荧光探针分子固载到二氧化硅表面,得到了对金属离子具有传感性能的核壳型的上转换纳米复合材料。在近红外激发下能够显示明亮的上转换绿光发射,同时对金属离子具有较好的选择性、较高的灵敏度,并且其荧光强度表现出对汞离子浓度的线性响应。这种纳米复合材料的上转换光学性质、汞离子传感性能使它们在分析化学、生物化学等领域有潜在的应用价值。Abstract: As one of research hotspots, organic-inorganic nanocomposite materials combine virtues from both components at microcosmic level, achieving desired function and performance. This paper prepared a series of probe materials for Hg(Ⅱ), Cu(Ⅰ), Fe(Ⅲ) etc. using starting chemicals of rhodamine, triphenylamine and emissive metal complexes. These probes were embedded into proper matrixes to construct composite materials, realizing naked-eye colourimetric sensing towards metal and anion ions. Different ions and their sequence led to spectral variations of absorption and emission spectra. Molecular logic gates were simulated using metal ions or oxygen as input, absorption/emission as output, respectively, widening application of these probes. Hexagonal β-NaYF4 nanocystals were prepared and used as excitation source to eliminate background light interference. Probe molecules were covalently grafted onto these silica coated β-NaYF4 nanocystals, giving core-shell structured up-conversion sensing composites. Upon IR radiation, up-conversion green light was observed, showing good selectivity and sensitivity to metal ions with linear response. Above up-conversion and sensing features made corresponding nanocomposites a promising candidate in analytical chemistry and biochemistry.
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Key words:
- composite materials /
- naked-eye colourimetric analysis /
- sensing /
- luminescence /
- magnetic
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图 5 不同亚硝酸根离子浓度下Rh 6G-SiO2(0.4 mg/mL)的荧光光谱(λex = 510 nm)
Figure 5. Emission spectra of Rh 6G-SiO2(0.4 mg/mL) with various nitrite ion concentrations(λex=510 nm)
图 7 多功能纳米复合材料Ru(bpy)2Phen-MMS的制备过程及氧传感机理
Figure 7. Construction route and sensing mechanism of Ru(bpy)2Phen-MMS
图 8 在不同氧气含量下Ru(bpy)2Phen-MMS的发射光谱(λex=468 nm)
Figure 8. Emission spectra of Ru(bpy)2Phen-MMS under various O2 concentrations(λex=468 nm)
图 9 Ru(bpy)2Phen-MMS发光强度的变化I0/I与氧气浓度的Stern-Volmer关系曲线
Figure 9. Stern-Volmer curve of Ru(bpy)2Phen-MMS with I0/I vs. O2 concentration
图 10 多功能纳米复合材料的制备过程及控制释放原理示意图
Figure 10. Construction route and release mechanism diagram of the composite Azo-MMS
图 11 Azo-MMS在450 nm的持续光照射下溶液中罗丹明6G的发射光谱变化
Figure 11. Emission spectra of rhodamine 6G in Azo-MMS solution under continuous radiation at the wavelength of 450 nm
图 12 Azo-MMS在450 nm持续光照和黑暗条件下对罗丹明6G的释放曲线
Figure 12. Release character of rhodamine 6G in Azo-MMS under continuous radiation(450 nm) and dark
图 13 Azo-MMS在光照和黑暗间歇性变换条件下溶液中的罗丹明6G在542 nm处发射强度和时间的关系
Figure 13. Emission of rhodamine 6G at 542 nm in Azo-MMS under periodical variation of radiation and dark
图 14 Azo-MMS在外加磁场下对罗丹明6G的靶向运输和在指定位点的光控释放情况
Figure 14. Target transportation and light-controlled release of rhodamine 6G in Azo-MMS under magnetic field
图 15 卟啉化合物共价嫁接的介孔薄膜材料的制备路线
Figure 15. Construction route for our mesoporous film modified with porphyrin
图 16 RS触发器的状态图(a)和器件稳定性的循环测试(b)
Figure 16. Status of RS latch(a) and its stability test cycle(b)
图 19 (a)铕配合物在各种阴离子条件下的光谱响应；(b)铕配合物的光谱响应情况(氯离子,溴离子和高氯酸根离子，浓度为50 μmol/L；磷酸二氢根离子，氟离子和醋酸根离子，浓度为20 μmol/L)。插图：364 nm照射下配合物对不同阴离子的响应，检测波长为610 nm
Figure 19. (a)PL spectra response of Eu(DBM)3DPPZ(5 μmol/L) to various metal ions；(b)PL spectra response of Eu(DBM)3DPPZ to 50 μmol/L of Cl-, ClO-4， Br-； 20 μmol/L of H2PO-4, AcO-, F-. Inset:corresponding photos under UV radiation(λExcitation=365 nm, λemission=610 nm)
图 20 铕配合物(5 μmol/L)在不同浓度醋酸根离子条件下的发光光谱，激发光波长为365 nm
Figure 20. Emission spectra of Eu(DBM)3DPPZ(5 μmol/L) with various concentrations of AcO-(λex=365 nm)
图 21 铕配合物的发光(a)和IMP逻辑电路与真值表(b)
Figure 21. (a)Emission spectra of Eu(DBM)3DPPZ; (b)molecular logic and truth table of IMP
图 23 受体1的吸收和发光光谱随阴离子的变化情况，激发光波长为342 nm
Figure 23. Absorption and emission spectra of acceptor 1 with different anions(λex=342 nm)
图 24 受体1的吸收和发光光谱随阳离子的变化情况，激发光波长为342 nm
Figure 24. Absorption and emission spectra of acceptor 1 with different cations(λex=342 nm)
图 25 受体1执行逻辑功能的真值表(a)以及对应的组合逻辑电路(b)
Figure 25. Truth table of acceptor 1(a) and corresponding combinational logic circuit(b)
图 28 吸收峰(■)和发射峰强度(●)与溶液极性的关系
Figure 28. Correlation between solvent dipole and absorption(■)/emission(●)
图 31 金属离子与探针分子作用后的颜色变化
Figure 31. Color change of probe in CH3CN-water and ethanol-water
图 32 3种探针分子的吸收(a)及荧光强度(b)随时间变化的曲线
Figure 32. Change curves of (a)absorption and (b)emission monitoring upon continuous reaction time of the three prebes
图 34 化合物TPA-BDP1-3在365 nm照射下不同溶剂中的荧光图片
Figure 34. Photos of TPA-BDP1-3 under UV radiation at the wavelength of 365 nm
图 35 化合物TPA-BDP1-3甲苯溶液中的激光光谱和ASE光斑图像
Figure 35. Laser emission spectra and ASE photo of TPA-BDP1-3 in toluene
图 37 加入金属离子后溶液在365 nm激发下荧光强度变化(λex=365 nm)
Figure 37. Emission photos under various metal ions(λex=365 nm)
图 38 Fe3+和Hg2+离子的浓度与荧光强度的变化
Figure 38. Change curves of emission intensity variation upon various concentrations of Fe3+ and Hg2+ ions
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