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1.
利用分子氧对八乙基铂卟啉(PtDEP)具有荧光猝灭作用的特点,制备了一种新型氧敏感膜用于测定有机溶剂中溶解氧。以聚乙烯醇(PVA)为载体,八乙基铂卟啉为氧敏感指示剂制备氧敏感膜,并运用该膜测定有机溶剂中的溶解氧。实验结果表明,在涂膜量为0.5mL(膜厚度75μm),八乙基铂卟啉溶液浓度为1.0×10-3 mol/L,加入量为2mL时对氧的响应灵敏度最高,且对氧有较快的响应时间、良好的响应可逆性以及较好的稳定性。对1,3-丁二醇、N,N-二甲基甲酰胺、三氯甲烷和甲苯进行了溶解氧测定,检出限分别为0.62、0.40、0.31、0.53 mg/L,相对标准偏差(RSD,n=10)分别为0.13%、0.18%、0.22%和0.27%。  相似文献   

2.
以聚乙烯醇缩丁醛(PVB)为共聚前驱体,联吡啶钌([Ru(bpy)3]Cl2·6H2O)为氧荧光指示剂,制备了一种新型氧敏感膜,据此建立了采用流动注射荧光光度法测定非水溶剂中微量溶解氧的新方法.在涂膜液中联吡啶钌浓度为1 mmol/L,涂膜液用量为2.5 mL,20 ℃下放置24 h,40 ℃恒温干燥48 h时,制备的氧敏感膜(膜厚0.5 mm)对氧响应的灵敏度最高.当激发波长为465 nm,溶液流速为1.0 mL/min时,该敏感膜对氧有较快的响应时间、良好的响应可逆性、较好的稳定性.对1,2-丙二醇和PEG-400中溶解氧的测定结果表明,两者的Stern-Volmer曲线的线性范围分别为0 ~69.12 mg/L和0 ~109.54 mg/L,检出限分别为4.25 mg/L和0.56 mg/L,RSD(n=6)分别为2.0%和1.8%.  相似文献   

3.
设计并制备了一种基于高分子聚合物(甲基丙烯酸甲酯-丙烯酸丁酯共聚物,MMA-BA)和碳纳米复合材料的固接离子选择性电极来检测水中铅离子Pb~(2+).电极使用高聚物MMA-BA作为传感膜的骨架,利用其优良的性质以及多壁碳纳米管的作用显著提高电极的传感性质.电极具有在低检测范围内的响应的特性,可将其应用在饮用水的实际检测中.  相似文献   

4.
静电组装金纳米粒子制备局域表面等离子体共振传感膜   总被引:4,自引:1,他引:3  
采用聚电解质自组装技术制备局域表面等离子体共振(LSPR)传感膜的方法, 在玻璃基片上依次沉积聚电解质PDDA, PSS和PVTC, 并通过静电吸附构建胶体金纳米粒子自组装膜形成LSPR传感膜. 利用扫描电镜对LSPR传感膜表面形貌以及膜中金纳米粒子的粒径进行了表征, 同时通过紫外-可见消光光谱对其灵敏度和渗透深度等重要参数进行检测. 研究结果表明, 所制备的LSPR传感膜粒子分布均匀、单分散性好、稳定性高、重现性好; 消光峰位对样品溶液折射率的检测灵敏度为71 nm/RIU, 相应的峰强检测灵敏度为0.21 AU/RIU, 对表面吸附层的渗透深度约为16 nm.  相似文献   

5.
根据锂的萃取化学,以1-(苯基偶氮)萘酚-2(ST-I)及氧化三辛基膦(TOPO)为载体和协萃剂制备了PVC膜锂离子选择性电极.考察了增塑剂等因素对电极响应性能的影响,并对膜组成进行优化.以含4.5mgST-I,9.0mgTOPO及180mg磷酸三丁酯的膜制备的电极在pH8.5的tris缓冲底液中对锂呈线性电位响应,斜率为51.7mV/pC,线性范围为2.0×10-5~1.0×10-1mol/L,检测下限为4.0×10-6mol/L.电极用于碳酸锂片剂中锂含量测定,结果满意.  相似文献   

6.
制备了一种新型氧敏感膜用于测定水中的溶解氧。以乙酸纤维素(CA)为载体,八乙基铂卟啉(Pt OEP)为氧敏感指示剂制备氧敏感膜,并通过添加Si O2改善膜体的光学性能。膜片对氧饱和水溶液和氮饱和水溶液测定的相对标准偏差分别为1.1%(n=10)和0.92%(n=10),响应时间分别为19 s和23 s,线性相关系数为0.9972。敏感膜对氧有较快的响应时间、良好的响应可逆性以及较好的稳定性。  相似文献   

7.
利用种子生长法制备金纳米棒,将其分散于聚乙烯醇溶液中,以戊二醛为交联剂,制备了对Hg2+有光学响应性的化学交联聚乙烯醇/金纳米棒(PVA/GNRs)复合凝胶膜。利用紫外-可见光谱法表征了该复合凝胶膜对Hg2+的传感性能。结果表明,在还原剂抗坏血酸的辅助下,PVA/GNRs凝胶对Hg2+有良好的光学响应和选择性,测量线性范围为0.1~3.0μmol/L,相关系数为0.997,响应时间为5 min。以PVA/GNRs复合凝胶膜构建的光学传感器具有制备方法简便、稳定性高等优点,可用于水样中微量Hg2+的检测。  相似文献   

8.
采用光聚合法在一次性丝网印刷电极上制备琥珀酸氯霉素分子印迹膜,然后将丝网印刷电极通过电极插口与电化学分析装置相连接,组装成检测琥珀酸氯霉素残留的电化学传感仪.使用与传感装置相连接的记录仪记录响应的结果.采用本传感仪建立了检测氯霉素的标准曲线并测试了实际牛奶样品中氯霉素含量.电镜学观察表明,与非印迹膜相比,在印迹膜表面形成大量直径约为100 nm的印迹微孔.本传感仪装置检测琥珀酸氯霉素具有很高的灵敏度和特异性,检出限为2×10-9 mol/L,检测线性范围为1×10-8~1.2×10-5 mol/L,基于牛奶样品的检测回收率介于93.5%~95.5%之间.  相似文献   

9.
以化学交联的聚乙烯醇(PVA)凝胶为基质,固定由沉淀聚合法制备的聚(丙烯酰胺-co-甲基丙烯酸)[P(AM-co-MAA)]微凝胶和刚果红,构筑了对p H有光学响应性的新型复合凝胶膜。采用连接有紫外-可见分光光度计的测试系统对复合凝胶膜的传感性能进行了研究,并考察了复合凝胶膜的响应时间和稳定性。结果表明,P(AM-co-MAA)微凝胶和刚果红对光吸收性能有明显的协同增效作用,复合凝胶膜的p H响应范围为4.1~0.5,响应时间小于100 s,显示出比固定单一p H敏感物更优越的性能。  相似文献   

10.
采用N,N′-亚甲基双丙烯酰胺(MBA)为功能单体、钯纳米粒子为掺杂剂、马来松香丙烯酸乙二醇酯为交联剂,在玻碳电极上热聚合具有三甲氧苄啶(TMP)识别性能的钯纳米材料修饰的分子印迹传感膜.采用扫描电镜及红外光谱对合成的钯纳米材料、印迹传感膜的形貌及其结构进行了表征;采用循环伏安法(CV)、交流阻抗法(EIS)对钯纳米粒子掺杂的印迹电极与无掺杂电极的电化学性能进行了研究.结果表明,纳米粒子掺杂的印迹电极与无掺杂电极的表面形貌及电化学性能明显不同.差分脉冲伏安法(DPV)表征结果表明,TMP的浓度在5.0×10-7~4.0 ×10-3 mol/L范围内与脉冲峰电流呈良好的线性关系(R=0.9995),检出限为3.2×10-8 mol/L (S/N=3).此钯纳米粒子掺杂的印迹传感器具有较高的灵敏度.即时电流测定结果表明,新诺明(SMZ)、磺胺嘧啶(SDZ)、葡萄糖 (Glu)、尿素 (Urea)对三甲氧苄啶(TMP)的测定不产生干扰.将此印迹传感器用于实际样品中TMP的检测,加标回收率为96.8%~102.0%.  相似文献   

11.
Polarization-based oxygen sensor   总被引:2,自引:0,他引:2  
A new approach to oxygen sensing based on the luminescence polarization observed from a novel type of sensor is described. The oxygen sensor consists of an oxygen-sensitive silicone film containing tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) chloride [Ru(dpp)3Cl2] and an oxygen-insensitive film of Styryl 7 in poly(vinyl alcohol). Polarizers are used to select orthogonally polarized emission components from Ru(dpp)3Cl2 and Styryl 7. The polarization of the combined emission was found to be highly sensitive to the partial pressure of oxygen. This method of polarization sensing is generic and can be used with any fluorophore which displays an analyte-dependent change in intensity.  相似文献   

12.
本文根据氧分子能有效地猝灭金属有机络合物的荧光的原理,研制了一种氧传感器。  相似文献   

13.
An organically modified silicate(ORMOSIL) based optical sensor response to gaseous O2 or O2 dissolved in water is presented. The oxygen sensing film mechanism is based on the principle of fluorescence quenching of tris(4,7-diphenyl-l , 10-phenanthroline) ruthenium ( ) ([Ru(dpp)3]2+), which has been entrapped in a porous ORMOSIL film. In order to establish optimum film-processing parameters, comprehensive investigations, including the effects of the polarity and the hydrophobicity of the sensing film on oxygen quenching response and response time, were carried out. The film hydrophobicity increased as a function of dimethyl-dimethoxysilane (DiMe-DMOS) content, which is correlated with enhanced oxygen sensor performance. The sensor developed in the present work exhibits the advantages of fast response time and good reversibility. The detection limits are 0. 5 % and 0. 3 g/mL for O2 in the gaseous and the aqueous phases, respectively.  相似文献   

14.
The measurement of local oxygen level in 3D cell culture is desired but remains as a challenge problem. We developed a 3D cell scaffold with luminescence-based oxygen sensing capability that opens the possibility of 3D mapping of oxygen level during cell growth. Hydrogel inverted opal scaffold was prepared by photo-polymerization of poly(2-hydroxyethyl methacrylate (pHEMA) and poly(methacryloyloxy)ethyl-trimethylammonium chloride (pMEATAC) monomer using close-packed bead assembly as template. Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium chloride (Ru(dpp)(3)), was coated on the pHEMA-pMEATAC 3D scaffolds by layer-by-layer (LBL) assembly. pHEMA-pMEATAC copolymer was coated on top of the Ru(dpp)(3) layer as a protection layer. The fluorescence emission of Ru(dpp)(3) can be dynamically quenched by oxygen. By measuring the emission intensity of the scaffold, the local oxygen level can be monitored. The hydrogel scaffolds are transparent, and thus 3D fluorescence intensity can be mapped by confocal microscopy. Human bone marrow stromal cells HS-5 were successfully cultured on the oxygen sensing scaffold, and the observed Ru(dpp)(3) emission intensity from the scaffold was stronger in cell rich area, which indicates a lower oxygen level due to the consumption of the cells.  相似文献   

15.
A Water-Soluble Luminescence Oxygen Sensor   总被引:1,自引:0,他引:1  
We developed a water-soluble luminescent probe for dissolved oxygen. This probe is based on (Ru[dpp(SO3Na)2]3) Cl2, which is a sulfonated analogue of the well-known oxygen probe (Ru[dpp]3)Cl2. The compound dpp is 4,7-diphenyl-1,10-phenanthroline and dpp(SO3Na)2 is a disulfonated derivative of the same ligand. In aqueous solution in the absence of oxygen (Ru[dpp(SO3Na)2]3)Cl2 displays a lifetime of 3.7 μs that decreases to 930 ns on equilibrium with air and 227 ns on equilibrium with 100% oxygen. The Stern–Vohner quenching constant is 11330 M−1. This high oxygen-quenching constant means that the photoluminescence of Ru(dpp[SO3Na]2)3Cl2 is 10% quenched at an oxygen concentration of 8.8 x 10−6 M , or equilibration with 5.4 torr of oxygen. The oxygen probe dissolved in water displays minimal interactions with lipid vesicles composed of dipalmityl-L-α-phosphatidyl glycerol but does appear to interact with human serum albumin. The absorption maximum near 480 nm, long lifetime and large Stokes'shift allow this probe to be used with simple instrumentation based on a light-emitting diode light source, allowing low-cost oxygen sensing in aqueous solutions. To the best of our knowledge this is the first practical water-soluble oxygen sensor.  相似文献   

16.
A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.  相似文献   

17.
为减少荧光指示剂被水萃取流失,提高荧光膜的使用寿命,将5-氨基-邻菲咯啉与二(4,7-二苯基-邻菲咯啉)二氯化钌(Ⅱ)络合,合成带氨基的荧光指示剂[Ru(dpp)2(phen-NH2)]Cl2,并经氨基键合到有机玻璃表面。以核磁、质谱、红外验证合成荧光指示剂的结构,研究键合条件对染色有机玻璃荧光发射的影响,监测荧光强度随水浸泡时间的变化。合成荧光指示剂的荧光发射峰值波长为570 nm,键合到有机玻璃后发射光谱红移20 nm,荧光强度受溶解氧影响,响应时间约为10 s,氧猝灭比达4。染色有机玻璃的荧光稳定性好,在50 ℃水中浸泡7个月,荧光强度下降小于1%。  相似文献   

18.
Mononuclear [Ru(II)(tptz)(acac)(CH3CN)]ClO4 ([1]ClO4) and mixed-valent dinuclear [(acac)2Ru(III){(mu-tptz-Eta+)-}Ru(II)(acac)(CH3CN)]ClO4 ([5]ClO4; acac = acetylacetonate) complexes have been synthesized via the reactions of Ru(II)(acac)2(CH3CN)2 and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), in 1:1 and 2:1 molar ratios, respectively. In [1]ClO4, tptz binds with the Ru(II) ion in a tridentate N,N,N mode (motif A), whereas in [5]ClO4, tptz bridges the metal ions unsymmetrically via the tridentate neutral N,N,N mode with the Ru(II) center and cyclometalated N,C- state with the Ru(III) site (motif F). The activation of the coordinated nitrile function in [1]ClO4 and [5]ClO4 in the presence of ethanol and alkylamine leads to the formation of iminoester ([2]ClO4 and [7]ClO4) and amidine ([4]ClO4) derivatives, respectively. Crystal structure analysis of [2]ClO4 reveals the formation of a beautiful eight-membered water cluster having a chair conformation. The cluster is H-bonded to the pendant pyridyl ring N of tptz and also with the O atom of the perchlorate ion, which, in turn, makes short (C-H- - - - -O) contacts with the neighboring molecule, leading to a H-bonding network. The redox potentials corresponding to the Ru(II) state in both the mononuclear {[(acac)(tptz)Ru(II)-NC-CH3]ClO4 ([1]ClO4) > [(acac)(tptz)Ru(II)-NH=C(CH3)-OC2H5]ClO4 ([2]ClO4) > [(acac)(tptz)Ru(II)-NH2-C6H4(CH3)]ClO4 ([3]ClO4) > [(acac)(tptz)Ru(II)-NH=C(CH3)-NHC2H5]ClO4 ([4]ClO4)} and dinuclear {[(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(NC-CH3)]ClO4 ([5]ClO4), [(acac)2Ru(III){(mu-tptz-H+(N+-O-)2)-}Ru(II)(acac)(NC-CH3)]ClO4 ([6]ClO4), [(acac)2Ru(III){(mu-tptz-H+)-}Ru(II)(acac)(NH=C(CH3)-OC2H5)]ClO4 ([7]ClO4), and [(acac)2Ru(III){(mu-tptz-Eta+)-}Ru(II)(acac)(NC4H4N)]ClO4 ([8]ClO(4))} complexes vary systematically depending on the electronic nature of the coordinated sixth ligands. However, potentials involving the Ru(III) center in the dinuclear complexes remain more or less invariant. The mixed-valent Ru(II)Ru(III) species ([5]ClO4-[8]ClO4) exhibits high comproportionation constant (Kc) values of 1.1 x 10(12)-2 x 10(9), with substantial contribution from the donor center asymmetry at the two metal sites. Complexes display Ru(II)- and Ru(III)-based metal-to-ligand and ligand-to-metal charge-transfer transitions, respectively, in the visible region and ligand-based transitions in the UV region. In spite of reasonably high K(c) values for [5]ClO4-[8]ClO4, the expected intervalence charge-transfer transitions did not resolve in the typical near-IR region up to 2000 nm. The paramagnetic Ru(II)Ru(III) species ([5]ClO4-[8]ClO4) displays rhombic electron paramagnetic resonance (EPR) spectra at 77 K (g approximately 2.15 and Deltag approximately 0.5), typical of a low-spin Ru(III) ion in a distorted octahedral environment. The one-electron-reduced tptz complexes [Ru(II)(tptz.-)(acac)(CEta3CN)] (1) and [(acac)2Ru(III){(mu-tptz-Eta+).2-}Ru(II)(acac)(CH3CN)] (5), however, show a free-radical-type EPR signal near g = 2.0 with partial metal contribution.  相似文献   

19.
Zigler DF  Wang J  Brewer KJ 《Inorganic chemistry》2008,47(23):11342-11350
Bimetallic complexes of the form [(bpy)(2)Ru(BL)RhCl(2)(phen)](PF(6))(3), where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and BL = 2,3-bis(2-pyridyl)pyrazine (dpp) or 2,2'-bipyrimidine (bpm), were synthesized, characterized, and compared to the [{(bpy)(2)Ru(BL)}(2)RhCl(2)](PF(6))(5) trimetallic analogues. The new complexes were synthesized via the building block method, exploiting the known coordination chemistry of Rh(III) polyazine complexes. In contrast to [{(bpy)(2)Ru(dpp)}(2)RhCl(2)](PF(6))(5) and [{(bpy)(2)Ru(bpm)}(2)RhCl(2)](PF(6))(5), [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) and [(bpy)(2)Ru(bpm)RhCl(2)(phen)](PF(6))(3) have a single visible light absorber subunit coupled to the cis-Rh(III)Cl(2) moiety, an unexplored molecular architecture. The electrochemistry of [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) showed a reversible oxidation at 1.61 V (vs Ag/AgCl) (Ru(III/II)), quasi-reversible reductions at -0.39 V, -0.74, and -0.98 V. The first two reductive couples corresponded to two electrons, consistent with Rh reduction. The electrochemistry of [(bpy)(2)Ru(bpm)RhCl(2)(phen)](PF(6))(3) exhibited a reversible oxidation at 1.76 V (Ru(III/II)). A reversible reduction at -0.14 V (bpm(0/-)), and quasi-reversible reductions at -0.77 and -0.91 V each corresponded to a one electron process, bpm(0/-), Rh(III/II), and Rh(II/I). The dpp bridged bimetallic and trimetallic display Ru(dpi)-->dpp(pi*) metal-to-ligand charge transfer (MLCT) transitions at 509 nm (14,700 M(-1) cm(-1)) and 518 nm (26,100 M(-1) cm(-1)), respectively. The bpm bridged bimetallic and trimetallic display Ru(dpi)-->bpm(pi*) charge transfer (CT) transitions at 581 nm (4,000 M(-1) cm(-1)) and 594 nm (9,900 M(-1) cm(-1)), respectively. The heteronuclear complexes [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) and [{(bpy)(2)Ru(dpp)}(2)RhCl(2)](PF(6))(5) had (3)MLCT emissions that are Ru(dpi)-->dpp(pi*) CT in nature but were red-shifted and lower intensity than [(bpy)(2)Ru(dpp)Ru(bpy)(2)](PF(6))(4). The lifetimes of the (3)MLCT state of [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) at room temperature (30 ns) was shorter than [(bpy)(2)Ru(dpp)Ru(bpy)(2)](PF(6))(4), consistent with favorable electron transfer to Rh(III) to generate a metal-to-metal charge-transfer ((3)MMCT) state. The reported synthetic methods provide means to a new molecular architecture coupling a single Ru light absorber to the Rh(III) center while retaining the interesting cis-Rh(III)Cl(2) moiety.  相似文献   

20.
为提高极性荧光指示剂Ru(dpp)3Cl2在非极性硅橡胶中的分散性,以沉淀白炭黑、气相白炭黑和甲基MQ树脂,载负荧光指示剂Ru(dpp)3Cl2,再填充到二甲基硅橡胶(PDMS)中,制备氧敏感荧光膜.以分光光度计和荧光光谱仪,研究载体种类对Ru(dpp)3Cl2的吸附性、荧光特性及氧敏感荧光膜性能的影响.白炭黑载负Ru(dpp)3Cl2的荧光发射光谱相对其稀溶液约红移20 nm.载体表面的甲基可减弱SiO2载体对Ru(dpp)3Cl2分子的吸附性和相互作用,减少荧光发射光谱的红移12 nm,提高荧光强度近10倍.白炭黑有助改善Ru(dpp)3Cl2在PDMS中的分散性和氧敏感荧光膜的荧光输出和猝灭比,尤以MQ树脂的效果最为显著.  相似文献   

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