CN103994993A - Photoelectric sensor based on functionalized triphenylamine dye TiO2 nano composite - Google Patents
Photoelectric sensor based on functionalized triphenylamine dye TiO2 nano composite Download PDFInfo
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- CN103994993A CN103994993A CN201410214438.XA CN201410214438A CN103994993A CN 103994993 A CN103994993 A CN 103994993A CN 201410214438 A CN201410214438 A CN 201410214438A CN 103994993 A CN103994993 A CN 103994993A
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Abstract
The invention discloses a photoelectric sensor based on a functionalized triphenylamine dye TiO2 nano composite, and an application of the photoelectric sensor in biological micromolecule photoelectric detection. The photoelectric sensor consists of three parts, namely, a photoelectrode, titanium dioxide nano particles and functionalized triphenylamine dye, wherein the titanium dioxide nano particles are fixed on the surface of the photoelectrode through sintering so as to adsorb the functionalized triphenylamine dye through coordination with carboxyl, and forming a photoelectric sensing interface on the photoelectrode; in excitation of visible light, transmitting photoelectrons to the photoelectrode when the photoelectric sensing interface is amplified by ascorbic acid, so as to generate initial light current; and soaking the photoelectric sensing interface into a biologic thiol solution, performing addition reaction on the functionalized triphenylamine dye modified on the sensing interface with the biologic thiol through recognition groups, so as to reduce the capability of the functionalized triphenylamine dye in transmitting the photoelectrons to the photoelectrode. By adopting the sensor, photoelectric detection on the biologic thiol is achieved, the sensitivity and the selectivity are good, the analysis speed is fast, the reproducibility is good, the detection cost is low, and the equipment is small and exquisite.
Description
Technical field
The present invention relates to a kind of based on function triphenyl amine dyes-TiO
2the photoelectric sensor of nano-complex and the application in biological micromolecule Photoelectric Detection thereof, be, and there is the photoelectricity identification interface of little molecular specificity reactivity as a kind of photoelectric sensor of base growth taking a kind of, and then realize the selective light electro-detection of biological micromolecule in complex system.
Background technology
In living things system, biological micromolecule as: biological thiol, active oxygen, nitrogen monoxide, dopamine etc. have all participated in many important physiological reactions, and the abnormal and numerous disease of its concentration is all closely related.Develop biological micromolecule detection method highly sensitive, high selectivity, the micromolecular original position of target biology, on-line monitoring, for the essence of understanding biological phenomena, the effective means that discloses generation, development and the control of searching disease of disease all has great importance.
At present, chromatography mass spectrometry is still the micromolecular analysis means of the most frequently used detection of biological.The features such as application of gas chromatorgraphy/mass method has that analysis speed is fast, separation efficiency good, highly sensitive and applied range, but it is with high content of technology, sample pretreatment is loaded down with trivial details, running program relative complex, instrument are expensive, and need specific experiment condition and professional to operate, be unsuitable for the on-line analysis to biological sample.Utilize the micromolecular redox property of part biological, as biological thiol can be at metal and the direct oxidized generation disulfide of carbon electrodes, and producing the oxidation current being directly proportional to its concentration, electrochemical method is also widely used in the mensuration of biological micromolecule.Than chromatography, electrochemical method is highly sensitive, equipment needed thereby is simple, testing cost is low.But, due to miscellaneous oxidation-reduction quality material that conventionally coexisted in complex system, be difficult to realize the micromolecular selective determination of particular organisms with electrochemical method.At present, poor selectivity and electrode passivation be serious etc., and problem is still the subject matter that electrochemical method faces in little Molecular Detection.In recent years, target has obtained development fast in the online fluorescent probe technique detecting of biological micromolecule.Last decade, millions of well behaved fluorescence probes are developed, and part probe can be successfully for living cells imaging, becomes one of important means of biological micromolecule in current detecting cell.But, how to eliminate the interference of biological substrate background fluorescence, life-span and the excitation wavelength of raising fluorescence probe, and how to avoid the optical damage of cell in testing process and improve the high selectivity identification of fluorescence probe in complex system remaining significant challenge and the technological difficulties that fluorescent probe technique faces in biological micromolecule detects.Therefore, find simpler, sensitive, selectivity is good, can Real-Time Monitoring and the analytical approach of biological micromolecule with low cost be still the hot issue that analytical chemistry worker pays close attention to.
Photoelectric sensing method is that one is utilized dyestuff and the peculiar photoelectric property of semiconductor nano material, and the light energy conversion that dyestuff can be absorbed becomes electric energy output, and the emerging analytical approach of according to the variation of electric signal, analyzed component being carried out quantitative measurement.The method is owing to excitaton source can being separated with detection resources, thereby can effectively reduce background interference, improves the sensitivity detecting; In addition, the method also has that the peculiar cost of electricity analytical method is low, equipment is simple and probe is easy to the remarkable advantages such as microminiaturized, has all shown huge application potential at cell and live body on-line analysis field.Traditional photoelectric analysis method is in the time detecting for biological micromolecule, normally used strategy is all the redox property (as biological thiol) that utilizes biological micromolecule, set it as the electron donor of photovoltaic reaction, by electron donor, the amplification of photocurrent is measured.This method is highly sensitive, but because the oxidation-reduction quality material coexisting in complex system is many, is difficult to realize the selective determination to target molecule.Active and functional dye reacts the variation of front and back photocurrent with biological micromolecule to the specific reaction of biological micromolecule to utilize reactive dye, can realize the selective determination of biological micromolecule, due to the effective problem separating of photoelectric analysis method excitaton source and detection resources, can avoid the interference of background signal simultaneously.Therefore, based on reactive dye-TiO
2nano composite material photoelectric sensor can have the advantages such as high sensitivity, high selectivity and equipment is small and exquisite, simple to operate concurrently simultaneously.
Summary of the invention
The invention provides a kind of based on function triphenyl amine dyes-TiO
2the photoelectric sensor of nano-complex, realized it and in complex system, the high selectivity of biological micromolecule detected, and solved that biological micromolecule in complex system is difficult to detect and the problem of poor selectivity.
The present invention includes two parts core content:
(1) structure of photoelectric sensor function interface;
(2) application of photoelectric sensor in biological micromolecule mercaptan selectivity detects.
The present invention is achieved through the following technical solutions:
A kind of based on function triphenyl amine dyes-TiO
2the photoelectric sensor of nano-complex, this photoelectric sensor comprises optoelectronic pole, titanium dioxide nano-particle and function triphenyl amine dyes; The particle diameter of described titanium dioxide nano-particle is below 100nm, after sintering is removed organic additive by being mixed and made into slurry with terpinol, cellulose, be coated on and be fixed on optoelectronic pole surface, obtain having the titanium dioxide nano-particle function photoelectricity interface of loose and porous structure, by with the coordination adsorption function triphenyl amine dyes of carboxyl; Described function triphenyl amine dyes is mainly made up of three parts: electron donor (trianilino group), recognition group (α, alpha, beta-unsaturated ketone) and acceptor (carboxyl).
Under excited by visible light, the generation photoelectron that can be excited of the electron donor part in functional dye, and transmit photoelectron to optoelectronic pole under the effect of electron withdraw group carboxyl, produce Primary photocurrent.Described sensing interface is soaked in biological thiol solution, the function triphenyl amine dyes of modifying on sensing interface is by recognition group α, alpha, beta-unsaturated ketone and biological thiol generation addition reaction, become singly-bound by the reduction in former functional dye structure, causes the destruction of its conjugated system.In the case with this sensor of excited by visible light, triphenylamine cannot be transmitted to optoelectronic pole by the photoelectron that optical excitation produced, and causes the reduction of photocurrent.Therefore, before and after reacting with triphenylamine functional dye by function interface, transmit the difference of photoelectron ability to optoelectronic pole, can realize the selectivity of biological micromolecule mercaptan is detected.
During the biological micromolecule mercaptan selectivity that can be used in above-mentioned photoelectric sensor detects, detecting step is as follows:
1. in ascorbic acid solution (electron donor, the variation that can amplify photocurrent), under suitable voltage, with the Primary photocurrent of chronoamperometry recording light electric transducer;
2. optoelectronic pole is soaked in sample solution, makes the functional dye generation chemical reaction on biological micromolecule and sensing interface; After rinsing with washing fluid, according to 1. step detection and the reacted photocurrent of biological micromolecule;
3. calculate photocurrent variations rate, investigate the relation of current changing rate and biological micromolecule concentration, obtain the concentration of biological micromolecule sample from typical curve.
The functional dye of this sensor has the energy level matching with titania conduction band; Titanium dioxide nano-particle has that uniform particle diameter distributes, large specific surface area and excellent photoelectric conversion capacity.In the time that functional dye does not occur to interact with halfcystine, under optical excitation, functional dye can be transferred to optoelectronic pole by the electronics on triphenylamine, produces Primary photocurrent PI
0; When functional dye is by recognition group α, alpha, beta-unsaturated ketone and halfcystine occur after specific Michael addition reaction, the conjugated structure that can destroy original dye, blocking light excites the electronics transferring path of lower electron donor to optoelectronic pole, generates the photocurrent PI reducing
1.Due to the rate of change (PI of photocurrent
0-PI
1)/PI
0be directly proportional to the concentration of halfcystine, utilize the quantitative relationship between photocurrent variations rate and little molecular conecentration, realize high selectivity and the high-sensitive Photoelectric Detection of biological micromolecule.In this detection system, functional dye is made up of electron donor, electron accepter and the large main modular of little molecular recognition group three, therefore, by changing the composition of disparate modules, can work as this sensing strategy flexibly for the micromolecular selective determination of other biological.
Photoelectric sensor of the present invention for compared with the photoelectric sense technology of little Molecular Detection, has following characteristics with existing:
(1) the present invention utilizes reactive dye to react the difference of front and back to optoelectronic pole transmission photoelectron ability with biological micromolecule, and in conjunction with the signal amplification of titanium dioxide nano-particle, the high selectivity that can realize biological micromolecule detects.The selectivity that described photoelectric sensor can be realized biological micromolecule in complex system detects, and can get rid of the interference of uric acid in urine sample, each amino acid and various reductibility reagent.
(2) this photoelectric sensor combines with the high specific reactivity of biological micromolecule functional dye with photoelectric analysis method, in having high sensitivity and high selectivity concurrently, also have that analysis speed is fast, the low and equipment of favorable reproducibility, testing cost is small and exquisite is easy to the advantages such as microminiaturized.
(3) titania on described photoelectric sensing interface has loose porous structure, can support more dyestuff and be convenient to the diffusion of little molecule on function interface with the contacting of functional dye, therefore described sensor has the advantages such as highly sensitive and response is quick.
(4) titanium dioxide nano-particle on described photoelectric sensor surface is fixed on optoelectronic pole surface by agglomeration, makes this sensor have higher stability, is easy to preserve.
Brief description of the drawings
Fig. 1 is based on reactive dye-TiO
2the schematic diagram that the photoelectric analysis method of nano-complex detects halfcystine.
Fig. 2 (A) is the halfcystine photoelectric response figure that the described photoelectric sensor interference material that is 1.0mM to concentration or concentration are 0.2mM:
Fig. 2 (B) is the halfcystine fluorescence response figure that the functional dye TTA interference material that is 1.0mM to concentration or concentration are 0.2mM.
Embodiment
Embodiment 1: by reference to the accompanying drawings 1, illustrate that this is based on reactive dye-TiO
2the photoelectric analysis method of nano-complex detects the selectivity of biological micromolecule halfcystine.
(1) electro-conductive glass FTO is cut into the rectangle fritter of 5 × 20mm, after washing powder solution, deionized water, acetone, ethanol branch process, N
2dry up; FTO electrode after treatment is immersed in to the TiC1 of 50mM
4in aqueous solution, pre-service half an hour at 70 DEG C, form fine and close TiO on its surface
2stratum granulosum.The slurry that 4 μ L is consisted of to ethyl cellulose, terpinol and titania nanoparticles is coated on optoelectronic pole, forms titanium dioxide photoelectric functional membrane.Dry under state of nature, sintering at 450 DEG C.Gained TiO
2nanoparticle Modified optoelectronic pole is immersed in triphenylamine reactive dye (TTA) CH of variable concentrations
2cl
2in solution, soak absorbing dye, obtain the photoelectric sensor of target cysteine assay, be abbreviated as: TTA-TiO
2/ FTO.
(2), in the phosphate buffered solution containing 2mM ascorbic acid, pH=7.0, under the optical excitation of 420nm, measure TTA-TiO with electric current-time curve at-0.2V
2the Primary photocurrent of/FTO, is designated as PI
0.
(3) by TTA-TiO
2/ FTO is immersed in the halfcystine solution of variable concentrations, after 10 minutes, takes out, and according to (2) step measurements and the reacted photocurrent of halfcystine, is designated as PI
1.According to photocurrent variations rate (PI
0-PI
1)/PI
0and the quantitative relationship between semicystinol concentration, realizes the quantitative measurement to halfcystine.
Embodiment 2: by reference to the accompanying drawings, TTA-TiO is described
2the antijamming capability of/FTO to disturbance ion.
With TTA-TiO
2/ FTO is respectively to ever-present interfering material in blood, and as ascorbic acid, uric acid, adrenaline, glutathione and each amino acid are measured, its concentration is to be 5 times of semicystinol concentration.Contrast disturbance reagent is at TTA-TiO
2response on/FTO optoelectronic pole.Meanwhile, using TTA as fluorescence probe, the measurement result of contrast fluorescence probe to variable concentrations interfering ion and halfcystine.Shown in Fig. 2 A, TTA-TiO
2/ FTO has shown extremely strong antijamming capability, and except homocysteine, other little molecule is at TTA-TiO
2/ FTO does not produce photoelectric response.But when using TTA as fluorescence probe, as shown in Figure 2 A: TTA has demonstrated poor antijamming capability, some amino acid, as glutamic acid and arginine all can suppress the fluorescence signal of TTA.
Embodiment 3: by reference to the accompanying drawings 1, TTA-TiO is described
2the mensuration accuracy rate of/FTO to halfcystine in urine sample.
(1) with TTA-TiO
2/ FTO measures the cysteine content in Healthy People urine sample.Get 4 Healthy People urine samples, dilute one times with the phosphate buffered solution of pH=7.0, will survey the TTA-TiO of Primary photocurrent
2/ FTO is immersed in urine sample, reacts after 10 minutes, measures photoelectricity flow valuve.According to the concentration of halfcystine in photocurrent variations rate and regression curve reckoning urine sample.
(2) to the cysteine standard solution that adds concentration known in the urine sample of diluting, the TTA-TiO of Primary photocurrent will be tested
2/ FTO is soaked in wherein 10 minutes, again measures photoelectricity flow valuve.Add semicystinol concentration according to gained photocurrent variations rate and linear regression curve calculating.
(3) record the difference of semicystinol concentration and the addition calculate recovery rate of known halfcystine according to step (2) and step (1), remember in table 1.As seen from the data in Table 1, the determination of recovery rates result of 4 healthy urine samples, between 102-115%, illustrates that the method has excellent selectivity.
Described in table 1., photoelectric sensor is measured and recovery data cysteine content in urine sample
Claims (2)
1. one kind based on function triphenyl amine dyes-TiO
2the photoelectric sensor of nano-complex, is characterized in that, this photoelectric sensor comprises optoelectronic pole, titanium dioxide nano-particle and function triphenyl amine dyes; The particle diameter of described titanium dioxide nano-particle is below 100nm, after sintering is removed organic additive by being mixed and made into slurry with terpinol, cellulose, be coated on and be fixed on optoelectronic pole surface, obtain having the titanium dioxide nano-particle function photoelectricity interface of loose and porous structure, by with the coordination adsorption function triphenyl amine dyes of carboxyl; Described function triphenyl amine dyes is mainly made up of three parts: electron donor (trianilino group), recognition group (α, alpha, beta-unsaturated ketone) and acceptor (carboxyl).
2. photoelectric sensor claimed in claim 1 detects for biological micromolecule mercaptan selectivity, it is characterized in that detecting step is as follows:
1. at ascorbic acid solution, with the Primary photocurrent of chronoamperometry recording light electric transducer;
2. optoelectronic pole is soaked in sample solution, makes the functional dye generation chemical reaction on biological micromolecule and sensing interface; After rinsing with washing fluid, according to 1. step detection and the reacted photocurrent of biological micromolecule;
3. calculate photocurrent variations rate, investigate the relation of current changing rate and biological micromolecule concentration, obtain the concentration of biological micromolecule sample from typical curve.
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Application publication date: 20140820 |