CN107817285A - A kind of electrochemical luminescence nm logic operated device and preparation method - Google Patents
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Abstract
The invention discloses a kind of electrochemical luminescence nm logic operated device and preparation method, its preparation method content includes：The preparation of BPEA nano wires, the preparation of electrochemical luminescence sensor, basic boom using BPEA nanowire electrochemicals luminescence sensor as Molecular Logic Gates, detection molecules are needed as input condition with another using triphenylamine, the Strength Changes for the ECL signals that BPEA nano wires are sent are output result, so as to realize logical operation.The electrochemical luminescence nm logic operated device, it is made by preparation method as described above, there is excellent performance, cheap, technique to be simple and convenient to operate for it, low manufacture cost, wide and environment-friendly compared to inorganic nano material and traditional organic nano material applicability, can be applied in different field.
Description
Technical field
The present invention relates to a kind of electrochemical luminescence nm logic operated device and preparation method.
Background technology
Gate can be used in the information processing in chemical molecular field, including nano molecular etc..For molecular device function
Material, because its unique advantage and wide prospect turn into the research emphasis of 21 century, be construed to most to be expected to substitution tradition with
Device material based on silicon.Since the contact between molecular switch and Molecular Logic Gates is recognized, point based on chemical system
Sub- gate fast development, the Molecular Logic Gates of basic boolean logic function unit are achieved based on chemical system.Molecule
Reconstruct, combination and the combinational logic molecular system by complexity of gate are programmed and cause scientists greatly to be paid close attention to.
At present, generally carried out for Molecular Logic Gates, its input and output signal by molecular biology manipulations,
It is also possible to be carried out by phosphor reader.Electrochemical luminescence (electrochemiluminescence, ECL) is electric energy
Switching to radiation energy, under certain potentials, excitation state is formed by electron transmission, excited state molecule produces photon when becoming ground state, and
ECL methods are simple, high sensitivity, the range of linearity are wide.Electrochemical luminescence logical operation based on electrochemical luminescence structure has sensitive
The advantages that spending height, being not required to mark and be easy to operate, Molecular Logic Gates based on this foundation have certain biochemical information,
The discriminating and quantitative determination of corresponding molecule can be used for.
The content of the invention
It is an object of the invention to provide a kind of electrochemical luminescence nm logic operated device and preparation method, for one
The discriminating and quantitative determination of a little materials.
The invention discloses a kind of novel electrochemical luminescence nm logic operated device and its preparation method is disclosed,
By the basic boom that BPEA nanowire electrochemicals luminescence sensor is Molecular Logic Gates, so as to be used for detecting triphenylamine
(TprA), the material such as dopamine (DA), proline (Pro), methylene blue (MB).
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions：
A kind of preparation method of electrochemical luminescence nm logic operated device, its content comprise the following steps：
Step 1：The preparation of BPEA nano wires, BPEA nano wires are prepared using the method for physical vapour deposition (PVD), make its deposition
In substrate；
A certain amount of BPEA powder is weighed to be dissolved in organic solvent and move on in 100mL two mouthfuls of flasks；Flask is put
In oil bath, organic solvent evaporation is made to oil bath heating with heater, rotary flask makes BPEA in flask in evaporation process
Bottom of bottle form uniform film；Substrate is suspended in again the top of BPEA powder beds, inserts thermometer flatly from flask, pass through oil
The change of bath temperature, and then the temperature in flask is adjusted；After oil bath temperature reaches predetermined temperature, BPEA gas phase point
Son is just nucleated and grown in substrate, is consequently formed BPEA nano wires；
Step 2：The preparation of electrochemical luminescence sensor, the BPEA nano wire modified conducting vitreous electricities prepared using step 1
Pole, so as to prepare electrochemical luminescence sensor；
The preparation of ECL sensors：First, it is 2.0 × 4.5cm electro-conductive glass (ITO) to be cut into size2Cuboid, then
It is cleaned according to the following steps：
The first step, electro-conductive glass (ITO) is immersed in and added in the running water of detergent, and put it to the super of 53MHz
Ultrasonic cleaning 20min is carried out in sound wave washer；
Second step, the detergent on electro-conductive glass (ITO) surface is rinsed with enough running water, untill without foam；
3rd step, electro-conductive glass (ITO) is eluted 4 times respectively with absolute ethyl alcohol and ultra-pure water；
4th step, it is standby after using high-purity argon gas, electro-conductive glass (ITO) is dried up；Then, physical vapour deposition (PVD) is utilized
Method prepare BPEA nano wires, making BPEA nanowire depositions, ECL sensors are successfully prepared on electro-conductive glass；
Step 3：ECL based on BPEA nano wires detects the Molecular Logic Gates constructed：Sent out with BPEA nanowire electrochemicals
Optical sensor is the basic boom of Molecular Logic Gates, using triphenylamine and another material for needing detection molecules as input condition, BPEA
The Strength Changes for the ECL signals that nano wire is sent are output result, so as to realize logical operation.
As the restriction to aforesaid way, in step 1, the organic solvent is ethanol, or can be dissolved from other
BPEA but the not organic solvent with BPEA reactions.
As the restriction to aforesaid way, in step 1, the predetermined temperature of the oil bath is 60 DEG C, and passes through regulation
Oil bath temperature and growth time it is controllable go out different size and density BPEA nano wires.
As the restriction to aforesaid way, in step 1, the substrate is electro-conductive glass.
As the restriction to aforesaid way, in step 3, another material for needing detection molecules is dopamine, dried meat ammonia
Acid and any one in methylene blue.As a kind of preferred scheme, the triphenylamine (TprA), proline (Pro), methylene
The detectable concentration of blue (MB) is 1 × 10-8Mol/L, the detectable concentration of dopamine (DA) is 3 × 10-5mol/L.Using in the present invention
The detectable other concentration of Molecular Logic Gates in rights protection.
As the restriction to aforesaid way, in step 3, the Molecular Logic Gates constructed can be two input logics
Door, i.e. OR gate (OR), XOR gate (XOR), INHIBITORY-gate (INHIBIT), or three input logic gates and four input logic gates.
Meanwhile a kind of electrochemical luminescence nm logic operated device of the invention, it is made by preparation method as described above；
The Molecular Logic Gates of ECL detection framework of the electrochemical luminescence nm logic operated device based on BPEA nano wires, its is basic
Framework is to be based on BPEA nanowire electrochemical luminescence sensors, with triphenylamine (TprA) and dopamine, proline and methylene blue
In any one be input condition, the Strength Changes of the ECL signals sent using BPEA nano wires is output results；To there is triphen
It is 1 that amine (TprA), dopamine (DA), proline (Pro), methylene blue (MB), which participate in mark input, is not then 0, output knot
Fruit is：If electrochemical luminescence intensity is 0 less than 1000, electrochemical luminescence intensity is 1 if higher than 1000；This result is multiple
Verification experimental verification.
The gate operation that the electrochemical luminescence nm logic operated device is related to has two input logic gates, i.e. OR gate
(OR), XOR gate (XOR), INHIBITORY-gate (INHIBIT)；
The OR gate (OR)：Built with triphenylamine (TprA) and proline (Pro) for input condition；By BPEA nanometers
Line modification establishes ECL sensors on electro-conductive glass (ITO), and triphenylamine (TprA) and proline (Pro) are detected；
The XOR gate (XOR)：Built with triphenylamine (TprA) and dopamine (DA) for input condition；BPEA is received
Rice noodles modification establishes ECL sensors on electro-conductive glass (ITO), and triphenylamine (TprA) and dopamine (DA) are detected；
The INHIBITORY-gate (INHIBIT)：Built with triphenylamine (TprA) and methylene blue (MB) for input condition；Will
ECL sensors are established in the modification of BPEA nano wires on ITO, and triphenylamine (TprA) and methylene blue (MB) are detected.
Logical operation of the present invention and preparation method have following positive beneficial effect：
1. providing a kind of method that different electrochemical luminescence logical operation is constructed by electrochemical luminescence sensor, it has
There is high sensitivity, need not mark, be easy to operate, and Molecular Logic Gates based on this foundation can be used for Molecular Detection.
2. it is to realize one in specific detection with the logical operation that BPEA nanowire electrochemicals luminescence sensor is established
Important breakthrough, it is expected to develop into a kind of molecular device of more advanced functionalization.
3. the electrochemical luminescence nm logic operated device prepared using the inventive method, it has excellent performance, price
Cheap, technique is simple and convenient to operate, low manufacture cost, is applicable compared to inorganic nano material and traditional organic nano material
Property is wide and environment-friendly, can be applied in different field；The selection of electrochemical luminescence nm logic operated device is expanded significantly
Scope, also provide a kind of thinking as the research for constructing nm logic operated device material for organic micro-nano material；Corresponding
Tempting application prospect is shown in the discriminating and quantitative determination of molecule.
Brief description of the drawings
Fig. 1 is the installation drawing that physical vaporous deposition (PVD) prepares BPEA nano wires；
The preparation process schematic diagram of Fig. 2 ECL sensors；
Fig. 3 is BPEA nano wire fluorescence micrographs；
Fig. 4 is to make input signal, schematic diagram of the ECL signals as the OR gate of output signal with triphenylamine and proline；
Fig. 5 is with triphenylamine, proline, logical operation equivalent circuit diagram of the dopamine as input signal；
Fig. 6 is with triphenylamine, proline, dopamine, logical operation equivalent circuit diagram of the methylene blue as input signal.
Embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
A kind of preparation method of electrochemical luminescence nm logic operated device of the present invention, its content comprise the following steps：
Step 1：The preparation of BPEA nano wires (BPEA NWs), BPEA nanometers are prepared using the method for physical vapour deposition (PVD)
Line, it is set to be deposited in substrate；
A certain amount of BPEA powder 5 is weighed to be dissolved in ethanol and move on in 100mL two mouthfuls of flasks；Then, by Fig. 1 institutes
Show, flask is placed in oil bath 2, make organic solvent evaporation to the heating of oil bath 2 with heater 6, the rotary combustion in evaporation process
Bottle makes BPEA form uniform film in the bottom of bottle of flask；3 N is passed through from flask flatly2As protection gas, unnecessary N2It is another from flask
4 discharge flatly.Electro-conductive glass (ITO) 1 is suspended in again the top of BPEA powder beds 5,3 inserts thermometer flatly from flask, pass through
The change of the temperature of oil bath 2, and then the temperature in flask is adjusted；After the temperature of oil bath 2 reaches 60 DEG C of predetermined temperature, BPEA
Gas molecule in space be just nucleated and grown on electro-conductive glass (ITO) 1, be consequently formed BPEA nano wires, Fig. 3 show BPEA
Nano wire fluorescence micrograph；
Step 2：The preparation of electrochemical luminescence sensor, the BPEA nano wire modified conducting vitreous electricities prepared using step 1
Pole, so as to prepare electrochemical luminescence sensor；
The preparation of ECL sensors：First, it is 2.0 × 4.5cm electro-conductive glass (ITO) to be cut into size2Cuboid, then
It is cleaned according to the following steps：
The first step, electro-conductive glass (ITO) is immersed in and added in the running water of detergent, and put it to the super of 53MHz
Ultrasonic cleaning 20min is carried out in sound wave washer；
Second step, the detergent on electro-conductive glass (ITO) surface is rinsed with substantial amounts of running water, untill without foam；
3rd step, electro-conductive glass (ITO) is eluted 4 times respectively with absolute ethyl alcohol and ultra-pure water；
4th step, it is standby after using high-purity argon gas, electro-conductive glass (ITO) is dried up；Then, physical vapour deposition (PVD) is utilized
Method prepare BPEA NWs, BPEA NWs is deposited on electro-conductive glass, ECL sensors are successfully prepared；As shown in Figure 2.
Step 3：ECL based on BPEA nano wires detects the Molecular Logic Gates constructed：Sent out with BPEA nanowire electrochemicals
Optical sensor is the basic boom of Molecular Logic Gates, using detectable concentration as 1 × 10-8Mol/L triphenylamine and detectable concentration be 3 ×
10-5Mol/L dopamines are input condition, it is also possible to which detectable concentration is 1 × 10-8Mol/L proline (Pro), or detection are dense
Spend for 1 × 10-8It is 3 × 10 that mol/L methylene blue (MB), which replaces detectable concentration,-5Mol/L dopamines, BPEA nano wires are sent
The Strength Changes of ECL signals be output result, so as to realize logical operation.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.Embodiment
1st, the two input molecular logic operations based on electrochemical luminescence sensor
1) structure of two input logic operations-OR gate
First, triphenylamine and proline are made input signal, the ECL signals of BPEA nano wires are worked as output signal, passed through
The ECL sensors of BPEA nano wires have constructed OR gate to the detection mechanism of triphenylamine and proline.For OR gate, i.e., when two
As long as to have one in input signal be 1, its output signal is exactly 1.We modify BPEA nanometers first on electro-conductive glass
Line, set up ECL sensors.Then, when triphenylamine and proline are all not present, input signal is (0,0), BPEA nano materials
Electrochemical luminescence, output signal 0 can not be produced.But when adding triphenylamine or proline, that is, input signal is (1,0)
Or when (0,1), using amine substance as coreagent, acted on BPEA nano wires and produce electrochemical luminescence signals, mechanism is preceding
Face has been discussed, output signal 1.When adding triphenylamine and proline simultaneously, that is, when input signal is (1,1), triphen
Amine and proline play synergy jointly, produce electrochemical luminescence signals, output signal 1.This result illustrates that this is one
Typical OR gate, its logic circuit is as shown in figure 4, as shown in Table 1 below it exports truth table.
Table 1：OR gate truth table
Other two input logics operations can be also constructed in the same way, such as：The structure of XOR gate and INHIBITORY-gate
Structure, here, being no longer described in detail one by one.
Embodiment 2, the three input molecular logic operations based on electrochemical luminescence sensor
1) three input logic gate --- [(A or B) XOR C]
Two input logics more than operate, and further demonstrate based on BPEA nano material electrochemical luminescence sensors
Three input Boolean logic operations [(A or B) XOR C], wherein In1=triphenylamines, In2=proline, In3=dopamines are as schemed
Shown in 5, the truth table of this logical operation is as shown in Table 2 below.
Table 2：Output=[(A or B) XOR C] logical operation truth table
2) in addition, three Molecular Logic Gates [(A or B) forbids C] and [(A XOR B) taboo can also be constructed after the same method
Only C], it will not be described in detail herein.
Embodiment 3, the four input molecular logic operations based on electrochemical luminescence sensor
Logical operation more than, further demonstrate four inputs of the tactility apparatus that lighted based on BPEA nanowire electrochemicals
Boolean logic operation [(A or B) XOR C] forbids D, wherein In1=triphenylamines, In2=proline, In3=dopamines, In4=
Methylene blue as shown in fig. 6, the truth table of this Boolean logic operation as shown in Table 3 below.
Table 3：Output=[(A or B) XOR C] forbids D logical operation truth tables
Claims (8)
- A kind of 1. preparation method of electrochemical luminescence nm logic operated device, it is characterised in that：This method content includes as follows Step：Step 1：The preparation of BPEA nano wires, BPEA nano wires are prepared using the method for physical vapour deposition (PVD), it is deposited on base On bottom；A certain amount of BPEA powder is weighed to be dissolved in organic solvent and move on in 100mL two mouthfuls of flasks；Flask is placed in oil In bath, organic solvent evaporation is made to oil bath heating with heater, rotary flask makes BPEA in the bottle of flask in evaporation process Bottom forms uniform film；Substrate is suspended in again the top of BPEA powder beds, inserts thermometer flatly from flask, pass through oil bath temperature The change of degree, and then the temperature in flask is adjusted；After oil bath temperature reaches predetermined temperature, BPEA gas molecule in space is just It is nucleated and is grown in substrate, is consequently formed BPEA nano wires；Step 2：The preparation of electrochemical luminescence sensor, the BPEA nano wire modified conducting glass electrodes prepared using step 1, from And prepare electrochemical luminescence sensor；The preparation of ECL sensors：First, it is 2.0 × 4.5cm electro-conductive glass (ITO) to be cut into size2Cuboid, then by following Step is cleaned to it：The first step, electro-conductive glass (ITO) is immersed in and added in the running water of detergent, and put it to 53MHz ultrasonic wave Ultrasonic cleaning 20min is carried out in washer；Second step, the detergent on electro-conductive glass (ITO) surface is rinsed with enough running water, untill without foam；3rd step, electro-conductive glass (ITO) is eluted 4 times respectively with absolute ethyl alcohol and ultra-pure water；4th step, it is standby after using high-purity argon gas, electro-conductive glass (ITO) is dried up；Then, the side of physical vapour deposition (PVD) is utilized Method prepares BPEA nano wires, and making BPEA nanowire depositions, ECL sensors are successfully prepared on electro-conductive glass；Step 3：ECL based on BPEA nano wires detects the Molecular Logic Gates constructed：Passed so that BPEA nanowire electrochemicals are luminous Sensor is the basic boom of Molecular Logic Gates, using triphenylamine and another material for needing detection molecules as input condition, BPEA nanometers The Strength Changes for the ECL signals that line is sent are output result, so as to realize logical operation.
- A kind of 2. preparation method of electrochemical luminescence nm logic operated device according to claim 1, it is characterised in that： In step 1, the organic solvent is ethanol, or can dissolve BPEA but the not organic solvent with BPEA reactions from other.
- A kind of 3. preparation method of electrochemical luminescence nm logic operated device according to claim 1, it is characterised in that： In step 1, the predetermined temperature of the oil bath be 60 DEG C, and by adjust oil bath temperature and growth time it is controllable go out difference The BPEA nano wires of size and density.
- A kind of 4. preparation method of electrochemical luminescence nm logic operated device according to claim 1, it is characterised in that： In step 1, the substrate is electro-conductive glass.
- A kind of 5. preparation method of electrochemical luminescence nm logic operated device according to claim 1, it is characterised in that： In step 3, another material for needing detection molecules is any one in dopamine, proline and methylene blue.
- A kind of 6. preparation method of electrochemical luminescence nm logic operated device according to claim 1, it is characterised in that： In step 3, the Molecular Logic Gates constructed can be two input logic gates, i.e. OR gate (OR), XOR gate (XOR), forbid Door (INHIBIT), or three input logic gates and four input logic gates.
- A kind of 7. preparation method of electrochemical luminescence nm logic operated device according to claim 5, it is characterised in that： The triphenylamine (TprA), proline (Pro), the detectable concentration of methylene blue (MB) are 1 × 10-8Mol/L, dopamine (DA) Detectable concentration is 3 × 10-5mol/L。
- A kind of 8. electrochemical luminescence nm logic operated device, it is characterised in that：It is as any one of claim 1~7 Preparation method be made；The Molecular Logic Gates of ECL detection framework of the electrochemical luminescence nm logic operated device based on BPEA nano wires, its Basic boom is to be based on BPEA nanowire electrochemical luminescence sensors, with triphenylamine (TprA) and dopamine, proline and methylene Any one in base basket is input condition, and the Strength Changes of the ECL signals sent using BPEA nano wires is output results；To have It is 1 that triphenylamine (TprA), dopamine (DA), proline (Pro), methylene blue (MB), which participate in mark input, is not then 0, defeated Going out result is：If electrochemical luminescence intensity is 0 less than 1000, electrochemical luminescence intensity is 1 if higher than 1000；The gate operation that the electrochemical luminescence nm logic operated device is related to has two input logic gates, i.e. OR gate (OR), XOR gate (XOR), INHIBITORY-gate (INHIBIT)；The OR gate (OR)：Built with triphenylamine (TprA) and proline (Pro) for input condition；BPEA nano wires are repaiied Decorations establish ECL sensors on electro-conductive glass (ITO), and triphenylamine (TprA) and proline (Pro) are detected；The XOR gate (XOR)：Built with triphenylamine (TprA) and dopamine (DA) for input condition；By BPEA nano wires Modification establishes ECL sensors on electro-conductive glass (ITO), and triphenylamine (TprA) and dopamine (DA) are detected；The INHIBITORY-gate (INHIBIT)：Built with triphenylamine (TprA) and methylene blue (MB) for input condition；By BPEA ECL sensors are established in nano wire modification on ITO, and triphenylamine (TprA) and methylene blue (MB) are detected.
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| CN110113044A (en) * | 2019-05-22 | 2019-08-09 | 燕山大学 | A kind of upper conversion logic door construction method and system |
| CN113866235A (en) * | 2021-08-16 | 2021-12-31 | 哈尔滨工业大学（深圳） | Electrochemical luminescence-colorimetric dual-mode sensing detection device based on closed bipolar electrode and construction method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110113044A (en) * | 2019-05-22 | 2019-08-09 | 燕山大学 | A kind of upper conversion logic door construction method and system |
| CN110113044B (en) * | 2019-05-22 | 2020-11-06 | 燕山大学 | Method and system for constructing up-conversion logic gate |
| CN113866235A (en) * | 2021-08-16 | 2021-12-31 | 哈尔滨工业大学（深圳） | Electrochemical luminescence-colorimetric dual-mode sensing detection device based on closed bipolar electrode and construction method and application thereof |
| CN113866235B (en) * | 2021-08-16 | 2023-09-29 | 哈尔滨工业大学（深圳） | Electrochemiluminescence-colorimetric dual-mode sensing detection device based on closed bipolar electrode and construction method and application thereof |
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