CN108875893A

CN108875893A - 16 kinds of Molecular Logic Gates construction methods based on quantum dot, ruthenium complex

Info

Publication number: CN108875893A
Application number: CN201810529061.5A
Authority: CN
Inventors: 王明茹; 石硕; 王丽
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2018-05-29
Filing date: 2018-05-29
Publication date: 2018-11-23

Abstract

The present invention relates to one kind to be based on quantum dot, 16 kinds of Molecular Logic Gates construction methods of ruthenium complex, with quantum dot, ruthenium complex, gold nanoclusters, DNA, metal ion, three kinds or more substances in ethylenediamine tetra-acetic acid construct Molecular Logic Gates, with quantum dot solution, quantum dot and cadmium ion mixed solution, ruthenium complex solution, ruthenium complex and gold nanoclusters mixed solution, or it is template that Ru complex and DNA mixed solution is any, using in five kinds of substances as the two or more substances in other three kinds outside template or five kinds of substances as input signal, using the normalization numerical value of the fluorescence intensity of quantum dot or ruthenium complex as output signal, construction logic door；The normalization numerical value of fluorescence intensity is the ratio of the florescent intensity value of quantum dot or ruthenium complex and highest florescent intensity value in the logic gate in each logic gate.The present invention uses less substance, constructs 16 kinds of Molecular Logic Gates based on the interaction relationship between six kinds of substances, method efficient and sensible is simple.

Description

16 kinds of Molecular Logic Gates construction methods based on quantum dot, ruthenium complex

Technical field

The present invention relates to molecular computer technical fields, and in particular to a kind of based on quantum dot, 16 kinds of ruthenium complex Molecular Logic Gates construction method.

Background technique

Logic gate is to realize the basis of operation and logical operation, is the core group of the conditional electronic computer based on silicon At part.Theoretically all basic operations of electronic computer can be realized by a combination thereof.With microelectronics information skill Art towards the development increasingly of nanoelectronics and photon information process field, increasingly ground by the building of nano photoelectronic devices The extensive concern for the person of studying carefully.Device based on molecule can receive and handle various chemistry, physics and optical input signal, Then corresponding different output signals are provided, can wirelessly complete various logic operation on a molecular scale.Therefore, One advantage of molecular logic device is exactly to possess potential huge computing capability, this point in narrow nano-scale range It is that traditional electronic device based on silicon is helpless.

The nano particle that quantum dot (also known as semiconductor nanocrystal) is made of II-VI race and III-group Ⅴ element, Since it is with excellent optical property, the broad interest of scientific circles has been caused.The size of quantum dot is about 1 ~ 10 nm, It, can because the pattern of quantum dot can be regulated and controled by reaction time, temperature and ligand classes etc., therefore by control reaction condition To obtain the adjustable quantum dot of fluorescence.The width of quantum dot excite narrow emitting performance that single excitation light source may be implemented under the conditions of it is more Color imaging.Common quantum dot mainly has II-VI type（CdTe,CdSe,CdS,CdTe/CdS,HgCdTe,HgTe）With III- V type（InAs,InAs_xP_1-x）Semiconductor-quantum-point.In numerous quanta point materials, Aqueous phase prepares CdTe quantum technique It is relatively mature.In aqueous environment, particle diameter distribution can be obtained by relatively mild reaction condition uniform, fluorescence The continuously adjustable CdTe quantum of launch wavelength.

Ruthenium is easily formed the complex of hexa-coordinate and variation of valence itself is abundant, it is made to have physicochemical property abundant. Ruthenium complex thermodynamic stability is good, photochemical light physical message is abundant, excited state reaction activity is high and the service life is long and photism It can be good.

Gold nano cluster (gold nanoclusters, Au NCs) is a kind of novel fluorescent nano material, by it is several to Several hundred a atom compositions, are closely sized to Fermi's wavelength in electronics.Due to quantum size effect, gold nano cluster shows uniqueness Optical characteristics.There is fluorescence gold nano cluster good small size, good water solubility, photophysical property, large specific surface area, surface to be easy to The advantages that modification and photoluminescent property are with size adjustable, shows unique value in fields such as nano-device, bio-sensings.

Summary of the invention

The purpose of the present invention is to provide a kind of efficient and sensible, it is simple, quickly based on quantum dot, ruthenium complex 16 Kind Molecular Logic Gates construction method.

A kind of 16 kinds of Molecular Logic Gates construction methods based on quantum dot, ruthenium complex proposed by the present invention, described point Sub- logic gate includes YES1, YES2, NOT1, NOT2, INHIBIT1, INHIBIT2, IMPLY1, IMPLY2, OR, NOR, PASS1, 16 kinds of Molecular Logic Gates of PASS0, XNOR, XOR, AND and NAND, specific step is as follows：

With the three kinds or more object in quantum dot, ruthenium complex, gold nanoclusters, DNA, metal ion, ethylenediamine tetra-acetic acid Texture builds the Molecular Logic Gates of 16 groups of dual inputs one output, with quantum dot solution or quantum dot and cadmium ion mixed solution, or In ruthenium complex solution or ruthenium complex and five kinds of substances of gold nanoclusters mixed solution or Ru complex and DNA mixed solution Any is template, using in five kinds of substances as two or more substance in other three kinds outside template or five kinds of substances For input signal, using the normalization numerical value of the fluorescence intensity of quantum dot or ruthenium complex as output signal, construction logic door；It is described The normalization numerical value of fluorescence intensity is in the florescent intensity value of quantum dot or ruthenium complex in each logic gate and the logic gate The ratio of highest florescent intensity value.

In the present invention, 16 kinds of Molecular Logic Gates construction method difference are as follows：

（1）Taking ruthenium complex solution is template, is input signal, DNA and ruthenium with one or both of DNA or quantum dot solution Complex interacts, so that the fluorescence intensity of ruthenium complex enhances, with ruthenium complex phase interaction occurs for quantum dot solution With, so that the fluorescence intensity of ruthenium complex declines, and using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal, building YES1 type logic gate；

（2）Taking ruthenium complex solution is template, with Cd²⁺Or one or both of gold nanoclusters are input signal, Cd²⁺With ruthenium Complex can not make the fluorescence intensity of ruthenium complex change without effect, and gold nanoclusters and ruthenium complex occur mutually Effect, so that the fluorescence intensity of ruthenium complex enhances, using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal, structure Build YES2 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（3）Take quantum dot and Cd²⁺Mixed solution be template, with one or both of gold nanoclusters or DNA be input letter Number, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, gold nanoclusters and quantum dot occur mutually Effect, DNA interacts with quantum dot, so that the fluorescence intensity of quantum dot declines, but in Cd²⁺Existing solution environmental In, DNA reduces the quenching effect of quantum dot fluorescence so that the fluorescence intensity of quantum dot does not have significant change, with quantum dot and Cd²⁺The normalization numerical value of the fluorescence intensity of effect is output signal, constructs NOT1 type logic gate；Cd²⁺It is mole dense with quantum dot Degree is than being 3：1；

（4）Take quantum dot and Cd²⁺Mixed solution be template, with one or both of DNA or EDTA solution be input letter Number, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, DNA interacts with quantum dot, So that the fluorescence intensity of quantum dot declines, but in Cd²⁺In existing solution environmental, quenching effect of the DNA to quantum dot fluorescence Reduce, so that the fluorescence intensity of quantum dot does not have significant change, EDTA interacts with quantum dot, so that quantum dot is glimmering Optical quenching, with quantum dot and Cd²⁺The normalization numerical value of the fluorescence intensity of effect is output signal, constructs NOT2 type logic gate；Cd² ⁺Molar concentration rate with quantum dot is 3：1；

（5）Taking ruthenium complex solution is template, with quantum dot and gold nanoclusters mixed solution or Cd²⁺It is mixed with gold nanoclusters molten One or both of liquid is input signal, and gold nanoclusters interact with ruthenium complex, so that the fluorescence of ruthenium complex Stronger interaction occurs for enhanced strength, quantum dot and gold nanoclusters, so that the fluorescent quenching of ruthenium complex, Cd²⁺With ruthenium Complex can not make the fluorescence intensity of ruthenium complex change without effect, with the normalizing of the fluorescence intensity of ruthenium complex Change numerical value is output signal, constructs INHIBIT1 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（6）Taking ruthenium complex solution is template, with DNA and gold nanoclusters mixed solution or quantum dot and gold nanoclusters mixed solution One or both of be input signal, gold nanoclusters interact with ruthenium complex, so that the fluorescence of ruthenium complex is strong Degree enhancing, DNA interacts with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, quantum dot and gold nanoclusters Stronger interaction occurs, so that the fluorescent quenching of ruthenium complex, with the normalization numerical value of the fluorescence intensity of ruthenium complex For output signal, INHIBIT2 type logic gate is constructed；

（7）Take quantum dot and Cd²⁺Mixed solution be template, with one or both of DNA or ruthenium complex solution be input Signal, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, with quantum dot phase interaction occurs for DNA With, so that the fluorescence intensity of quantum dot declines, but in Cd²⁺In existing solution environmental, DNA makees the quenching of quantum dot fluorescence With reduction, so that the fluorescence intensity of quantum dot does not have significant change, ruthenium complex interacts with quantum dot, so that quantum Stronger interaction occurs for point fluorescent quenching, DNA and ruthenium complex, and in Cd²⁺Protective effect under, the fluorescence of quantum dot Restore, with quantum dot and Cd²⁺The normalization numerical value of the fluorescence intensity of effect is output signal, constructs IMPLY1 type logic gate；Cd² ⁺Molar concentration rate with quantum dot is 1：2；

（8）Taking quantum dot solution is template, with ruthenium complex and Cd²⁺Mixed solution or DNA and Cd²⁺One of mixed solution Or two kinds are input signal, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, DNA and quantum dot Interaction occurs so that the fluorescence intensity of quantum dot declines, but in Cd²⁺In existing solution environmental, DNA is glimmering to quantum dot The quenching effect of light reduces, so that the fluorescence intensity of quantum dot does not have significant change, with quantum dot phase interaction occurs for ruthenium complex With so that quantum dot fluorescence quenches, stronger interaction occurs for DNA and ruthenium complex, and in Cd²⁺Protective effect under, The fluorescence of quantum dot restores, and using the normalization numerical value of the fluorescence intensity of quantum dot as output signal, constructs IMPLY2 type logic gate； Cd²⁺Molar concentration rate with quantum dot is 1：2；

（9）Taking ruthenium complex solution is template, is input signal, gold nanoclusters with one or both of gold nanoclusters or DNA It interacts with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, DNA interacts with ruthenium complex, So that the fluorescence intensity of ruthenium complex enhances, using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal, OR is constructed Type logic gate；

（10）Taking quantum dot solution is template, with one or both of EDTA solution or ruthenium complex solution for input signal, EDTA interacts with quantum dot, so that the fluorescent quenching of quantum dot, ruthenium complex interact with quantum dot, makes Quantum dot fluorescence quenching is obtained, using the normalization numerical value of the fluorescence intensity of quantum dot as output signal, constructs NOR type logic gate；

（11）Using the mixed solution of ruthenium complex and gold nanoclusters as template, with DNA or Cd²⁺One or both of for input Signal, gold nanoclusters interact with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, DNA and ruthenium complex It interacts, so that the fluorescence intensity of ruthenium complex enhances, Cd²⁺With ruthenium complex without effect, can not ruthenium be cooperated The fluorescence intensity of object changes, and the normalization numerical value of the fluorescence intensity acted on ruthenium complex and gold nanoclusters is output letter Number, construct PASS1 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（12）Taking ruthenium complex solution is template, with one or both of quantum dot or EDTA solution for input signal, quantum Point interacts with ruthenium complex, so that the fluorescence intensity of ruthenium complex declines, EDTA and ruthenium complex are without effect, not The fluorescence intensity of ruthenium complex can be made to change, quantum dot interacts with EDTA, so that the fluorescence of ruthenium complex Quenching constructs PASS0 type logic gate using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal；

（13）Taking ruthenium complex solution is template, in gold nanoclusters and DNA mixed solution or quantum dot and DNA mixed solution One or two are input signal, and gold nanoclusters interact with ruthenium complex, so that the fluorescence intensity of ruthenium complex increases By force, DNA interacts with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, quantum dot and ruthenium complex occur Interaction, so that the fluorescence intensity of ruthenium complex declines, but quantum dot is strong to the fluorescence of ruthenium complex in the environment for having DNA It spends the effect slackened to reduce, using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal, constructs XOR type logic gate；

（14）Taking quantum dot solution is template, with Cd²⁺In ruthenium complex mixed solution or DNA and ruthenium complex mixed solution One or two be input signal, ruthenium complex interacts with quantum dot, so that the fluorescent quenching of quantum dot, only Cd²⁺Or in the presence of one of DNA the fluorescence of quantum dot can not restore, work as Cd²⁺It could make when being existed simultaneously with DNA The fluorescence of quantum dot restores, and using the normalization numerical value of the fluorescence intensity of quantum dot as output signal, constructs XNOR type logic gate； Cd²⁺Molar concentration rate with quantum dot is 3：1；

（15）Taking ruthenium complex solution is template, with quantum dot or Cd²⁺One or both of be input signal, quantum dot with Ruthenium complex interacts, so that the fluorescence intensity of ruthenium complex declines, Cd²⁺With ruthenium complex without effect, can not make The fluorescence intensity for obtaining ruthenium complex changes, quantum dot, Cd²⁺Interaction occurs between ruthenium complex three so that ruthenium is matched The fluorescence intensity enhancing for closing object, constructs AND type logic gate by output signal of the normalization numerical value of the fluorescence intensity of ruthenium complex； Cd²⁺Molar concentration rate with quantum dot is 3：1；

（16）The mixed solution for taking Ru complex and DNA is template, is defeated with one or both of quantum dot or EDTA solution Entering signal, DNA interacts with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, quantum dot and ruthenium complex Interact so that the fluorescence intensity of ruthenium complex declines, but in the environment for having DNA quantum dot to the glimmering of ruthenium complex The effect that luminous intensity slackens reduces, and EDTA and ruthenium complex can not make the fluorescence intensity of ruthenium complex change without effect Become, quantum dot is with EDTA generation interaction so that the fluorescent quenching of ruthenium complex, strong with the fluorescence that Ru complex and DNA acts on The normalization numerical value of degree is that output signal constructs NAND type logic gate.

In the present invention, the quantum dot is CdTe-MPA quantum dot, and the ruthenium complex is [Ru (phen)₂Baippe]·(PF₆)₂, the DNA is single stranded DNA, and sequence is：5'-TCCAGCGGCGGG-3', the metal ion are Cadmium ion Cd²⁺。

In the present invention, the theoretical calculation molar concentration of the quantum dot solution is 1mM, ruthenium complex solution it is mole dense Degree is 200 μM, and the theoretical calculation molar concentration of gold nanoclusters solution is 20mM, and the molar concentration of DNA solution is 100 μM, cadmium from The molar concentration of sub- solution is 1mM, and the molar concentration of EDTA solution is 40mM.

In the present invention, Cd²⁺Interaction occurs so that the fluorescence intensity of quantum dot enhances, with Cd with quantum dot²⁺It is dense Degree increases, and the fluorescence intensity of quantum dot gradually increases until reaching equilibrium level.

In the present invention, step（1）~（16）Described in ruthenium complex and the molar concentration rate of quantum dot be 1：20, DNA Molar concentration rate with quantum dot is 1：20, EDTA and the molar concentration ratio of quantum dot be 20：1, gold nanoclusters and amount The molar concentration ratio of son point is 20：1.

Compared with prior art, the beneficial effects of the present invention are embodied in the following aspects：

（1）The present invention utilizes six kinds of quantum dot, ruthenium complex, gold nanoclusters, DNA, metal ion, ethylenediamine tetra-acetic acid etc. for the first time Substance constructs 16 kinds of base molecule logic gates, including the Molecular Logic Gates include YES1, YES2, NOT1, NOT2, 16 kinds of INHIBIT1, INHIBIT2, IMPLY1, IMPLY2, OR, NOR, PASS1, PASS0, XNOR, XOR, AND, NAND etc. Molecular Logic Gates.

（2）Using the normalization numerical value of the fluorescence intensity of quantum dot or ruthenium complex as output signal, instead of traditional organic Fluorescent dye, method are more efficient sensitive, simple, quick.

Detailed description of the invention

Fig. 1 is the schematic diagram of YES1 type logic gate；

Fig. 2 is that YES1 type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Fig. 3 is the schematic diagram of YES2 type logic gate；

Fig. 4 is that YES2 type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Fig. 5 is the schematic diagram of NOT1 type logic gate；

Fig. 6 is NOT1 type logic gate quantum dot and Cd in varying input signal²⁺The fluorescence intensity of effect normalizes numerical value figure；

Fig. 7 is the schematic diagram of NOT2 type logic gate；

Fig. 8 is NOT2 type logic gate quantum dot and Cd in varying input signal²⁺The fluorescence intensity of effect normalizes numerical value figure；

Fig. 9 is the schematic diagram of INHIBIT1 type logic gate；

Figure 10 is that INHIBIT1 type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 11 is the schematic diagram of INHIBIT2 type logic gate；

Figure 12 is that INHIBIT2 type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 13 is the schematic diagram of IMPLY1 type logic gate；

Figure 14 is IMPLY1 type logic gate quantum dot and Cd in varying input signal²⁺Effect（Cd²⁺It is mole dense with quantum dot Degree ratio is 1：2）Fluorescence intensity normalize numerical value figure；

Figure 15 is the schematic diagram of IMPLY2 type logic gate；

Figure 16 is IMPLY2 type logic gate quantum dot and Cd in varying input signal²⁺Effect（Cd²⁺It is mole dense with quantum dot Degree ratio is 1：2）Fluorescence intensity normalize numerical value figure；

Figure 17 is the schematic diagram of OR type logic gate；

Figure 18 is that OR type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 19 is the schematic diagram of NOR type logic gate；

Figure 20 is that NOR type logic gate quantum dot fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 21 is the schematic diagram of PASS1 type logic gate；

Figure 22 is the fluorescence intensity normalization of PASS1 type logic gate ruthenium complex and gold nanoclusters effect in varying input signal Numerical value figure；

Figure 23 is the schematic diagram of PASS0 type logic gate；

Figure 24 is that PASS0 type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 25 is the schematic diagram of XOR type logic gate；

Figure 26 is that XOR type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 27 is the schematic diagram of XNOR type logic gate；

Figure 28 is that XNOR type logic gate quantum dot fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 29 is the schematic diagram of AND type logic gate；

Figure 30 is that AND type logic gate ruthenium complex fluorescence intensity in varying input signal normalizes numerical value figure；

Figure 31 is the schematic diagram of NAND type logic gate；

Figure 32 is that the NAND type logic gate fluorescence intensity that Ru complex and DNA acts in varying input signal normalizes numerical value Figure；

Figure 33 is in different Cd²⁺With quantum dot molar concentration ratio（1：2,1：1,2：1,3：Isosorbide-5-Nitrae：1,5：1）Under quantum dot Fluorescence spectra.

（Cd in IMPLY1 type logic gate and IMPLY2 type logic gate²⁺Molar concentration ratio with quantum dot is 1：2, Remaining Cd in 14 logic gates²⁺Molar concentration ratio with quantum dot is 3：1.）.

Specific embodiment

It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.

Embodiment 1

The synthesis of quantum dot：

The preparation of NaHTe precursor liquid：Accurately weigh Na₂TeO₃0.1108g, NaBH₄The round-bottomed flask 1 of 0.045g addition 50mL In, the dissolution of 5mL ultrapure water is added, leads to argon gas protection, is stirred to react 30min at a temperature of 90 DEG C.

Accurately weigh CdCl₂0.0367g is added in the round-bottomed flask 2 of 50mL, and the dissolution of 20mL ultrapure water is added, is then added 40 μ L mercaptopropionic acids are uniformly mixed, use NaOH（1M）Solution adjusts pH=9.0.

It takes NaHTe precursor liquid 1mL to rapidly join in round-bottomed flask 2, leads to argon gas protection, be stirred to react 3h at a temperature of 90 DEG C. After reaction, it is saved backup at a temperature of 4 DEG C.

100 μ L quantum dot solutions are taken, the dilution of 900 μ L ultrapure waters is added, the theoretical calculation of the quantum dot solution after dilution is rubbed Your concentration is 1mM.It is saved backup at a temperature of 4 DEG C.

The preparation of ruthenium complex solution（10mL, 200 μM）：Ruthenium complex about 2.0mg is weighed, 150 μ LDMSO dissolution is added. Add ultrapure water be configured to total volume be 10mL complex solution, ultrasonic vibration, shake up it is spare.

The synthesis of gold nanoclusters：

HAuCl₄The preparation of solution（50mL, 0.5M）：Accurately weigh HAuCl₄0.8495g is dissolved with 50mL ultrapure water, and mixing is equal Even, 4 DEG C of temperature are kept in dark place, spare.

Glutathione（GSH）The preparation of solution（30mL, 125mM）：GSH 1.5366g is accurately weighed, with 50mL ultrapure water Dissolution is uniformly mixed, and 4 DEG C of temperature save, spare.

NaBH₄The preparation of solution（50mL, 0.1M）：Accurately weigh NaBH₄0.227g quickly uses 60mL ultrapure water（Ice water Mixture）Dissolution, it is ready-to-use, it is uniformly mixed and uses.

It takes 100mL methanol to be added in the round-bottomed flask of 250mL first, 10mL chlorauric acid solution is added（50mM）, then plus Enter 40mL glutathione solution（0.1M）, it is uniformly mixed, ice bath 30min is then quickly added into the freshly prepared hydroboration of 50mL Sodium solution（0.1M）, ice bath is vigorously stirred, the reaction was continued 1h.After reaction, with centrifuge with 5000rpm revolving speed carry out from There is black particle accumulation, uses methanol in the heart：Water（3：1）Cleaning three times removes unreacted raw material, and drying is for 24 hours.

Product after drying is dissolved in 25mL ultrapure water, the GSH of 614mg is added, is uniformly mixed, is stirred at 55 DEG C anti- Answer 2h.It is kept in dark place at a temperature of 4 DEG C after reaction spare.The theoretical calculation molar concentration of gold nanoclusters solution is 20mM.

The preparation of EDTA solution（50mL, 40mM）：EDTA 0.7445g is accurately weighed, the dissolution of 50mL ultrapure water is added, mixes It closes uniformly, is stored at room temperature, it is spare.

Cd²⁺The preparation of solion（30mL, 1mM）：Accurately weigh CdCl₂5.5mg is added the dissolution of 30mL ultrapure water, mixes It closes uniformly, is stored at room temperature, it is spare.

The preparation of DNA solution（100μM）：It first uses centrifuge to be centrifuged 1min with 12000r/min the DNA primer of purchase, makes DNA falls to centrifugation bottom of the tube, then takes the ultrapure water of corresponding volume on centrifuge tube to be added in DNA primer, after mixing Sealing, stands 8min in 90 DEG C of baking ovens, then cools to room temperature, save at a temperature of 4 DEG C, spare.

Quantum dot solution described in 16 kinds of logic gates（1mM）Take 20 μ L, ruthenium complex solution（200μM）Take 5 μ L, gold nanoclusters solution（20mM）Take 20 μ L, EDTA solution（40mM）Take 10 μ L, DNA solution（100μM）10 μ L are taken, are removed Cd described in IMPLY1 type logic gate and IMPLY2 type logic gate²⁺Solution（1mM）10 μ L are taken, institute in remaining 14 logic gate The Cd stated²⁺Solution（1mM）Take 60 μ L.Ultrapure water, which is added, makes the last total volume of each sample be 1000 μ L.

It is standard with 0.49, output signal is greater than 0.49, and corresponding true value is 1, and less than 0.49, corresponding true value is 0。

The building of YES1 type logic gate, schematic diagram is as shown in Figure 1, in varying input signal, the fluorescence of ruthenium complex Intensity normalizes numerical value figure as shown in Fig. 2, returning its corresponding truth table as shown in table 1.

1 YES1 type logic gate truth table of table

Input 1（DNA）	Input 2（Quantum dot）	Output（Ruthenium complex）
			0	0	0
1	0	1
			0	1	0
1	1	1

The building of YES2 type logic gate, schematic diagram is as shown in figure 3, in varying input signal, the fluorescence intensity of ruthenium complex Numerical value figure is normalized as shown in figure 4, returning its corresponding truth table as shown in table 2.

2 YES2 type logic gate truth table of table

Input 1（Cd²⁺）	Input 2（Gold nanoclusters）	Output（Ruthenium complex）
			0	0	0
1	0	0
			0	1	1
1	1	1

The building of NOT1 type logic gate, schematic diagram is as shown in figure 5, in varying input signal, quantum dot and Cd²⁺Effect Fluorescence intensity normalizes numerical value figure as shown in fig. 6, returning its corresponding truth table as shown in table 3.

3 NOT1 type logic gate truth table of table

Input 1（Gold nanoclusters）	Input 2（DNA）	Output（Quantum dot+Cd²⁺）
			0	0	1
1	0	0
			0	1	1
1	1	0

The building of NOT2 type logic gate, schematic diagram is as shown in fig. 7, in varying input signal, quantum dot and Cd²⁺Effect Fluorescence intensity normalizes numerical value figure as shown in figure 8, returning its corresponding truth table as shown in table 4.

4 NOT2 type logic gate truth table of table

Input 1（DNA）	Input 2（EDTA）	Output（Quantum dot+Cd²⁺）
			0	0	1
1	0	1
			0	1	0
1	1	0

The building of INHIBIT1 type logic gate, schematic diagram is as shown in figure 9, in varying input signal, the fluorescence of ruthenium complex Intensity normalization numerical value figure is as shown in Figure 10, returns its corresponding truth table as shown in table 5.

5 INHIBIT1 type logic gate truth table of table

Input 1（Quantum dot+gold nanoclusters）	Input 2（Cd²⁺+ gold nanoclusters）	Output（Ruthenium complex）
			0	0	0
1	0	0
			0	1	1
1	1	0

The building of INHIBIT2 type logic gate, schematic diagram is as shown in figure 11, in varying input signal, the fluorescence of ruthenium complex Intensity normalization numerical value figure is as shown in figure 12, returns its corresponding truth table as shown in table 6.

6 INHIBIT2 type logic gate truth table of table

Input 1（DNA+ gold nanoclusters）	Input 2（Quantum dot+gold nanoclusters）	Output（Ruthenium complex）
			0	0	0
1	0	1
			0	1	0
1	1	0

The building of IMPLY1 type logic gate, schematic diagram is as shown in figure 13, in varying input signal, quantum dot and Cd²⁺Effect （Cd²⁺Molar concentration ratio with quantum dot is 1：2）Fluorescence intensity normalization numerical value figure it is as shown in figure 14, return its corresponding true It is as shown in table 7 to be worth table.

7 IMPLY1 type logic gate truth table of table

Input 1（DNA）	Input 2（Ruthenium complex）	Output（Quantum dot+Cd²⁺）
			0	0	1
1	0	1
			0	1	0
1	1	1

The building of IMPLY2 type logic gate, schematic diagram is as shown in figure 15, in varying input signal, quantum dot and Cd²⁺Effect （Cd²⁺Molar concentration ratio with quantum dot is 1：2）Fluorescence intensity normalization numerical value figure it is as shown in figure 16, return its corresponding true It is as shown in table 8 to be worth table.

8 IMPLY1 type logic gate truth table of table

Input 1（Ruthenium complex+Cd²⁺）	Input 2（DNA+Cd²⁺）	Output（Quantum dot）
			0	0	1
1	0	0
			0	1	1
1	1	1

The building of OR type logic gate, schematic diagram is as shown in figure 17, in varying input signal, ruthenium complex fluorescence intensity normalizing It is as shown in figure 18 to change numerical value figure, returns its corresponding truth table as shown in table 9.

9 OR type logic gate truth table of table

Input 1（Gold nanoclusters）	Input 2（DNA）	Output（Ruthenium complex）
			0	0	0
1	0	1
			0	1	1
1	1	1

The building of NOR type logic gate, schematic diagram is as shown in figure 19, in varying input signal, quantum dot fluorescence intensity normalizing It is as shown in figure 20 to change numerical value figure, returns its corresponding truth table as shown in table 10.

10 NOR type logic gate truth table of table

Input 1（EDTA）	Input 2（Ruthenium complex）	Output（Quantum dot）
			0	0	1
1	0	0
			0	1	0
1	1	0

The building of PASS1 type logic gate, schematic diagram is as shown in figure 21, in varying input signal, ruthenium complex and gold nano The fluorescence intensity normalization numerical value figure of cluster effect is as shown in figure 22, returns its corresponding truth table as shown in table 11.

11 PASS1 type logic gate truth table of table

Input 1（DNA）	Input 2（Cd²⁺）	Output（Ruthenium complex+gold nanoclusters）
			0	0	1
1	0	1
			0	1	1
1	1	1

The building of PASS0 type logic gate, schematic diagram is as shown in figure 23, in varying input signal, ruthenium complex fluorescence intensity It is as shown in figure 24 to normalize numerical value figure, returns its corresponding truth table as shown in table 12.

12 PASS0 type logic gate truth table of table

Input 1（Quantum dot）	Input 2（EDTA）	Output（Ruthenium complex）
			0	0	0
1	0	0
			0	1	0
1	1	0

The building of XOR type logic gate, schematic diagram is as shown in figure 25, and in varying input signal, ruthenium complex fluorescence intensity is returned One change numerical value figure is as shown in figure 26, returns its corresponding truth table as shown in table 13.

13 XOR type logic gate truth table of table

Input 1（Gold nanoclusters+DNA）	Input 2（Quantum dot+DNA）	Output（Ruthenium complex）
			0	0	0
1	0	1
			0	1	1
1	1	0

The building of XNOR type logic gate, schematic diagram is as shown in figure 27, in varying input signal, quantum dot fluorescence intensity normalizing It is as shown in figure 28 to change numerical value figure, returns its corresponding truth table as shown in table 14.

14 XNOR type logic gate truth table of table

Input 1（Cd²⁺+ ruthenium complex）	Input 2（DNA+ ruthenium complex）	Output（Quantum dot）
			0	0	1
1	0	0
			0	1	0
1	1	1

The building of AND type logic gate, schematic diagram is as shown in figure 29, and in varying input signal, ruthenium complex fluorescence intensity is returned One change numerical value figure is as shown in figure 30, returns its corresponding truth table as shown in Table 15.

15 AND type logic gate truth table of table

Input 1（Quantum dot）	Input 2（Cd²⁺）	Output（Ruthenium complex）
			0	0	0
1	0	0
			0	1	0
1	1	1

The building of NAND type logic gate, schematic diagram is as shown in figure 31, and in varying input signal, ruthenium complex fluorescence intensity is returned One change numerical value figure is as shown in figure 32, returns its corresponding truth table as shown in table 16.

16 NAND type logic gate truth table of table

Input 1（Quantum dot）	Input 2（EDTA）	Output（Ruthenium complex+DNA）
			0	0	1
1	0	1
			0	1	1
1	1	0

Claims

1. a kind of 16 kinds of Molecular Logic Gates construction methods based on quantum dot, ruthenium complex, which is characterized in that the molecule is patrolled Volume door includes YES1, YES2, NOT1, NOT2, INHIBIT1, INHIBIT2, IMPLY1, IMPLY2, OR, NOR, PASS1, 16 kinds of Molecular Logic Gates of PASS0, XNOR, XOR, AND and NAND, specific step is as follows：

2. construction method according to claim 1, it is characterised in that：16 kinds of Molecular Logic Gates construction methods are respectively such as Under：

（2）Taking ruthenium complex solution is template, with Cd²⁺Or one or both of gold nanoclusters are input signal, Cd²⁺Match with ruthenium Object is closed without effect, the fluorescence intensity of ruthenium complex can not be made to change, with ruthenium complex phase interaction occurs for gold nanoclusters With, so that the fluorescence intensity of ruthenium complex enhances, and using the normalization numerical value of the fluorescence intensity of ruthenium complex as output signal, building YES2 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（3）Take quantum dot and Cd²⁺Mixed solution be template, be input signal with one or both of gold nanoclusters or DNA, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, with quantum dot phase interaction occurs for gold nanoclusters With, DNA interacts with quantum dot, so that the fluorescence intensity of quantum dot declines, but in Cd²⁺Existing solution environmental In, DNA reduces the quenching effect of quantum dot fluorescence so that the fluorescence intensity of quantum dot does not have significant change, with quantum dot and Cd²⁺The normalization numerical value of the fluorescence intensity of effect is output signal, constructs NOT1 type logic gate；Cd²⁺It is mole dense with quantum dot Degree is than being 3：1；

（4）Take quantum dot and Cd²⁺Mixed solution be template, with one or both of DNA or EDTA solution for input signal, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, DNA interacts with quantum dot, so that The fluorescence intensity of quantum dot declines, but in Cd²⁺In existing solution environmental, DNA reduces the quenching effect of quantum dot fluorescence, So that the fluorescence intensity of quantum dot does not have significant change, EDTA interacts with quantum dot, so that the fluorescence of quantum dot is sudden It goes out, with quantum dot and Cd²⁺The normalization numerical value of the fluorescence intensity of effect is output signal, constructs NOT2 type logic gate；Cd²⁺With The molar concentration rate of quantum dot is 3：1；

（5）Taking ruthenium complex solution is template, with quantum dot and gold nanoclusters mixed solution or Cd²⁺With gold nanoclusters mixed solution One or both of be input signal, gold nanoclusters interact with ruthenium complex, so that the fluorescence of ruthenium complex is strong Stronger interaction occurs for degree enhancing, quantum dot and gold nanoclusters, so that the fluorescent quenching of ruthenium complex, Cd²⁺Match with ruthenium Object is closed without effect, the fluorescence intensity of ruthenium complex can not be made to change, with the normalization of the fluorescence intensity of ruthenium complex Numerical value is output signal, constructs INHIBIT1 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（8）Taking quantum dot solution is template, with ruthenium complex and Cd²⁺Mixed solution or DNA and Cd²⁺One of mixed solution or Two kinds are input signal, Cd²⁺It interacts with quantum dot, so that the fluorescence intensity of quantum dot enhances, DNA and quantum dot are sent out Raw interaction is so that the fluorescence intensity of quantum dot declines, but in Cd²⁺In existing solution environmental, DNA is to quantum dot fluorescence Quenching effect reduce so that the fluorescence intensity of quantum dot does not have significant change, ruthenium complex interacts with quantum dot, So that quantum dot fluorescence quenches, stronger interaction occurs for DNA and ruthenium complex, and in Cd²⁺Protective effect under, quantum The fluorescence of point restores, and using the normalization numerical value of the fluorescence intensity of quantum dot as output signal, constructs IMPLY2 type logic gate；Cd²⁺ Molar concentration rate with quantum dot is 1：2；

（11）Using the mixed solution of ruthenium complex and gold nanoclusters as template, with DNA or Cd²⁺One or both of for input letter Number, gold nanoclusters interact with ruthenium complex, so that the fluorescence intensity of ruthenium complex enhances, DNA and ruthenium complex are sent out Raw interaction, so that the fluorescence intensity of ruthenium complex enhances, Cd²⁺With ruthenium complex without effect, ruthenium complex can not be made Fluorescence intensity change, the normalization numerical value of the fluorescence intensity acted on using ruthenium complex and gold nanoclusters as output signal, Construct PASS1 type logic gate；Cd²⁺Molar concentration rate with quantum dot is 3：1；

（14）Taking quantum dot solution is template, with Cd²⁺In ruthenium complex mixed solution or DNA and ruthenium complex mixed solution One or two are input signal, and ruthenium complex interacts with quantum dot, so that the fluorescent quenching of quantum dot, only Cd²⁺Or in the presence of one of DNA the fluorescence of quantum dot can not restore, work as Cd²⁺It could make when being existed simultaneously with DNA The fluorescence of quantum dot restores, and using the normalization numerical value of the fluorescence intensity of quantum dot as output signal, constructs XNOR type logic gate； Cd²⁺Molar concentration rate with quantum dot is 3：1；

（15）Taking ruthenium complex solution is template, with quantum dot or Cd²⁺One or both of be input signal, quantum dot and ruthenium Complex interacts, so that the fluorescence intensity of ruthenium complex declines, Cd²⁺With ruthenium complex without effect, can not make The fluorescence intensity of ruthenium complex changes, quantum dot, Cd²⁺Interaction occurs between ruthenium complex three so that ruthenium cooperates The fluorescence intensity of object enhances, and constructs AND type logic gate by output signal of the normalization numerical value of the fluorescence intensity of ruthenium complex； Cd²⁺Molar concentration rate with quantum dot is 3：1；

3. construction method according to claim 1, which is characterized in that the quantum dot is CdTe-MPA quantum dot, institute The ruthenium complex stated is [Ru (phen)₂Baippe]·(PF₆)₂, the DNA is single stranded DNA, and sequence is：5'- TCCAGCGGCGGG-3', the metal ion are cadmium ion Cd²⁺。

4. construction method according to claim 1, which is characterized in that the theoretical calculation mole of the quantum dot solution is dense Degree is 1mM, and the molar concentration of ruthenium complex solution is 200 μM, and the theoretical calculation molar concentration of gold nanoclusters solution is 20mM, The molar concentration of DNA solution is 100 μM, and the molar concentration of cadmium-ion solution is 1mM, and the molar concentration of EDTA solution is 40mM.

5. construction method according to claim 2, which is characterized in that Cd²⁺Interaction occurs so that quantum with quantum dot The fluorescence intensity enhancing of point, with Cd²⁺Concentration increase, the fluorescence intensity of quantum dot gradually increases until reach equilibrium level.

6. construction method according to claim 1, which is characterized in that step（1）~（16）Described in ruthenium complex and amount The molar concentration rate of son point is 1：20, DNA and the molar concentration rate of quantum dot be 1：20, EDTA and quantum dot it is mole dense Degree ratio is 20：1, the molar concentration ratio of gold nanoclusters and quantum dot is 20：1.