CN104311465B - The two sulphur compound of ω-ethene sulfuryl, its preparation method and application - Google Patents
The two sulphur compound of ω-ethene sulfuryl, its preparation method and application Download PDFInfo
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Abstract
The present invention discloses the two sulphur compound of a kind of ω-ethene sulfuryl, its preparation method and application, and described compound has the structure of general formula I, and in this general formula I, n is the integer of 4 ~ 18.This compound can at the orderly self-assembled film of the precious metal surface height of formations such as gold and silver, the vinylsulfone group on self-assembled film surface can react with the biology/chemical molecular containing sulfydryl, amino and hydroxyl under certain conditions respectively, in order to molecule coupling, biological active materials preparation and biochemical sensitive chip modification etc.The self-assembled film using this compound to prepare has the advantages such as hydrolytic resistance, alkali resistance and reaction spectrum.
Description
Technical field
The present invention relates to two sulphur compound of a class ω-ethene sulfuryl and its preparation method and application.
Background technology
In modern biotechnology medical science, biochemical sensor becomes a kind of powerful as the basis of biotechnology automatization, thus causes and pay close attention to widely.Wherein unmarked biological chemistry sensing technology is because it is without the need to mark, and the advantages such as sample requirements is little, and sample is recyclable, reproducible, have promoted sensor and applied more widely at biomedical sector.
As one of the core of biochemical sensor, biochemical recognition system in biochemical sensor in occupation of critical positions.Biochemical recognition system is usually directed to the specific binding of tested biology/chemical molecular and chip surface, realizes the change of optical, electrical physical signalling such as grade, thus reaches and detect the specific quantification of biochemical molecule.Thus biology/chemically modified is carried out to sensor chip surface, thus carry out the fixing of biology/chemical molecular, reach the indispensable step that identification specificity becomes biosensor recognition system structure.
Current existing surface preparation with modification technique, organic sulfide in the self-assembly of precious metal surface in various fields extensive application.The method utilizes the combination between organic sulfide and precious metal atom, and by soaking the organic surface obtaining high-sequential at the bottom of precious metal-based in organic sulfide solution, realize precious metal surface protection, oilness changes, and changes biological activity etc.Due to its easy and simple to handle, surperficial order advantages of higher, in biological chemistry sensing, there is important application.
Existing biology/chemical molecular fixing means relates generally to amino and sulfydryl and active ester reaction, such as: amino and succinimide reacts, and sulfydryl and maleimide react.These methods have specificity mostly, can only react with the biochemical molecular containing fixing functional group.And succinimide and maleimide compounds are easy to be hydrolyzed in physiological conditions, be unfavorable for that the fixation procedure of biochemical molecule is carried out.Thus, a kind of fixing means with broad spectrum and hydrolytic resistance is needed at present badly.
Vinylsulfone group has reaction broad spectrum due to it and strong hydrolysis ability obtains in recent years and pays close attention to widely.Vinylsulfone group under certain conditions, can respectively at sulfydryl, and amino and hydroxyl reaction, is fixed multiple biochemical molecule.And this group has stronger alkali resistance and hydrolytic resistance, under physiological environment, there is satisfactory stability, become a kind of molecule coupling agent had a high potential.But, still do not have at present a kind ofly directly to prepare surface containing vinylsulfone group, realize the fixing Compounds and methods for of biology/chemical molecular.
Summary of the invention:
Namely object of the present invention is the compound containing vinylsulfone group providing a class new, this compounds should utilize sulfide to construct the surface containing vinylsulfone group at the self-assembling technique of precious metal surface, thus realizes fixing multiple biochemical molecule.
For achieving the above object, first the present invention provides a kind of ω-ethene sulfuryl two sulphur compound, has the structure of general formula I:
In general formula I, n is the integer of 4 ~ 18.
The present invention's object is on the other hand the preparation method providing the two sulphur compound of above-mentioned ω-ethene sulfuryl, comprises the steps:
(1) compound of formula II and triphenylphosphine reflux and within 4 hours, prepare the compound of formula III in 1:1.2 ~ 1.4 in molar ratio in tetracol phenixin;
Wherein, m=n-1;
(2) compound of formula III, Diisopropyl azodicarboxylate and mercaptoethanol react the compound of 3 hours preparation formula IV in 1:0.55:1.5 ~ 4 in molar ratio in sherwood oil under 70 ~ 90 DEG C of conditions;
(3) compound of formula IV and excessive hydrogen peroxide react the compound of 4 hours preparation formula V in acetic acid under 60 ~ 80 DEG C of conditions;
(4) compound of formula V and Sodium sulfhydrate in molar ratio 1:5 ~ 10 at C
1-4react 12 hours under 80 ~ 110 DEG C of conditions in low-carbon alcohol/aqueous systems, acidifying after system cooling, obtains white depositions;
White depositions is dissolved in ethyl acetate, adds the iodine of catalytic amount and excessive hydrogen peroxide, the compound of 30 ~ 40 DEG C of reactions, 2 hours preparation formula VI;
(5) compound of formula VI, triethylamine and Methanesulfonyl chloride react the compound of 2 hours preparation formula I in 1:8 ~ 20:2 ~ 4 in molar ratio in methylene dichloride under room temperature condition,
Moreover the present invention also provides the application of the two sulphur compound of above-mentioned ω-ethene sulfuryl in self-assembled film preparation.The preparation method of this self-assembled film, comprises the step being soaked in by precious metal support and carrying out self-assembly in mother liquor, and described mother liquor is the solution of the two sulphur compound of ω-ethene sulfuryl containing the invention described above, self-assembly temperature 4 ~ 30 DEG C, self-assembly time 2 ~ 72h.
On the one hand, by above-mentioned preparation method prepared self-assembled film be also an object of the present invention.
The two sulphur compound of ω of the present invention-ethene sulfuryl can at the orderly self-assembled film of the precious metal surface height of formations such as gold and silver, the vinylsulfone group on gained self-assembled film surface can react with the biology/chemical molecular containing sulfydryl, amino and hydroxyl under certain conditions respectively, in order to molecule coupling, biological active materials preparation and biochemical sensitive chip modification etc.And prepared film has high stability, hydrolytic resistance, alkali resistance, reaction broad spectrum and advantage easy and simple to handle.And with the two sulphur compound of ω of the present invention-ethene sulfuryl, for self-assembled film prepared by raw material, method is simple, and it is very convenient to apply.
Embodiment
The invention provides a kind of ω-ethene sulfuryl two sulphur compound, its preparation method and application.The two sulphur compound of ω of the present invention-ethene sulfuryl has the structure of general formula I:
In general formula I, n is the integer of 4 ~ 18; N is preferably the integer of 8 ~ 12; Be more preferably the integer of 9 ~ 11.
The preparation method of the two sulphur compound of ω provided by the present invention-ethene sulfuryl comprises the steps:
(1) compound of formula II and triphenylphosphine reflux and within 4 hours, prepare the compound of formula III in 1:1.2 ~ 1.4 in molar ratio in tetracol phenixin;
Wherein, m=n-1;
(2) compound of formula III, Diisopropyl azodicarboxylate (AIBN) and mercaptoethanol react the compound of 3 hours preparation formula IV in 1:0.55:1.5 ~ 4 in molar ratio in sherwood oil under 70 ~ 90 DEG C of conditions;
(3) compound of formula IV and excessive hydrogen peroxide react the compound of 4 hours preparation formula V in acetic acid under 60 ~ 80 DEG C of conditions;
(4) compound of formula V and Sodium sulfhydrate are in molar ratio 1: 5 ~ 10 at C
1-4react 12 hours under 80 ~ 110 DEG C of conditions in low-carbon alcohol/aqueous systems, acidifying after system cooling, obtains white depositions;
White depositions is dissolved in ethyl acetate, adds the iodine of catalytic amount and excessive hydrogen peroxide, the compound of 30 ~ 40 DEG C of reactions, 2 hours preparation formula VI;
In specific implementation process, add iodine as catalyzer according to 3 ~ 8% of white depositions molar weight, preferably 5% molar equivalent.
Wherein, described C
1-4low-carbon alcohol is understood according to the common mode in this area, comprises the straight or branched alcohol that carbonatoms is 1 ~ 4, comprises methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the trimethyl carbinol.
In embodiment, the low-carbon alcohol described in this step (4)/aqueous systems preferred alcohol/aqueous systems; Most preferred ethanol volumn concentration is the ethanol/water system of 70%, i.e. ethanol: the system of water (v/v)=7:3.
(5) compound of formula VI, triethylamine and Methanesulfonyl chloride react the compound of 2 hours preparation formula I in 1:8 ~ 20:2 ~ 4 in molar ratio in methylene dichloride under room temperature condition,
In embodiment, for avoiding violent heat production, first the compound of formula VI and triethylamine should be dissolved in methylene dichloride, then Methanesulfonyl chloride slowly be dripped under ice bath, react after being added dropwise to complete.
The preparation method of self-assembled film of the present invention with the two sulphur compound of above-mentioned ω-ethene sulfuryl for raw material, comprise the step being soaked in by precious metal support and carrying out self-assembly in mother liquor, described mother liquor is the solution containing the two sulphur compound of ω according to claim 1-ethene sulfuryl, self-assembly temperature 4-30 DEG C, preferably 25 ± 2 DEG C, self-assembly time 2-72h, preferably 24 ± 2h.
In embodiment, ω-ethene sulfuryl two sulfur compound concentration 1 ~ 10mmol, preferably 1 ~ 2mmol in mother liquor.Those skilled in the art can regulate according to need of production.
Again in a concrete embodiment, described parent solution solvents is methylene dichloride and the ethanol mixed solvent according to arbitrary proportion, and preferably the two is according to mixed solvent of volume ratio 1:1.
In concrete implementation process, use alcohol flushing after self-assembled film prepared according to the method described above completes preparation, then keep in Dark Place.
Following specific embodiment, for further illustrating the present invention, not should be understood to any type of restriction of the present invention.Without specified otherwise, key instrument that this part uses comprises:
Nuclear magnetic resonance analyser: BrukerAvanceII400M;
X-ray photoelectron spectroscopy: ThermoESCALAB250Xi, detection angle is 90 °;
Contact angle instrument: Daheng DH-HV1351UM, condition determination 25 DEG C, 2 μ L water;
QCM (Quartz Crystal Microbalance): BiolinscientificQ-sense-DE1, condition determination 25 DEG C.
Embodiment 1
The preparation (n=10) of compound i, comprises the following steps:
(1) compound of compound ii and triphenylphosphine in molar ratio 1:1.2 reflux in tetracol phenixin and prepare compound iii, 94.6% in 4 hours.
1HNMR(400MHz,CDCl
3):δ5.80(m,1H,CH=CH
2),4.97(dd,2H,J
1=16.8,J
2=10.0,CH=CH
2),3.53(t,2H,J=6.8,ClCH
2),2.03(m,2H,CH
2CH=CH
2),1.77(m,2H,ClCH
2CH
2),1.28~1.44(m,12H,othersCH
2).
13CNMR(100MHz,CDCl
3):δ139.2(CH=CH
2),114.1(CH=CH
2),45.2(ClCH
2),33.8(CH
2=CHCH
2),32.7(ClCH
2CH
2),26.9(ClCH
2CH
2CH
2),28.9~29.4(otherCH
2).MS(EI
+):m/z[M]
+188.13。
(2) compound iii and Diisopropyl azodicarboxylate (AIBN), mercaptoethanol in molar ratio 1:0.55:1.5 in sherwood oil under 84 DEG C of conditions reaction within 3 hours, prepare compound iv, yield is 88.2%.
1HNMR(400MHz,CDCl
3,):δ3.72(t,2H,J=6.0,CH
2OH),3.53(t,2H,J=6.8,ClCH
2),2.73(t,2H,J=6.0,SCH
2CH
2OH),2.52(t,2H,J=7.6,SCH
2CH
2CH
2),2.28(s,1H,CH
2OH),1.78(m,2H,ClCH
2CH
2),1.58(m,2H,SCH
2CH
2CH
2),1.28~1.44(m,14H,othersCH
2).
13CNMR(100MHz,CDCl
3):δ60.2(CH
2OH),45.2(ClCH
2),35.3(SCH
2CH
2OH),32.6(ClCH
2CH
2),31.7(SCH
2CH
2CH
2),26.9(ClCH
2CH
2CH
2),28.8~29.7(otherCH
2).MS(EI
+):m/z[M]
+266.15
(3) compound iv and excessive hydrogen peroxide react under 77 DEG C of conditions and prepare compound v in 4 hours in acetic acid, and yield is 90.2%.
1HNMR(400MHz,DMSO-d
6):δ3.77(t,2H,J=5.6,CH
2OH),3.61(t,2H,J=6.4,ClCH
2),3.18(t,2H,J=6.0,SO
2CH
2CH
2OH),3.09(t,2H,J=8.0,SO
2CH
2CH
2CH
2),1.68(m,4H,SO
2CH
2CH
2CH
2&ClCH
2CH
2),1.26~1.37(m,14H,othersCH
2).
13CNMR(100MHz,DMSO-d
6):δ56.3(SO
2CH
2CH
2OH),54.9(SO
2CH
2CH
2CH
2),54.6(SO
2CH
2CH
2OH),45.2(ClCH
2),32.6(ClCH
2CH
2),26.8(ClCH
2CH
2CH
2),21.8(SO
2CH
2CH
2CH
2),28.4~29.3(otherCH
2).MS(ESI
+):[M+H]
+299.20,[M+NH
4]
+316.18,[M+Na]
+321.19.
Compound v and Sodium sulfhydrate in molar ratio 1:10 in ethanol/water system (70% ethanol, v%) 90 DEG C reaction 12 hours, system cooling after acidifying, obtain white depositions, and be dissolved in ethyl acetate.Estimation white depositions mole number, add the iodine of 5% molar equivalent and excessive hydrogen peroxide, 30 DEG C of reactions prepare compound vi in 2 hours, and yield is 73.4%.
1HNMR(400MHz,DMSO-d
6):δ3.78(t,4H,J=6.8,CH
2OH),3.18(t,4H,J=5.6,SO
2CH
2CH
2OH),3.09(t,4H,J=8.0,SO
2CH
2CH
2CH
2),2.69(t,4H,J=6.8,SSCH
2),1.62~1.68(m,8H,SO
2CH
2CH
2CH
2&SSCH
2CH
2),1.26~1.36(m,28H,othersCH
2).
13CNMR(100MHz,DMSO-d
6):δ55.5(SO
2CH
2CH
2OH),55.2(SO
2CH
2CH
2CH
2),54.0(SO
2CH
2CH
2OH),38.3(SCH
2),21.5(SO
2CH
2CH
2CH
2),28.3~29.4(otherCH
2).MS(ESI
+):[M+K]
+629.23.
Compound vi and triethylamine in molar ratio 1:10 are dissolved in methylene dichloride, and are slowly dripped under ice bath by 2.5 molar equivalent Methanesulfonyl chlorides, and be added dropwise to complete rear room temperature reaction and prepare compound i in 2 hours, yield is 88.6%.
1HNMR(400MHz,CDCl
3):δ6.63(dd,2H,J
1=16.6,J
2=10.0,SO
2CH=CH
2),6.42(d,2H,J=16.6,SO
2CH=CH
2),6.18(d,2H,J=10.0,SO
2CH=CH
2),2.98(t,4H,J=8.4,SO
2CH
2CH
2),2.68(t,4H,J=7.6,SSCH
2),1.78(m,4H,SO
2CH
2CH
2),1.65(m,4H,SSCH
2CH
2),1.27~1.43(m,28H,othersCH
2).
13CNMR(100MHz,DCCl
3):δ136.1(SO
2CH=CH
2),130.5(SO
2CH=CH
2),54.3(SO
2CH
2CH
2),39.1(SCH
2),22.3(SO
2CH
2CH
2CH
2),28.4~29.4(otherCH
2).MS(ESI
+):[M+H]
+555.30,[M+NH
4]
+572.36,[M+Na]
+577.39.
Embodiment 2
The preparation of self-assembled film and sign thereof
(1) with the compound i prepared by embodiment 1 for self-assembled material prepares self-assembled film:
A. prepare mother liquor: be mixed into solvent with methylene dichloride and ethanol according to volume ratio 1:1, abundant dissolved compound i, preparation concentration is the self-assembly mother liquor of 1mmol;
B. golden chip is soaked in the self-assembly mother liquor obtained by step a, under 25 ± 2 DEG C of conditions, leaves standstill 24 hours;
C. gained self-assembled film alcohol flushing, keeps in Dark Place.
(2) the XPS characterization result of the self-assembled film prepared by step (1) is as follows
1BindingEnergy=84.2eV
2BindingEnergy=162.0eV
3BindingEnergy=168.4eV
4BindingEnergy=285.0eV
5BindingEnergy=286.2eV
6BindingEnergy=531.8eV
Embodiment 3
Self-assembled film stability test
Self-assembled film prepared by embodiment 2 kept in Dark Place 30 days or soak 10 hours in pH5-9 damping fluid, detecting self-assembled film contact angle, the results are shown in Table 1:
Table 1 self-assembled film keeps in Dark Place and contact angle after damping fluid process
Treatment process | Contact angle (°) |
Before process | 66.9±0.6 |
Keep in Dark Place 30 days | 66.8±0.8 |
PH5 damping fluid soaks | 66.2±0.8 |
PH6 damping fluid soaks | 66.8±0.7 |
PH7 damping fluid soaks | 67.1±0.6 |
PH8 damping fluid soaks | 66.0±0.9 |
PH9 damping fluid soaks | 67.1±0.6 |
From detected result, before and after process, test membrane contact angle has no considerable change, and show that this self-assembled film obviously hydrolysis does not occur or destroys, surface test film has high stability.
Embodiment 4
Self-assembled film hydrolytic resistance and alkali resistance test
Detect self-assembled film contact angle after self-assembled film prepared by embodiment 2 is soaked 4 hours in the damping fluid of pH6.5-11.5, the results are shown in Table 2:
The contact angle after 4 hours of compound self-assembled film damping fluid process described in table 2
Treatment process | Contact angle (°) |
Before process | 66.9±0.6 |
PH6.5 damping fluid soaks | 66.2±0.8 |
PH7.5 damping fluid soaks | 66.3±0.6 |
PH8.5 damping fluid soaks | 66.0±0.7 |
PH9.5 damping fluid soaks | 67.1±0.6 |
PH10.5 damping fluid soaks | 67.1±0.9 |
PH11.5 damping fluid soaks | 66.4±0.8 |
From detected result, before and after process, test membrane contact angle has no considerable change, shows that this self-assembled film obviously hydrolysis does not occur or destroys.And the self-assembled film that traditional method N-hydroxy-succinamide and maleimido are formed hydrolysis degree >70% in 4 hours under pH8 condition, the self-assembled film showing described compound has hydrolytic resistance and alkali resistance.
Embodiment 5
The test of self-assembled film reaction broad spectrum
Carry out contact angle detection by soaking reaction in the mercaptoethanol of self-assembled film in pH5.5 ~ 11.5, monoethanolamine and ethylene glycol solution after 4 hours, result is as table 3:
The contact angle after 4 hours of compound self-assembled film mercaptoethanol, monoethanolamine and ethylene glycol process described in table 3
Process | Mercaptoethanol | Monoethanolamine | Ethylene glycol |
Untreated | 66.9±0.6 | 66.9±0.6 | 66.9±0.6 |
pH6.5 | 60.7±0.5 | 66.5±0.4 | 66.4±0.2 |
pH7.5 | 49.2±0.1 | 66.4±0.5 | 66.5±0.3 |
pH8.5 | 49.5±0.6 | 48.1±0.2 | 66.4±0.5 |
pH9.5 | 49.0±0.2 | 48.3±0.6 | 66.2±0.6 |
pH10.5 | 49.1±0.5 | 49.0±0.7 | 65.9±0.8 |
pH11.5 | 48.7±0.2 | 47.8±0.4 | 52.8±0.6 |
Find that the self-assembled film contact angle soaked in mercaptoethanol reduces in pH >=6.5 are interval; The self-assembled film contact angle soaked in monoethanolamine reduces in pH >=8.5 are interval; The self-assembled film contact angle soaked in ethylene glycol reduces in pH >=10.5 are interval.Show that this self-assembled film reacts respectively at mercaptoethanol, monoethanolamine and ethylene glycol in corresponding pH interval.
Embodiment 6
Self-assembled film is used for gsh, N
α, N
αthe fixing experiment of-dicarboxyl Methionin and oligosaccharides
The present embodiment object is to carry out the application of protein binding assays checking self-assembled film in concrete biological micromolecule is fixed by QCM (Quartz Crystal Microbalance) (QCM).QCM chip surface being carried out self-assembly is immersed in reactant damping fluid: glutathione solution pH7.5, N
α, N
α-dicarboxyl lysine solution pH8.5, in mannose solution pH10.5 4 hours, water rinsed, and reaction completes.Reacted chip is placed in QCM system, pass into Thiadiazolidine isomerase albumen respectively, histidine-tagged protein, concanavalin A and bovine serum albumin (blank), find the chip specific binding Thiadiazolidine isomerase albumen reacted with gsh, with N
α, N
αthe chip specific binding histidine-tagged protein of-dicarboxyl Methionin reaction, the chip specific binding concanavalin A reacted with seminose.And three kinds of reacted chips all do not occur specific adsorption to bovine serum albumin, show surperficial gsh, N
α, N
α-dicarboxyl Methionin and oligosaccharides are fixed successfully.
Embodiment 7
Bibliographical information (BioconjugateChem., 2011,22,50-57) at hydroxyl surface by reacting with divinylsulfone the surface can prepared containing vinyl sulphone under alkaline condition.The present embodiment utilizes document report method to prepare containing vinylsulfone group surface as contrast, and the self-assembled film prepared with method described in this patent contrasts.XPS sign is carried out on the surface of two kinds of methods being prepared, and carries out integral and calculating to element sulphur in its spectrogram, obtains the sulfur content (table 4) of different valence state.Result shows, the surperficial vinylsulfone group content that literature method obtains is lower than 40%, and this patent method obtains surperficial vinylsulfone group density far above literature method, and theoretical content is 100%.
Method described in table 4 literature procedure and this patent prepares vinyl sulphone surface sulfuryl XPS constituent content
XPS constituent content | Sulfuryl sulphur | Gold sulfide linkage sulphur |
Literature method | 1.2% | 3.3% |
This patent method | 3.3% | 3.3% |
Claims (10)
1. the two sulphur compound of ω-ethene sulfuryl, has the structure of general formula I:
In general formula I, n is the integer of 4 ~ 18.
2. the two sulphur compound of ω according to claim 1-ethene sulfuryl, it is characterized in that, described n is the integer of 8 ~ 12.
3. the preparation method of the two sulphur compound of ω according to claim 1-ethene sulfuryl, comprises the steps:
(1) compound of formula II and triphenylphosphine reflux and within 4 hours, prepare the compound of formula III in 1:1.2 ~ 1.4 in molar ratio in tetracol phenixin;
Wherein, m=n-1;
(2) compound of formula III, Diisopropyl azodicarboxylate and mercaptoethanol react the compound of 3 hours preparation formula IV in 1:0.55:1.5 ~ 4 in molar ratio in sherwood oil under 70 ~ 90 DEG C of conditions;
(3) compound of formula IV and excessive hydrogen peroxide react the compound of 4 hours preparation formula V in acetic acid under 60 ~ 80 DEG C of conditions;
(4) compound of formula V and Sodium sulfhydrate in molar ratio 1:5 ~ 10 at C
1-4react 12 hours under 80 ~ 110 DEG C of conditions in low-carbon alcohol/aqueous systems, acidifying after system cooling, obtains white depositions; Described C
1-4low-carbon alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol;
White depositions is dissolved in ethyl acetate, adds the iodine of catalytic amount and excessive hydrogen peroxide, the compound of 30 ~ 40 DEG C of reactions, 2 hours preparation formula VI;
(5) compound of formula VI, triethylamine and Methanesulfonyl chloride react the compound of 2 hours preparation formula I in 1:8 ~ 20:2 ~ 4 in molar ratio in methylene dichloride under room temperature condition,
4. the preparation method of the two sulphur compound of ω according to claim 3-ethene sulfuryl, it is characterized in that, the low-carbon alcohol/aqueous systems described in step (4) is ethanol/water system.
5. the preparation method of the two sulphur compound of ω according to claim 4-ethene sulfuryl, it is characterized in that, in described ethanol/water system, ethanol contend per-cent is 70%.
6. the preparation method of a self-assembled film, it is characterized in that, comprise the step being soaked in by precious metal support and carrying out self-assembly in mother liquor, described mother liquor is the solution containing the two sulphur compound of ω according to claim 1-ethene sulfuryl, self-assembly temperature 4-30 DEG C, self-assembly time 2-72h.
7. the preparation method of self-assembled film according to claim 6, is characterized in that, described parent solution solvents is methylene dichloride and the ethanol mixed solvent according to arbitrary proportion.
8. the preparation method of self-assembled film according to claim 6, is characterized in that, described self-assembly temperature 25 ± 2 DEG C; 24 ± 2 hours self-assembly time.
9. the preparation method of self-assembled film according to claim 6, characterized by further comprising the step of alcohol flushing after self-assembly.
10. the self-assembled film prepared by the method in claim 6 ~ 9 described in arbitrary claim.
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