CN106188222A - A kind of double dipeptide structure supermolecular gel factor and preparation method thereof - Google Patents

A kind of double dipeptide structure supermolecular gel factor and preparation method thereof Download PDF

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CN106188222A
CN106188222A CN201610566158.4A CN201610566158A CN106188222A CN 106188222 A CN106188222 A CN 106188222A CN 201610566158 A CN201610566158 A CN 201610566158A CN 106188222 A CN106188222 A CN 106188222A
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amino acid
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杨勇
张肖阳
肖婷婷
费林
杜飞
王小凤
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Nanjing University of Science and Technology
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    • C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
    • C07K5/06—Dipeptides
    • C07K5/06139—Dipeptides with the first amino acid being heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
    • C07K5/06—Dipeptides
    • C07K5/06008—Dipeptides with the first amino acid being neutral
    • C07K5/06078—Dipeptides with the first amino acid being neutral and aromatic or cycloaliphatic

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Abstract

The invention discloses a kind of double dipeptide structure supermolecular gel factor, prepared by following steps: a) use aliphatic long-chain diamidogen or aromatic diamine that two molecule valines are carried out coupling, obtain double valine diamine derivative；B) use aromatic formaldehyde and chiral amino acid to carry out Schiff's base preparation and reduction, obtain chiral amino acid arene derivatives；C) through amide condensed, double valine diamine derivatives and chiral amino acid arene derivatives are carried out coupling, obtain double dipeptide structure supermolecular gel factor.Double dipeptide structure supermolecular gel factors of the present invention can be self-assembly of supermolecular gel in most organic solvents, and the supermolecular gel formed is respectively provided with response to metal ion, pH, temperature, stress stimulation, can be used for the fields such as sensor, slow release, absorption.

Description

A kind of double dipeptide structure supermolecular gel factor and preparation method thereof
Technical field
The invention belongs to Supramolecular self assembly gel intelligence soft material technical field, be specifically related to a kind of double dipeptide structure and surpass Molecular gel factor and preparation method thereof.
Background technology
Supermolecular gel is micromolecular compound by intermolecular hydrogen bonding, Van der Waals force, π-π to be piled up and coordinate bond etc. is non- Covalent bond effect, is self-assembly of line style, threadiness or banded microstructure, then forms three-dimensional net structure, will be the most molten Agent molecule is strapped in its cyberspace the macroscopic visual material formed.Supermolecular gel compared with polymer gel, its gel Being fitted together by non-covalent bond effect between the factor, adhesion is more weak, and irritant reaction to external world is very sensitive and rapid, with Time there is reversibility feature, thus there is in terms of smart sensing material special applications and be worth.Aminoacid has abundant sense Group be, it is easy to be designed, modify and connect can respond or intelligence functional group, molecular chiral can induce gelator from group Dress forms the spiral fiber with secondary structure, constructs group as gel, can bring special answering for supermolecular gel system By value.
Along with organic synthesis and the continuous progress of supermolecular gel technology of preparing, large quantities of oversubscription with specific response function Sub-gel rubber material arises at the historic moment, the synthesizing new supermolecular gel factor to study its gelling performance be the most active current research Field.Chinese patent 201110310768.5 discloses a kind of Thermo-sensitive supermolecular gel based on host-guest interaction, this gel State is heated at 40 DEG C～70 DEG C, 1min～30min can be converted into dissolved colloidal state, has reversible temperature sensitivity feature, but Stimulating metal ion, organic molecule etc. and do not have response, function is the most single.Chinese patent 201310208511.8 is public Opened a kind of can the gel of Selective recognition fluorion, DMSO gel rubber system run into fluorion can specificity variable color, but This gelator can not be self-assembly of gel in other solvent.Wang et al. have studied based on 4-pyridine carboxaldehyde and color Propylhomoserin reacts the gelator prepared, and this gel can only form gel with single metal ion, and range of application has bigger Limitation (Wang XJ, et al.Nanoscale, 2016,8 (12): 6479-6483.).
More than understanding, exploitation multifunctional supramolecular gel rubber material, for widening its range of application, promotes supermolecular gel Material is of great significance at the application in intelligent sensing field, tool.
Summary of the invention
Can only respond indivedual stimulation for existing supermolecular gel material, function is the most single, range of application Limited deficiency, the invention provides a kind of double dipeptide structure supermolecular gel factor and preparation method thereof, and this gelator will Chain hydrophobic effect, π-π pile up and combine with hydrogen bond action, are simultaneously introduced aminoacid as chiral induction element, it is possible in second Acetoacetic ester, oxolane, DMF (dimethylformamide), DMSO (dimethyl sulfoxide) contour polar solvent are self-assembly of solidifying The soft material of glue, pyridine, the introducing of imidazole group can provide condition for this gelator with metal ion generation self assembly, to temperature again Degree, pH, stress stimulation are respectively provided with good response, can be used for multiple fields such as sensor, slow release, absorption.
The technical solution of the present invention is:
A kind of double dipeptide structure supermolecular gel factor, is derived with chiral amino acid aromatic hydrocarbons by double valine diamine derivatives Thing is obtained by condensation coupling reaction, and its general structure is:
Wherein, R1It is selected fromIn one, m is 8～20；
R2It is selected fromIn one；
R3It is selected fromIn one.
The preparation method of a kind of pair of dipeptide structure supermolecular gel factor, by double valine diamine derivatives and chirality ammonia Base acid arene derivatives carries out being condensed coupling reaction, and reaction equation is as follows:
Specifically comprise the following steps that
Step 1, the preparation of chiral amino acid arene derivatives: by aminoacid and Na2CO3It is dissolved in distilled water, is stirred at room temperature Dissolve, be slowly added dropwise the methanol solution of aromatic formaldehyde, be stirred at room temperature 3～6h, be cooled to 0～-5 DEG C, be slowly added to NaBH4, Stirring reaction 8～12h, with second acid for adjusting pH to 5～6, continues stirring 1～3h after being warmed to room temperature, rotation adds ethanol after steaming, 50～ Heating for dissolving at 80 DEG C, filters, and rotation steaming obtains chiral amino acid arene derivatives；
Step 2, the preparation of double dipeptide structure supermolecular gel factors: the tetrahydrochysene furan of preparation chiral amino acid arene derivatives Mutter solution, add EDC.HCL (1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate) and HOBt (1-hydroxy benzenes And triazole), it is cooled to 0～-5 DEG C, adds double valine diamine derivative, be warming up to 25～50 DEG C of reactions 10～24h, in distillation Water precipitates, filters, re-crystallizing in ethyl acetate, obtain double dipeptide structure supermolecular gel factor.
Described double valine diamine derivatives areWherein, R1It is selected from In one, m is 8～20.
In step 1, described aromatic formaldehyde is the one in 4-pyridine carboxaldehyde, 4-imidazole formaldehyde, benzaldehyde, described Aminoacid isOne in valine, leucine, tryptophan, alanine, glycine, phenylalanine.
In step 1, described aminoacid and Na2CO3Mol ratio be 1:0.4～1:0.6, distilled water rubs with amino acid whose You are 1:1～1:3 than for 1:10～1:25, aromatic formaldehyde and amino acid whose mol ratio, NaBH4With amino acid whose mol ratio it is 1:3～1:5, ethanol and amino acid whose mol ratio are 1:60～1:100.
In step 2, described EDC.HCL is 1:1.1～1:1.3 with the mol ratio of chiral amino acid arene derivatives, HOBt is 1:1.1～1:1.3 with the mol ratio of chiral amino acid arene derivatives, and distilled water is 1 with the volume ratio of reaction system: 30～1:50.
In step 2, the concentration of the tetrahydrofuran solution of described chiral amino acid arene derivatives be 0.02～ 0.05mol/L。
Double dipeptide structure supermolecular gel factors of the present invention are self-assembly of gel by two kinds of approach: 1) room temperature next The gelator mixed solution determining concentration (10-50mg/mL) forms gel under ultrasonication；2) finite concentration (10-50mg/ ML) gelator is heated in mixed solvent-cooling circulation, form gel.
Compared with prior art, the invention have the advantages that
(1) piled up by the π-π of the hydrophobic interaction of alkyldiamine, aromatic hydrocarbons and construct with the collaborative of amide hydrogen-bonding effect, this Bright double dipeptide structure supermolecular gel factors all have good gel formation ability in most solvents, the gel heat of formation Mechanics is reversible, and stability is preferable, and temperature, pH, stress stimulation are respectively provided with good response；
(2) chiral amino acid constructs group as gelator, induces gelator self assembly in multiple organic solvent Forming the fibre structure of unidimensional scale, and then pile up the formation netted system of porous three-dimensional, therefore double dipeptide structure of the present invention surpass The gel that the molecular gel factor is formed has relatively low critical gel strength and critical gel transition temperature；
(3) containing pyridine and imidazole functionalities in gelator, there is good metal-complexing ability, may be made with excellent Different mechanical property and the metal gel of optical property, have application potential at the aspect such as slow release, adsorbing metal ions.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the supermolecular gel factor that embodiment 3 prepares.
Fig. 2 is the nmr spectrum obtaining the supermolecular gel factor that embodiment 3 prepares.
Fig. 3 is supermolecular gel factor scanning of self assembly lyophilizing sample when ethanol/water is 1:2 that embodiment 3 prepares Electronic Speculum figure.
Fig. 4 is supermolecular gel factor transmission of self assembly lyophilizing sample when ethanol/water is 1:2 that embodiment 3 prepares Electronic Speculum figure.
Fig. 5 is supermolecular gel factor stimuli responsive of self assembly sample when ethanol/water is 1:2 that embodiment 3 prepares Sex reversal figure.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
The of the present invention pair of valine diamine derivative with reference to United States Patent (USP) [Bindl M, Herrmann R, KnaupG.U.S.Patent 9,126,896 [P] .2015-9-8.] prepare, method particularly includes: by valine: KOH: second Ethyl acetoacetic acid ethyl ester mol ratio is that 1:1:1.1 is equipped with in the four-hole boiling flask of water knockout drum, add with valine mol ratio be 1:8～ The isopropyl acetate of 1:10, produces in heating reflux reaction to water knockout drum and the water that valine mol ratio is 1:1.5～1:1.8, Obtain enamine valine potassium, add and the isopropyl acetate that valine mol ratio is 1:15～1:20, cooling, add and figured silk fabrics ammonia Acid mol ratio is the pivaloyl chloride of 1:1, is stirred at room temperature 0.5～1h, is cooled back to 5～10 DEG C, and addition with valine mol ratio is The aliphatic long-chain diamidogen of 1:0.45～1:0.48 or aromatic diamine, with three second that valine mol ratio is 1:1.1～1:1.2 Amine and with the isopropyl acetate that valine mol ratio is 1:12～1:15,10～15 DEG C reaction 0.5～2h, add rub with valine You are than being the distilled water of 1:70～1:80, and to be acidified to pH with hydrochloric acid be 1-2, separatory, discards organic facies, and aqueous phase NaOH adjusts PH to 10-11, adds isopropyl acetate extraction, separates organic facies, washing, is recrystallized to give double valine diamine derivative.
Described aliphatic long-chain diamidogen is carbon number one in the straight chain end group diamidogen of 8～20, aromatic series Diamidogen is p dimethylamine, the one in m-xylene diamine.
Embodiment 1:(R1ForM=12, R2ForR3For)
Take 5.860g (0.05mol) Valine, 3.300g (0.05mol) KOH, 7.0ml (0.055mol) acetoacetic acid Ethyl ester joins equipped with in the 500mL four-hole boiling flask of agitator, thermometer and water knockout drum, continuously adds the isopropyl acetate of 50.0ml Ester is dissolved, and is heated to reflux, until generating the water of about 1.6ml in water knockout drum, obtains the valine potassium of enamine.Above-mentioned The valine potassium system of enamine adds 88.5ml isopropyl acetate, reactant is cooled to 10 DEG C, add 6.029g spy penta Acyl chlorides, then temperature is risen to 17 DEG C, stir 45min, be then cooled to 10 DEG C.By 4.555g1,12-diamino dodecane, 5.768g triethylamine adds in 78.5ml isopropyl acetate, joins in above-mentioned reaction system, stirs 30min under room temperature.Will 68.0ml water adds reactant, with about 25.5ml concentrated hydrochloric acid, pH is adjusted to 1-2, isolates aqueous phase with separatory funnel, different with acetic acid Propyl ester washs, and discards organic facies.By NaOH solution, the pH of aqueous phase is adjusted to 10-11, adds the extraction of appropriate isopropyl acetate, separate Organic facies, washing, recrystallization obtains ten dimethylene-1, and 12-is double (N-L-valine), and productivity is 60%.Fusing point: 96～97 DEG C.
FT-IR:ν(N–H),3281cm-1；ν(C–H),3092cm-1；ν (C=O), 1632cm-1；ν(N–H),1540cm-1.
1H-NMR (500MHz, DMSO): δ=7.75 (t, J=6Hz, 2H), 3.10-2.99 (m, 4H), 2.88 (d, J= 6Hz, 2H), 1.85-1.80 (m, 2H), 1.58 (brs, 4H), 1.23 (s, 16H), 0.85 (d, J=6Hz, 6H), 0.78 (d, J= 6Hz,6H)ppm。
8.5mmol ALANINE, 4.25mmol Na2CO3Two kinds of raw materials add there-necked flask, add the distillation of 15.0mL Water, is stirred at room temperature dissolving, is slowly added dropwise the methanol solution containing 8.5mmol4-pyridine carboxaldehyde, methanol 5mL, 3h is stirred at room temperature, cold But to 0 DEG C, it is slowly added to 10.2mmol NaBH4, stirring reaction 12h, with the pH to 5～6 of acetic acid regulation reactant mixture, rise Continuing stirring 2h to room temperature, rotation is steamed to anhydrous, filters by 40mL ethanol heating for dissolving under the conditions of 50 DEG C, and filtrate rotation steaming obtains N- (4-picolyl)-ALANINE, productivity is 70%.
FT-IR: ν (NH), 3375cm-1；ν (OH), 3225cm-1；ν (CH), 3019cm-1；ν (CH), 2917cm-1；ν (C= O), 1720cm-1；ν (C=N), 1650cm-1.
1H-NMR (500MHz, DMSO): δ 8.597～8.606 (d, J=4.5Hz, 2H), 8.529～8.541 (d, J= 6Hz, 2H), 4.295～4.300 (d, J=2.5Hz, 2H), 3.735～3.778 (q, 1H), 1.525～1.539 (d, J=7Hz, 3H)。
Take N-(4-picolyl)-ALANINE 0.01mol to be dissolved in 200mL oxolane, add 0.013mol's The HOBt of EDC.HCL and 0.013mol, is cooled to 0 DEG C, adds the double valine diamidogen obtained in the step a) of 0.005mol and spreads out Biology, is warming up to 50 DEG C of reaction 14h, pours in the distilled water of 2000mL and precipitate, filter, the double dipeptide structure of re-crystallizing in ethyl acetate The supermolecular gel factor, productivity is 50%.
FT-IR:ν(NH),3215cm-1；ν(CH),3012cm-1；ν(CH),2987cm-1；ν (C=N), 1683cm-1；ν(C =O), 1690cm-1；ν(N-H),1580cm-1；ν (C=N), 1430cm-1；ν(C-N),1292cm-1.
1H-NMR (500MHz, DMSO): δ 8.568～8.580 (d, J=6Hz, 4H), 7.927～8.068 (m, 4H), 7.316～7.327 (d, J=5.5Hz, 4H), 4.122～4.155 (t, 2H), 3.556～3.828 (dd, 4H), 2.981～ 3.088 (m, 4H), 2.778～2.790 (d, J=6Hz, 2H), 1.750～1.934 (m, 2H) 1.350～1.361 (brs, 4H), 1.193～1.233 (s, 16H), 1.130～1.112 (dd, J1=7, J2=15.5Hz, 6H), 0.830～0.912 (dd, J1= 7, J2=15.5Hz, 12H) ppm.
Reaction equation:
Embodiment 2:(R1ForM=12, R2ForR3For)
The preparation method of ten dimethylene-1,12-double (N-L-valine) is with embodiment 1.
8.5mmolL-valine, 4.25mmol Na2CO3Two kinds of raw materials add there-necked flask, add the distilled water of 8.0mL, Dissolving is stirred at room temperature, is slowly added dropwise the methanol solution containing 8.5mmol benzaldehyde, methanol 5mL, 3h is stirred at room temperature, is cooled to 0 DEG C, it is slowly added to 10.2mmol NaBH4, stirring reaction 12h, with the pH to 5～6 of acetic acid regulation reactant mixture, it is warmed to room temperature Continuing stirring 2h, rotation is steamed to anhydrous, filters by 40mL ethanol heating for dissolving under the conditions of 50 DEG C, and filtrate rotation steaming obtains N-(benzene first Base)-Valine, productivity is 77%.
FT-IR: ν (NH), 3575cm-1；ν (O-H), 3400cm-1；-cm-1ν (-C=N-), 1650cm-1；ν (-C=C-), 1600cm-1；.
1H-NMR (500MHz, DMSO): δ 7.2746～7.3243 (q, 4H), 7.2011～7.2284 (d, J=13.6Hz 1H), 3.456～3.728 (dd, 4H), 2.768～2.780 (d, J=6Hz, 1H), 1.766～1.940 (m, 1H), 0.910～ 0.933 (d, J=11.5Hz, 6H) ppm.
Take N-(benzyl)-Valine 0.01mol to be dissolved in 200mL oxolane, add 0.013mol's The HOBt of EDC.HCL and 0.013mol, is cooled to 0 DEG C, adds the double valine diamidogen obtained in the step a) of 0.005mol and spreads out Biology, is warming up to 50 DEG C of reaction 14h, pours in the distilled water of 2000mL and precipitate, filter, the double dipeptide structure of re-crystallizing in ethyl acetate The supermolecular gel factor, productivity is 58%.
FT-IR:ν(NH),3282cm-1；ν(CH),3012cm-1；ν(CH),2987cm-1；ν (C=C), 1723cm-1；ν(C =O), 1690cm-1；ν(N-H),1580cm-1；ν(C-N),1292cm-1.
1H-NMR (500MHz, DMSO): δ 7.917～8.048 (m, 4H), 7.2746～7.3243 (q, 8H), 7.2011～ 7.2284 (d, J=13.6Hz 2H), 4.142～4.175 (t, 2H), 3.456～3.728 (dd, 4H), 2.982～3.089 (m, 4H), 2.768～2.780 (d, J=6Hz, 2H), 1.766～1.940 (m, 4H) 1.350～1.361 (brs, 4H), 1.193～ 1.233 (s, 16H), 0.830～0.912 (dd, J1=7, J2=15.5Hz, 24H) ppm.
Reaction equation:
Embodiment 3:(R1ForM=12, R2ForR3For)
The preparation method of ten dimethylene-1,12-double (N-L-valine) is with embodiment 1.
8.5mmolL-valine, 4.25mmol Na2CO3Two kinds of raw materials add there-necked flask, add the distilled water of 8.0mL, Dissolving is stirred at room temperature, is slowly added dropwise the methanol solution containing 8.5mmol 4-pyridine carboxaldehyde, methanol 5mL, 3h is stirred at room temperature, cooling To 0 DEG C, it is slowly added to 10.2mmol NaBH4, stirring reaction 12h, with the pH to 5～6 of acetic acid regulation reactant mixture, rise to Room temperature continues stirring 2h, and rotation is steamed to anhydrous, filters by 40mL ethanol heating for dissolving under the conditions of 50 DEG C, and filtrate rotation steaming obtains N- (4-picolyl)-Valine, productivity is 67%.
FT-IR: ν (NH), 3385cm-1；ν (OH), 3255cm-1；ν (CH), 3069cm-1；ν (CH), 2987cm-1；ν (C= O), 1690cm-1；ν (C=C), 1667；Cm-1 ν (C=N), 1430cm-1.
1H-NMR (500MHz, DMSO): δ 8.492～8.504 (d, J=6Hz, 2H), 7.362～7.372 (d, J=5Hz, 2H), 3.582～3.903 (dd, 2H), 2.828～2.839 (d, J=5.5,1H), 1.879～1.944 (m, 1H), 0.910～ 0.933(t,6H)ppm。
Take N-(4-picolyl)-Valine 0.01mol to be dissolved in 200mL oxolane, add 0.013mol's The HOBt of EDC.HCL and 0.013mol, is cooled to 0 DEG C, adds the double valine diamidogen obtained in the step a) of 0.005mol and spreads out Biology, is warming up to 50 DEG C of reaction 14h, pours in the distilled water of 2000mL and precipitate, filter, the double dipeptide structure of re-crystallizing in ethyl acetate The supermolecular gel factor, productivity is 58%.
IR(KBr,cm-1):ν(NH),3215cm-1；ν (C=C), 1723cm-1；ν (C=O), 1690cm-1；ν(N-H), 1580cm-1；ν (C=N), 1430cm-1；ν(C-N),1292cm-1, as shown in Figure 1.
1H-NMR (500MHz, DMSO): δ 8.468～8.480 (d, J=6Hz, 4H), 7.917～8.048 (m, 4H), 7.319～7.330 (d, J=5.5Hz, 4H), 4.142～4.175 (t, 2H), 3.456～3.728 (dd, 4H), 2.982～ 3.089 (m, 4H), 2.768～2.780 (d, J=6Hz, 2H), 1.766～1.940 (m, 4H) 1.350～1.361 (brs, 4H), 1.193～1.233 (s, 16H), 0.830～0.912 (dd, J1=7, J2=15.5Hz, 24H) ppm, as shown in Figure 2.
Reaction equation:
Embodiment 4:(R1ForM=12, R2ForR3For)
The preparation method of ten dimethylene-1,12-double (N-L-valine) is with embodiment 1.
8.5mmolL-tryptophan, 4.25mmol Na2CO3Two kinds of raw materials add there-necked flask, add the distilled water of 8.0mL, Dissolving is stirred at room temperature, is slowly added dropwise the methanol solution containing 8.5mmol 4-imidazole formaldehyde, methanol 5mL, 3h is stirred at room temperature, cooling To 0 DEG C, it is slowly added to 10.2mmol NaBH4, stirring reaction 12h, with the pH to 4～5 of acetic acid regulation reactant mixture, rise to Room temperature continues stirring 2h, and rotation is steamed to anhydrous, filters by 40mL ethanol heating for dissolving under the conditions of 50 DEG C, and filtrate rotation steaming obtains N- (4-imidazolmethyl)-L-Trp, productivity is 61%.
Take N-(4-imidazolmethyl)-L-Trp 0.01mol to be dissolved in 200mL oxolane, add 0.013mol's The HOBt of EDC.HCL and 0.013mol, is cooled to 0 DEG C, adds the double valine diamidogen obtained in the step a) of 0.005mol and spreads out Biology, is warming up to 50 DEG C of reaction 14h, pours in the distilled water of 2000mL and precipitate, filter, the double dipeptide structure of re-crystallizing in ethyl acetate The supermolecular gel factor, productivity is 55%.
Reaction equation:
Embodiment 5
Gelator is the performance measurement of self-assemble gels in organic solvent with water mixed solvent.
Take in the gelator addition gel tube that 0.01g embodiment 3 prepares, be added thereto to having of 0.2mL with liquid-transfering gun Gelator is dissolved by machine solvent, is added thereto to the water of different volumes, mix homogeneously subsequently, observes gel with being inverted test tube method Formation.
Table 1 is example 3 prepared gelator gelling performance in organic solvent with water mixed solvent
Note: G represents that gel, S represent dissolving.
Embodiment 6
The mensuration of the minimum gel strength under gelator room temperature.
Take gelator and a certain proportion of 1mL mixed solvent that appropriate example 3 prepares, be placed in sealing test tube, water-bath Heating makes it be completely dissolved, and is put by obtained solution when being cooled to just form gel at room temperature, gel strength now, The minimum gel strength being under this room temperature, result is as shown in table 2.
The minimum gel strength of table 2
Fig. 3 be gelator in mixed solvent by be self-assembly of supermolecular gel SEM scheme, can from figure Going out gelator in mixed solvent by being self-assembly of filamentary structure, it is three-dimensional netted that fibre structure assembles formation further System.Fig. 4 be gelator in mixed solvent by be self-assembly of supermolecular gel TEM scheme, as can be seen from the figure Gelator is by being self-assembly of network of fibers system in mixed solvent, and fibre diameter is at about 10nm.Fig. 5 be gel because of Son is at ethanol: assemble the stimuli responsive sex reversal figure of supermolecular gel formed when water is 1:2, gel heating, ultrasonic vibration, Soda acid all can be transformed into colloidal sol under stimulating, and has reversibility.

Claims (7)

1. double dipeptide structure supermolecular gel factor, it is characterised in that its general structure is:
Wherein, R1It is selected fromIn one, m is 8～20；
R2It is selected fromIn one；
R3It is selected fromIn one.
2. the preparation method of double dipeptide structure supermolecular gel factor as claimed in claim 1, it is characterised in that concrete steps As follows:
Step 1, the preparation of chiral amino acid arene derivatives: by aminoacid and Na2CO3It is dissolved in distilled water, is stirred at room temperature molten Solve, be slowly added dropwise the methanol solution of aromatic formaldehyde, be stirred at room temperature 3～6h, be cooled to 0～-5 DEG C, be slowly added to NaBH4, stir Mixing reaction 8～12h, with second acid for adjusting pH to 5～6, continue stirring 1～3h after being warmed to room temperature, rotation adds ethanol, 50～80 after steaming Heating for dissolving at DEG C, filters, and rotation steaming obtains chiral amino acid arene derivatives；
Step 2, the preparation of double dipeptide structure supermolecular gel factors: the oxolane of preparation chiral amino acid arene derivatives is molten Liquid, adds EDC.HCL and HOBt, is cooled to 0～-5 DEG C, adds double valine diamine derivative, is warming up to 25～50 DEG C of reactions 10～24h, precipitate in distilled water, filter, re-crystallizing in ethyl acetate, obtain double dipeptide structure supermolecular gel factor.
The preparation method of the most according to claim 2 pair of dipeptide structure supermolecular gel factor, its feature exists In, described double valine diamine derivatives areWherein, R1It is selected from In one, m is 8～20.
The preparation method of the most according to claim 2 pair of dipeptide structure supermolecular gel factor, it is characterised in that step 1 In, described aromatic formaldehyde is the one in 4-pyridine carboxaldehyde, 4-imidazole formaldehyde, benzaldehyde, and described aminoacid isOne in valine, leucine, tryptophan, alanine, glycine, phenylalanine.
The preparation method of the most according to claim 2 pair of dipeptide structure supermolecular gel factor, it is characterised in that step 1 In, described aminoacid and Na2CO3Mol ratio be 1:0.4～1:0.6, distilled water and amino acid whose mol ratio are 1:10～1: 25, aromatic formaldehyde and amino acid whose mol ratio are 1:1～1:3, NaBH4It is 1:3～1:5 with amino acid whose mol ratio, ethanol It is 1:60～1:100 with amino acid whose mol ratio.
The preparation method of the most according to claim 2 pair of dipeptide structure supermolecular gel factor, it is characterised in that step 2 In, described EDC.HCL is 1:1.1～1:1.3, HOBt and chiral amino acid with the mol ratio of chiral amino acid arene derivatives The mol ratio of arene derivatives is 1:1.1～1:1.3, and distilled water is 1:30～1:50 with the volume ratio of reaction system.
The preparation method of the most according to claim 2 pair of dipeptide structure supermolecular gel factor, it is characterised in that step 2 In, the concentration of the tetrahydrofuran solution of described chiral amino acid arene derivatives is 0.02～0.05mol/L.
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