CN107176913B - Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and its preparation method and application - Google Patents

Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and its preparation method and application Download PDF

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CN107176913B
CN107176913B CN201710468832.XA CN201710468832A CN107176913B CN 107176913 B CN107176913 B CN 107176913B CN 201710468832 A CN201710468832 A CN 201710468832A CN 107176913 B CN107176913 B CN 107176913B
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enantiomter
axial chirality
amphiphilic molecule
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CN107176913A (en
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贾丽华
郭祥峰
尹建新
赵振龙
于露
朱波
张立雨
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Beijing Chenxi Environmental Protection Engineering Co ltd
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Qiqihar University
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Abstract

Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and its preparation method and application, the present invention relates to axial chirality Gemini amphipathic compounds and its preparation method and application.The present invention provides a kind of novel axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomters and its preparation method and application.The chemical name of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the invention is respectively R-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N; N- alkyl dimethyl ammonium chloride and S-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N; N- alkyl dimethyl ammonium chloride, structural formula are as follows:Preparation method is by solvent, S (R)-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, and N- dimethyl-ethylenediamine and chloracetyl cetylamine are added in reactor, and heating reaction is dry to get product by smart purification of products.Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the invention can be used for preparing hydrogel, and can visualize identification L-arginine.

Description

Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and its preparation Methods and applications
Technical field
The present invention relates to Gemini amphipathic compounds and its preparation method and application.
Background technique
In recent years, hydrogel was due to its unique property and potentially using the extensive concern for having caused people. The important soft substance of one kind that supramolecular hydrogel is formed and forming three-dimensional space network structure for solvent water phase immobilization.It is solidifying The driving force that glue is formed is mainly non-covalent interaction, such as hydrogen bond, π-π interaction, hydrophobic interaction.Due to super Molecular gel can be formed quickly, and the nanostructure being self-assembly of is uniform, adjustable, and can be prepared on a large scale, therefore become oversubscription One of sub- chemistry, nanotechnology and important research direction of material science research, and extensive function is obtained in numerous areas Research and application extension, such as material pattern, optoelectronic switch, drug release, molecular recognition and in terms of have Numerous studies report studies carefully report.
Chirality function material is the important directions in materials chemistry, among supermolecular gel various functions, supermolecule hand Property and functional application be more important a part, but existing chiral supermolecular gel material is less.
Summary of the invention
The present invention is to solve the less technical problems of existing chiral supermolecular gel material, and provide a kind of novel Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and its preparation method and application.
The chemical name of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the invention is respectively R-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride and S-N- hexadecane Base acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride use R-C respectively16NDA and S- C16NDA represents two above compound, and structural formula is respectively as follows:
The preparation method of above-mentioned axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, by following step It is rapid to carry out:
One, solvent I is added to the container, by R-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (R- BEN) or S-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (S-BEN) rub with chloracetyl cetylamine You are than being 1:(1~6), be separately added into R-N- acetyl group-(2- join ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (R-BEN) or S-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (S-BEN) and chloracetyl cetylamine, is warming up to 100 DEG C ~150 DEG C and stirring for 24 hours~48h, obtain crude product；
Two, the crude product rotary evaporation for obtaining step 1, obtains thick lotion；
Three, thick lotion is recrystallized respectively using solvent II, obtains white solid, i.e. axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, uses R-C16NDA and S-C16NDA is indicated.
The method for preparing hydrogel using axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter:
By the volume of the quality and ultrapure water of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter Than for 1mg:(50~60) mL weighs the quality of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and super Pure water is simultaneously uniformly mixed, and being heated to 50~60 DEG C keeps axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter molten Then solution stands 5~6h at 20~25 DEG C, that is, gel is made.
The method for identifying L-arginine using the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, It sequentially includes the following steps:
Aqueous solution is made in amino acid to be identified, by the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule of 10mg Enantiomter is added in the amino acid solution of 1.0mL, is uniformly mixed and is obtained mixed liquor, being heated to 50~60 DEG C makes axis hand Property binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter be completely dissolved, be then cooled at 20~25 DEG C stand 5~ 6h, if foring gel, otherwise it is not L-arginine which, which is L-arginine,.
Axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C of the present invention16NDA and S-C16NDA's Preparation method reaction equation is as follows:
Advantages of the present invention is as follows:
1, the present invention is with R (S)-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine and chloracetyl 16 Amine is raw material, has been respectively synthesized axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C16NDA and S- C16NDA。
2, the Novel shaft hand-type Gemini amphiphile, amphiphilic molecule R-C that the present invention synthesizes16NDA and S-C16NDA enantiomter is A kind of axial chirality Gemini amphiphile, amphiphilic molecule, preparation method simple process, reaction condition is easily controllable, and product is easily isolated, purifies.
3, the axis hand-type Gemini amphiphile, amphiphilic molecule R-C synthesized16NDA and S-C16NDA enantiomter, it faces in water Boundary's micellar concentration is 0.21 and 0.22mmol/L, and critical micelle concentration is lower, surface-active with higher；
4, the R-C synthesized16NDA and S-C16NDA enantiomter compound can form stable hydrogel in water； Being formed by hydrogel has reversible stimulating responsive to heat, as the template of nano material, pharmaceutical carrier, molecular recognition Equal fields have a good application prospect.
5, axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the invention is formed in aqueous solution The critical gel strength of hydrogel is 50mg/mL, and hydrogel has reversible stimulating responsive to heat, that is, dissolves by heating, and is cooled down Form gel.
6, the gelling performance of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the invention is utilized L-arginine can be identified from 15 kinds of common amino acid.
Detailed description of the invention
Fig. 1 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-C prepared by embodiment 116NDA Circular dichroism figure.
Fig. 2 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-C prepared by embodiment 116NDA Surface tension-log concentration curve.
Fig. 3 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-C prepared by embodiment 116NDA Gel-forming and dissolution photo.
Fig. 4 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C prepared by embodiment 216NDA Circular dichroism figure.
Fig. 5 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C prepared by embodiment 216NDA Surface tension-log concentration curve.
Fig. 6 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C prepared by embodiment 216NDA Gel-forming and dissolution photo.
Specific embodiment
Specific embodiment 1: the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomerism of present embodiment The chemical name of body is respectively R-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- dimethyl Ammonium chloride and S-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride, point R-C is not used16NDA and S-C16NDA represents two above compound, and structural formula is respectively as follows:
Specific embodiment 2: axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule described in specific embodiment one The preparation method of enantiomter, sequentially includes the following steps:
One, solvent I is added to the container, by R-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (R- BEN) or S-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (S-BEN) rub with chloracetyl cetylamine You are than being 1:(1~6), be separately added into R-N- acetyl group-(2- join ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (R-BEN) or S-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine (S-BEN) and chloracetyl cetylamine, is warming up to 100 DEG C ~150 DEG C and stirring for 24 hours~48h, obtain crude product；
Two, the crude product rotary evaporation for obtaining step 1, obtains thick lotion；
Three, thick lotion is recrystallized respectively using solvent II, obtains white solid, i.e. axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, uses R-C16NDA and S-C16NDA is indicated.
Specific embodiment 3: present embodiment is to have from the solvent I unlike specific embodiment two in step 1 Machine mixed solvent；It is other to be identical with embodiment two.
Specific embodiment 4: present embodiment is isopropanol and methanol from solvent I unlike specific embodiment three Mixed solvent, isopropanol and water mixed solvent, n-butanol and water mixed solvent, acetone and methanol mixed solvent, ethyl alcohol and diformazan Sulfoxide mixed solvent, dimethyl sulfoxide and water mixed solvent, acetone and toluene Mixed Solvent, ethyl acetate and dimethyl sulfoxide mixing are molten Agent；It is other to be the same as the specific implementation mode 3.
Specific embodiment 5: unlike one of present embodiment and specific embodiment two to four in step 1, R- N- acetyl group-(2- join ethylnaphthalene oxygroup)-N, the quality sum of N- dimethyl-ethylenediamine (R-BEN) and chloracetyl cetylamine with it is molten The ratio of the volume of agent I is 1g:(1~100) mL；It is other identical as one of specific embodiment two to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to four in step 1, S- N- acetyl group-(2- join ethylnaphthalene oxygroup)-N, the quality sum of N- dimethyl-ethylenediamine (S-BEN) and chloracetyl cetylamine with it is molten The ratio of the volume of agent I is 1g:(1~100) mL；It is other identical as one of specific embodiment two to four.
Specific embodiment 7: unlike one of present embodiment and specific embodiment two to six in step 3, it is molten Agent II is the mixture of one or more of ester, ketone, pure and mild ether；It is other identical as one of specific embodiment two to six.
Specific embodiment 8: rotation described unlike one of present embodiment and specific embodiment two to seven is steamed Hair operating condition is: revolving speed is 100r/min~200r/min, and bath temperature is 60 DEG C~90 DEG C, other and specific embodiment One of two to seven is identical.
Specific embodiment 9: utilizing axial chirality binaphthol derivative Gemini type amphiphilic described in specific embodiment one The method that molecule enantiomter prepares hydrogel sequentially includes the following steps:
By mass ratio 1:(10~20 of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and water) It is uniformly mixed, being heated to 60~80 DEG C dissolves axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, so 5~6h is stood at 20~25 DEG C afterwards, that is, gel is made.
The axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of present embodiment forms facing for gel Boundary's gel strength be 50mg/mL, hydrogel to heat have reversible stimulating responsive, that is, be heated to 40 DEG C of hydrogels be dissolved into it is molten Liquid, 20~25 DEG C of cooling then form gel again.
Specific embodiment 10: utilizing axial chirality binaphthol derivative Gemini type amphiphilic described in specific embodiment one The method that molecule enantiomter identifies L-arginine, sequentially includes the following steps:
Aqueous solution is made in amino acid to be identified, by the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule of 10mg Enantiomter is added in the 10mmol/L amino acid solution of 1.0mL, is uniformly mixed and is obtained mixed liquor, is heated to 60~80 DEG C it is completely dissolved axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, is then cooled at 20~25 DEG C 5~6h is stood, if foring gel, otherwise it is not L-arginine which, which is L-arginine,.
L-arginine can induce axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-C16NDA and R- C16The formation of NDA gel, this is because L-arginine is to contain more polar group in long a chain molecule and molecule Such as carboxyl, amino, guanidine radicals, these groups can by interaction of hydrogen bond, electrostatic interaction preferably with compound molecule knot It closes, promotes the aggregation of molecule and form gel.And other common amino acid do not have such effect, can be incited somebody to action using this principle L-arginine is identified from the amino acid of 15 kinds of normal wind.
Beneficial effects of the present invention are verified with following embodiment:
Embodiment 1: the preparation of the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the present embodiment Method sequentially includes the following steps:
One, 10mL n-butanol and water (volume ratio 1:3) mixed solvent, 1.946g chloroethene are sequentially added into three-necked flask Acyl group cetylamine and 1.503g S-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine are 110 DEG C in temperature Under the conditions of stir 48h to get crude product；
It two, is 110r/min in revolving speed, bath temperature is rotary evaporation crude product under conditions of 60 DEG C, obtains thick cream Body；
Three, thick lotion is recrystallized using chloroform and acetone (volume ratio 1:1) mixed solvent, obtains white Solid, as axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-N- cetyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride uses S-C16NDA is indicated.
Using FT-IR,1H-NMR is to S-N- cetyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- Alkyl dimethyl ammonium chloride is characterized.
FT-IR(KBr pellet)νcm-1:3358(N-H amide),2917(-CH3),2847(-CH2), 1679 (C= O,amide),1593(Nr-O-R,ether),821-667(C-H,naphthalene hydrocarbon)。
1H NMR(600MHz,DMSO-d6): δ 8.82 (t, J=5.4Hz 1H), 8.25 (s, 1H), 8.08 (d, J= 9.0Hz, 1H), 7.97 (d, J=8.4Hz, 1H), 7.51 (d, J=9.0Hz, 1H), 7.38 (t, J=7.5Hz, 1H), 7.27 (t, J=7.8Hz, 1H), 6.96 (d, J=8.4Hz, 1H), 4.65 (d, J=15.6Hz, 1H), 4.47 (d, J=15.0Hz, 1H), 4.15 (s, 2H), 3.52 (s, 4H), 3.16 (s, 6H), 3.09-3.06 (m, J=6.6Hz, 2H), 1.41 (t, J=6.6Hz, 2H), 1.26-1.23 (br, 28H), 0.86 (t, J=6.9Hz, 3H).
By FT-IR,1H-NMR to S-N- cetyl acyl methyl-N- [2- (2- join ethylnaphthalene oxygen acetyl group)-ethyl]-N, The characterization of N- alkyl dimethyl ammonium chloride, it is known that S-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, The structural formula of N- alkyl dimethyl ammonium chloride are as follows:
Fig. 1 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-N- ten manufactured in the present embodiment Six alkyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (S-C16NDA) the CD of aqueous solution Spectrogram, it will be seen from figure 1 that S-C16There is the CD signal peak of minimum and maximum in 224nm and 236nm in the weak solution of NDA, Occur a crosspoint at 230nm, illustrates S-C16NDA still maintains S configuration.
Fig. 2 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-N- ten manufactured in the present embodiment Six alkyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (S-C16NDA) the table of aqueous solution Face tension with logC change curve.Figure it is seen that S-C16Its critical micelle concentration is 0.21mmol/L to NDA in water, Critical micelle concentration is lower, surface-active with higher.
By axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-N- 16 manufactured in the present embodiment Alkyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (S-C16NDA gel test) is carried out, Steps are as follows: by the S-C of 55mg16NDA is added in 1.0mL ultrapure water and is uniformly mixed, and being heated to 60 DEG C makes S-C16NDA dissolution, so 6h is stood at 20 DEG C afterwards, that is, gel is made.The gel is again heated to 40 DEG C, gel becomes solution again, and so on gel- Solution-gel-solution is multiple, and property is constant.The photo of change procedure is as shown in Figure 3.
Pass through the inverted method validation S-C of test tube16The critical gel strength of NDA, specific experimental method is as follows: by 10mg reality Apply 1 gained S-C of example16NDA is added in the vial containing 1.0mL ultrapure water；Heating makes S-C16NDA dissolution, then, at 20 DEG C Lower standing 6h sees whether vial inversion to form gel；If not forming gel, it is further continued for that 5.0mg S- is added C16NDA reheats dissolution, stands, sees whether to form gel；It steps be repeated alternatively until to form gel.Pass through above-mentioned experiment It was found that the critical gel strength of formed gel is 50mg/mL.
S-C prepared by the present embodiment 116The method that NDA identifies L-arginine, sequentially includes the following steps:
One, following amino acid is prepared into the amino acid solution of 10mmol/L:
Two, by the S-C of 10mg16NDA is dissolved in the amino acid solution that 1.0mL concentration is 10mmol/L, is uniformly mixed To mixed liquor, mixed liquor is heated to 60 DEG C to S-C16After NDA is completely dissolved, 6h is stood at 20 DEG C；Observe the formation of gel Situation；It was found that only L-arginine can induce S-C in the amino acid tested16NDA formation gel, and other mixed systems It is still clear solution.Therefore, S-C can be promoted by L-arginine16NDA forms this phenomenon of gel, visualizes from 15 kinds Amino acid (leucine, methionine, asparagine, threonine, cysteine, serine, tryptophan, histidine, tyrosine, Phenylalanine, proline, asparagine, glutamine, glutamic acid, L-arginine) in identify L-arginine.
L-arginine can induce axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter S-C16NDA gel Formation, this is because L-arginine is to contain more polar group such as carboxyl, ammonia in long a chain molecule and molecule Base, guanidine radicals, these groups can promote point by interaction of hydrogen bond, electrostatic interaction preferably in conjunction with compound molecule Son aggregation and form gel.And other common amino acid do not have such effect, it can be by L-arginine using this principle It is identified in the amino acid common from 15 kinds.
The S-C for being 8.5mM by concentration16Gel is made after the amino acid that 1.0mL concentration is 10mmol/L is added in NDA solution, The gel is a kind of transparent gel, and saves 20 days gel structures and do not change, and illustrates to be formed by gel stability preferable.
Embodiment 2: the preparation of the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter of the present embodiment Method sequentially includes the following steps:
One, sequentially added into three-necked flask 45mL acetone and dimethyl sulfoxide (volume ratio 1:5) mixed solvent, 15.625g chloracetyl cetylamine and 8.503g R-N- acetyl group-(2- joins ethylnaphthalene oxygroup)-N, N- dimethyl-ethylenediamine, in temperature Degree stirs 48h to get crude product under conditions of being 130 DEG C；
Two, in revolving speed 120r/min, bath temperature is rotary evaporation crude product under conditions of 80 DEG C, obtains thick lotion；
Three, thick lotion is recrystallized using acetone and hexamethylene (volume ratio 1:4) mixed solvent, is obtained white Color solid, as axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride are denoted as R-C16NDA。
Using FT-IR,1H-NMR to R-N- cetyl acyl methyl-N- [2- (2- join ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride is characterized.
FT-IR(KBr pellet)νcm-1:3358(N-H amide),2917(-CH3),2847(-CH2), 1679 (C= O,amide),1593(Nr-O-R,ether),821-667(C-H,naphthalene hydrocarbon)。
1H NMR(600MHz,DMSO-d6): δ 8.89 (d, J=6,1H), 8.33 (s, 1H), 8.08 (d, J=6.0Hz, 1H), 7.98 (d, J=12Hz, 1H), 7.51 (d, J=12Hz, 1H), 7.38 (t, J=9.0Hz, 1H), 7.27 (t, J= 9.0Hz, 1H), 6.95 (d, J=12Hz, 1H), 4.67 (d, J=18Hz, 1H), 4.48 (d, J=18Hz, 1H), 4.32 (s, 4H), 3.53 (s, 4H), 3.17 (s, 6H), 3.09 (m, 2H), 1.40 (d, J=6.0Hz, 2H), 1.28-1.22 (br, 26H), 0.86 (t, J=9.0Hz, 3H).
By FT-IR,1H-NMR to R-N- cetyl acyl methyl-N- [2- (2- join ethylnaphthalene oxygen acetyl group)-ethyl]-N, The characterization of N- alkyl dimethyl ammonium chloride, it is known that R-N- cetyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, The structural formula of N- alkyl dimethyl ammonium chloride are as follows:
Fig. 4 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-N- ten manufactured in the present embodiment Six alkyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (R-C16NDA) the CD of aqueous solution Spectrogram, from fig. 4, it can be seen that R-C16There is the CD signal peak of minimum and maximum in 224nm and 236nm in the weak solution of NDA, Occur a crosspoint at 230nm, illustrates R-C16NDA still maintains R configuration.
Fig. 5 is axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-N- ten manufactured in the present embodiment Six alkyl acyl methyl-N- [2- (2- ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (R-C16NDA) the table of aqueous solution Face tension with logC change curve.From fig. 4, it can be seen that R-C16Its critical micelle concentration is 0.22mmol/L to NDA in water, Critical micelle concentration is lower, surface-active with higher.
By axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-N- 16 manufactured in the present embodiment Alkyl acyl methyl-N- [2- (2- joins ethylnaphthalene oxygen acetyl group)-ethyl]-N, N- alkyl dimethyl ammonium chloride (R-C16NDA gel examination) is carried out It tests, steps are as follows:
By the R-C of 55mg16NDA is added in 1.0mL ultrapure water and is uniformly mixed, and being heated to 60 DEG C makes R-C16NDA dissolution, so 6h is stood at 20 DEG C afterwards, that is, gel is made.The gel is again heated to 40 DEG C, gel becomes solution again, and so on gel- Solution-gel-solution is multiple, and property is constant.
Pass through the inverted method validation R-C of test tube16The critical gel strength of NDA, specific experimental method is as follows: by 10mg reality Apply 2 gained R-C of example16NDA is added in the vial containing 1.0mL ultrapure water；Being heated to 60 DEG C makes R-C16NDA dissolution, then exists 6h is stood at 20 DEG C, sees whether vial inversion to form gel；If not forming gel, it is further continued for that 5.0mgR- is added C16NDA reheats dissolution, stands, sees whether to form gel；It steps be repeated alternatively until to form gel.Pass through above-mentioned experiment It was found that R-C16The critical gel strength of the formed gel of NDA is 50mg/mL.
R-C prepared by the present embodiment 216The method that NDA identifies L-arginine, sequentially includes the following steps:
One, by 15 kinds of common amino acid (leucine, methionine, asparagine, threonine, cysteine, silk ammonia Acid, tryptophan, histidine, tyrosine, phenylalanine, proline, asparagine, glutamine, glutamic acid, L-arginine) system The standby amino acid solution at 10mmol/L；
Two, the R-C of 10mg16NDA is dissolved in the amino acid solution that 1.0mL concentration is 10mmol/L, is uniformly mixed and is obtained Mixed liquor is heated to 60 DEG C to R-C by mixed liquor16After NDA is completely dissolved, 6h is stood at 20 DEG C；Observe the formation feelings of gel Condition；It was found that only L-arginine can induce R-C in the amino acid tested16NDA forms gel, and other mixed systems are still It is so clear solution.Therefore, R-C can be promoted by L-arginine16NDA forms this phenomenon of gel, visualizes from 15 kinds of ammonia L-arginine is identified in base acid.
L-arginine can induce axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter R-C16NDA gel Formation, this is because L-arginine is to contain more polar group such as carboxyl, ammonia in long a chain molecule and molecule Base, guanidine radicals, these groups can promote point by interaction of hydrogen bond, electrostatic interaction preferably in conjunction with compound molecule Son aggregation and form gel.And other common amino acid do not have such effect, it can be by L-arginine using this principle It is identified from the amino acid of 15 kinds of normal wind.
The R-C for being 8.5mM by concentration16Gel is made after the amino acid that 1.0mL concentration is 10mmol/L is added in NDA solution, The gel is a kind of transparent gel, and saves 20 days gel structures and do not change, and illustrates to be formed by gel stability preferable.

Claims (6)

1. axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, it is characterised in that the knot of the enantiomter Structure formula is respectively as follows:
2. the preparation method of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter described in claim 1, It is characterized in that this method sequentially includes the following steps:
One, solvent I is added to the container, is 1:(1~6 by the molar ratio of raw material I and raw material II), it is separately added into raw material I and original Material II is warming up to 100 DEG C~150 DEG C and stirs for 24 hours~48h, obtains crude product；Wherein the structural formula of raw material I isThe structural formula of raw material II isSolvent I is isopropanol and methanol mixed solvent, isopropanol and water mixed solvent, n-butanol and water Mixed solvent, acetone and methanol mixed solvent, ethyl alcohol and dimethyl sulfoxide mixed solvent, dimethyl sulfoxide and water mixed solvent, acetone With toluene Mixed Solvent either ethyl acetate and dimethyl sulfoxide mixed solvent；
Two, the crude product rotary evaporation for obtaining step 1, obtains thick lotion；
Three, thick lotion is recrystallized using solvent II, obtains white solid, i.e. axial chirality binaphthol derivative Gemini type two Affinity molecule enantiomter；Wherein solvent II is the mixture of one or more of ester, ketone, pure and mild ether.
3. the preparation side of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter according to claim 2 Method, it is characterised in that the ratio of the volume of the quality sum and solvent I of raw material I and raw material II is 1g:(1~100 in step 1) mL.
4. the preparation side of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter according to claim 2 Method, it is characterised in that roto-vap operation condition described in step 2 is: revolving speed is 100r/min~200r/min, water-bath temperature Degree is 60 DEG C~90 DEG C.
5. preparing water-setting using axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter described in claim 1 The method of glue, it is characterised in that this method sequentially includes the following steps:
By mass ratio 1:(10~20 of axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter and water) it mixes Uniformly, being heated to 60~80 DEG C dissolves axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter, then exists 5~6h is stood at 20~25 DEG C, that is, gel is made.
6. identifying L- using axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter body described in claim 1 Arginic method, sequentially includes the following steps:
Aqueous solution is made in amino acid to be identified, by the axial chirality binaphthol derivative Gemini type amphiphile, amphiphilic molecule mapping of 10mg Isomers is added in the amino acid solution of 1.0mL, is uniformly mixed and is obtained mixed liquor, being heated to 60~80 DEG C joins axial chirality Naphthol derivative Gemini type amphiphile, amphiphilic molecule enantiomter is completely dissolved, and is then cooled to 5~6h of standing at 20~25 DEG C, such as Fruit forms gel, then otherwise it is not L-arginine that the amino acid, which is L-arginine,.
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