CN101538276A - Nano-layered compound with regular arrays of amino acid and preparation method thereof - Google Patents

Nano-layered compound with regular arrays of amino acid and preparation method thereof Download PDF

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CN101538276A
CN101538276A CN200910133216A CN200910133216A CN101538276A CN 101538276 A CN101538276 A CN 101538276A CN 200910133216 A CN200910133216 A CN 200910133216A CN 200910133216 A CN200910133216 A CN 200910133216A CN 101538276 A CN101538276 A CN 101538276A
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silicon oxide
phenyl silicon
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stratiform compound
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姚建
刘婉君
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a nano-layered structure compound with regular arrays of amino acid and a preparation method thereof, belonging to the technical field of organic nano-layered compound preparation. The method comprises the steps of: using a synthesized nano-layered compound with regular arrays of acyl chloride to conduct amidation grafting reaction with natural (L-type) and racemization (DL-type) amino acid with protected active group except amino-group; then using protecting group remover to remove the protecting group in the amino acid; and finally obtaining a stable nano-layered compound with regular arrays of amino acid.

Description

A kind of nano-laminal compound and preparation method thereof with regular arrays of amino acid
Technical field
The present invention relates to a kind of Nano lamellar structure compound and preparation method thereof, belong to organic nano lamellar compound preparing technical field with regular arrays of amino acid.
Background technology
As everyone knows, nanometer material science is the emphasis of following Materials science development, and its research and development all has far-reaching influence to the every field of chemistry.And as an important component part in the nano material, if you would take off soil and the such laminar nano space material of hydrotalcite, because it has clear and definite nano level space structure and stable physics and chemical property, makes it be studied widely and use in fields such as catalytic chemistry, materials chemistry, electrochemistry and biological chemistries.In the laminar nano space, functional inorganic or organic molecule can exist with the form of unimolecular layer, this is can not be getable in macroscopical space, thereby might form the matrix material with brand-new performance, and obtain in macroscopical space the physics and the chemical property that can not have.
Polynite at present and hydrotalcite stratified material are in the catalytic chemistry application facet, as document Tetrahedron, 2000,56,9357-9364, Chem.Commun., 1998,1033-1034 and Chem.Mater., 2002,14, mainly show as among the 3823-3828 and can improve the catalytic performance that catalytic activity or performance make new advances; In the materials chemistry application facet, as patent CN02127254.9, CN03815807.8 and document Chem.Mater., 2002, mainly show as physical and chemical performance and the mechanical property that can significantly improve macromolecular material among the 14:4202-4208; And aspect electrochemical applications, mainly show the electrochemical activity that improves the electrochemical activity molecule or show the chemical property that in macroscopical space, is not had, as document J.Am.Chem.Soc., 1989,111,4139-4141, Chem.Mater., 2001,13:1976-1983, Macromolecules, 2002,35,1419-1423 and Langmuir, 2003,19,321-325; In the biological chemistry application facet, be mainly used in fields such as immobilized enzyme, medicament slow release, as document Beijing University of Chemical Technology journal (natural science edition), 2002,29 (3): 9-11 and Beijing University of Chemical Technology's journal, 2002,29 (1): 64-67.
In the laminar nano space, functional molecular is arranged in sheaf space, the interaction that is to say functional molecular and layer structure with and molecule between interaction, determine and influenced layer-functional molecular performance of composites.And regulate and control these interactional keys, be to provide suitable sheaf space environment, to reach the purpose of controlled function molecule regular arrangement in sheaf space for functional molecular.But because existing polynite and hydrotalcite stratified material lack functional laminar nano space environment, with and the sheaf space structure that be difficult to change, make to be difficult to the arrangement of effective controlled function molecule in its sheaf space, this makes the application of these materials be subjected to very big restriction.
Summary of the invention
The object of the present invention is to provide a kind of Nano lamellar structure compound material with regular arrays of amino acid.
A kind of nano-laminal compound of the present invention with regular arrays of amino acid, include (A) natural (L type) and racemize (DL type)-to amino acid succinic diamide phenyl silicon oxide stratiform compound, (B) natural (L type) and racemize (DL type)-to amino acid butylene diamide phenyl silicon oxide stratiform compound, (C) natural (L type) and racemize (DL type)-to amino acid glutaramide phenyl silicon oxide stratiform compound, its chemical chemical formula and structural formula are respectively:
(A) natural (L type) and racemize (DL type)-to amino acid succinic diamide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 2H 4CONHCHCOOHR
Structure is:
Table 1, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate
1 H Glycine To glycine succinic diamide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type
2 CH 3 L-Ala To L-Ala succinic diamide phenyl silicon oxide stratiform compound
3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan succinic diamide phenyl silicon oxide stratiform compound
4 CH 2CH(CH 3) 2 Leucine To leucine succinic diamide phenyl silicon oxide stratiform compound
5 CHCH 3C 2H 5 Isoleucine To Isoleucine succinic diamide phenyl silicon oxide stratiform compound
6 C 3H 6 Proline(Pro) To proline(Pro) succinic diamide phenyl silicon oxide stratiform compound The amino of proline(Pro) is than the hydrogen that lacks in the structure expression
7 CH 2C 6H 5 Phenylalanine To phenylalanine succinic diamide phenyl silicon oxide stratiform compound
8 CH 2C 6H 4OH Tyrosine To tyrosine succinic diamide phenyl silicon oxide stratiform compound
9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) succinic diamide phenyl silicon oxide stratiform compound
10 CH 2OH Serine To Serine succinic diamide phenyl silicon oxide stratiform compound
11 CHOHCH 3 Threonine To Threonine succinic diamide phenyl silicon oxide stratiform compound
12 CH 2COOH Aspartic acid To aspartic acid succinic diamide phenyl silicon oxide stratiform compound
13 C 2H 4COOH L-glutamic acid To L-glutamic acid succinic diamide phenyl silicon oxide stratiform compound
(B) natural (L type) and racemize (DL type)-to amino acid butylene diamide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 2H 2CONHCHCOOHR
Structure is:
Figure A20091013321600141
Table 2, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate
1 H Glycine To glycine butylene diamide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type
2 CH 3 L-Ala To L-Ala butylene diamide phenyl silicon oxide stratiform compound
3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan butylene diamide phenyl silicon oxide stratiform compound
4 CH 2CH(CH 3) 2 Leucine To leucine butylene diamide phenyl silicon oxide stratiform compound
5 CHCH 3C 2H 5 Isoleucine To Isoleucine butylene diamide phenyl silicon oxide stratiform compound
6 C 3H 6 Proline(Pro) To proline(Pro) butylene diamide phenyl silicon oxide stratiform compound The amino of proline(Pro) is than the hydrogen that lacks in the structure expression
7 CH 2C 6H 5 Phenylalanine To phenylalanine butylene diamide phenyl silicon oxide stratiform compound
8 CH 2C 6H 4OH Tyrosine To tyrosine butylene diamide phenyl silicon oxide stratiform compound
9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) butylene diamide phenyl silicon oxide stratiform compound
10 CH 2OH Serine To Serine butylene diamide phenyl silicon oxide stratiform compound
11 CHOHCH 3 Threonine To Threonine butylene diamide phenyl silicon oxide stratiform compound
12 CH 2COOH Aspartic acid To aspartic acid butylene diamide phenyl silicon oxide stratiform compound
13 C 2H 4COOH L-glutamic acid To L-glutamic acid butylene diamide phenyl silicon oxide stratiform compound
(C) natural (L type) and racemize (DL type)-to amino acid glutaramide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 3H 6CONHCHCOOHR
Structure is:
Figure A20091013321600161
Table 3, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate
1 H Glycine To glycine glutaramide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type
2 CH 3 L-Ala To L-Ala glutaramide phenyl silicon oxide stratiform compound
3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan glutaramide phenyl silicon oxide stratiform compound
4 CH 2CH(CH 3) 2 Leucine To leucine glutaramide phenyl silicon oxide stratiform compound
5 CHCH 3C 2H 5 Isoleucine To Isoleucine glutaramide phenyl silicon oxide stratiform compound
6 C 3H 6 Proline(Pro) To proline(Pro) glutaramide phenyl silicon oxide stratiform compound The amino of proline(Pro) is than the hydrogen that lacks in the structure expression
7 CH 2C 6H 5 Phenylalanine To phenylalanine glutaramide phenyl silicon oxide stratiform compound
8 CH 2C 6H 4OH Tyrosine To tyrosine glutaramide phenyl silicon oxide stratiform compound
9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) glutaramide phenyl silicon oxide stratiform compound
10 CH 2OH Serine To Serine glutaramide phenyl silicon oxide stratiform compound
11 CHOHCH 3 Threonine To Threonine glutaramide phenyl silicon oxide stratiform compound
12 CH 2COOH Aspartic acid To aspartic acid glutaramide phenyl silicon oxide stratiform compound
13 C 2H 4COOH L-glutamic acid To L-glutamic acid glutaramide phenyl silicon oxide stratiform compound
The present invention is a kind of to have nano-laminal compound (A), (B) of regular arrays of amino acid, the preparation method of (C); it is characterized in that utilizing synthetic to have the nano-laminal compound of regularly arranged acyl chloride; carry out the amidation graft reaction with active group protected natural (L type) and racemize (DL type) amino acid beyond amino; utilize the protecting group remover to remove amino acid whose protecting group then; thereby obtain stablely, have the nano-laminal compound of regular arrays of amino acid.Nano-laminal compound (A), (B), (C) preparation process and reactions steps separately is as follows:
A. natural (L type) and racemize (DL type)-to the preparation of amino acid succinic diamide phenyl silicon oxide stratiform compound (A);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is: at first sodium lauryl sulphate is dissolved in the deionized water, add the p-aminophenyl Trimethoxy silane then, follow slow dripping hydrochloric acid solution and regulate pH value to 2～3 of mixing solutions, and at room temperature magnetic agitation was carried out sol-gel process in 12 days; Last suction filtration, with deionized water, acetyl washing, vacuum-drying obtains p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound respectively;
Its chemical formula is :-SiO 1.5C 6H 4NH 3C 12H 25OSO 3
Structure is:
Figure A20091013321600181
(b) Succinic anhydried is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the THF, and then adds Succinic anhydried, be heated to 50 ℃, magnetic agitation 1 day; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 4COOH
Structure is:
Figure A20091013321600191
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's propionic acid amide phenyl silicon oxide, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying,
The final product that gets is to acyl chlorides butyramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 4COCl
Structure is:
Figure A20091013321600192
(d) with reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 1) beyond the amino, wherein carboxyl with the tert-butyl ester (tBu) protection, pendant hydroxyl group with 2-bromobenzene oxygen carbonyl (BrZ) protect, with above-mentioned acyl chlorides butyramide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester of carboxyl (tBu) protecting group is removed with trifluoroacetic acid (TFA) then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides butyramide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 3 hours; last suction filtration; use washing with alcohol, vacuum-drying, final product natural (L type) and racemize (DL type)-to amino acid succinic diamide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 2H 4The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 2H 4CONHCHCOOHR
The kind of R sees Table 1
B. natural (L type) and racemize (DL type)-to the preparation of amino acid butylene diamide phenyl silicon oxide stratiform compound (B);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is with (a) step among the above-mentioned A;
(b) maleic acid anhydride is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the THF, and then adds maleic acid anhydride, be heated to 50 ℃, magnetic agitation 12 hours; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's acrylamide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 2COOH
Structure is:
Figure A20091013321600201
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's acrylamide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's acrylamide phenyl silicon oxide, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides crotonamide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 2COCl
Structure is:
(d) with reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 2) beyond the amino, wherein carboxyl is protected with 2-bromobenzene oxygen carbonyl (BrZ) with the tert-butyl ester (tBu) protection, pendant hydroxyl group, with above-mentioned acyl chlorides crotonamide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester of carboxyl (tBu) protecting group is removed with trifluoroacetic acid (TFA) then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides crotonamide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 3 hours; last suction filtration; use washing with alcohol, vacuum-drying, final product natural (L type) and racemize (DL type)-to amino acid butylene diamide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 2H 2The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 2H 2CONHCHCOOHR
The kind of R sees Table 2
C. natural (L type) and racemize (DL type)-to the preparation of amino acid glutaramide phenyl silicon oxide stratiform compound (C);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method
With (a) step among the above-mentioned A;
(b) Pyroglutaric acid is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound is dispersed among the THF, add Pyroglutaric acid then, be heated to 50 ℃, magnetic agitation 1 day, last suction filtration, use washing with alcohol, vacuum-drying, the final product that gets is to carboxylic acid group's butyramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 3H 6COOH
Structure is:
Figure A20091013321600221
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's butyramide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's butyramide phenyl silicon oxide stratiform compound, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides valeramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 3H 6COCl
Structure is:
Figure A20091013321600231
(d) with reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 3) beyond the amino, wherein carboxyl is protected with 2-bromobenzene oxygen carbonyl (BrZ) with the tert-butyl ester (tBu) protection, pendant hydroxyl group, with above-mentioned acyl chlorides valeramide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester of carboxyl (tBu) protecting group is removed with trifluoroacetic acid (TFA) then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides valeramide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 2 hours; last suction filtration; use washing with alcohol, vacuum-drying, final product natural (L type) and racemize (DL type)-to amino acid glutaramide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 3H 6The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 3H 6CONHCHCOOHR
The kind of R sees Table 3
The invention provides the compound two-dimensional layer compound of the nano lamellar organic/inorganic with regular arrays of amino acid of a series of brand-new types.The compound two-dimensional layer compound of the novel organic/inorganic of this class has overcome the shortcoming that is difficult to the key-course space environment of existing polynite and hydrotalcite stratified material.Utilize amino acid regularly arranged in the two-dimensional layer space can effectively control two-dimensional layer nanometer spatial environment.By developing the functional stratiform nanometer spatialization compound that synthetic this class has regularly arranged organic group, arrangement and the interaction of controlled function molecule in the stratiform space effectively.This will synthesize the matrix material that has lamellar compound material different performance and application target, that have various nanometer space environments, has brand-new physics and chemical property for realizing design, open up a new approach.
Description of drawings
Fig. 1 is X-ray powder diffraction figure.Wherein (a) is p-aminophenyl silicon oxide-dodecyl sulphate compound,
(b) be p-aminophenyl silicon oxide-eight alkylsurfuric acid compound, (c) be p-aminophenyl silicon oxide-chlorine compound.
Fig. 2 is p-aminophenyl silicon oxide-dodecyl sulphate compound 13C CP/MAS nucleus magnetic resonance figure (is 0ppm with tetramethyl-alkane)
Fig. 3 is p-aminophenyl silicon oxide-dodecyl sulphate compound 29Si HPDEC/MAS nucleus magnetic resonance figure (is 0ppm with tetramethyl-alkane)
Fig. 4 is the transmission electron microscope picture of p-aminophenyl silicon oxide-dodecyl sulphate compound, and the upper right corner is the restricted areas electron-diffraction diagram of transmission electron microscope.
Fig. 5 is an infrared spectrogram.Wherein (a) is p-aminophenyl silicon oxide-dodecyl sulphate compound, (b) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.
Fig. 6 is 13C CP/MAS nucleus magnetic resonance figure (is 0ppm with tetramethyl-alkane).Wherein (a) is p-aminophenyl silicon oxide-dodecyl sulphate compound, (b) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.
Fig. 7 is X-ray powder diffraction figure.Wherein (a) is p-aminophenyl silicon oxide-dodecyl sulphate compound, (b) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.
Fig. 8 is an infrared spectrogram.Wherein (a) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, (b) is to acyl chlorides butyramide phenyl silicon oxide compounds.
Fig. 9 is an infrared spectrogram.Wherein (a) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, (b) is to leucine tert-butyl ester succinic diamide phenyl silicon oxide compounds.(c) be to leucine succinic diamide phenyl silicon oxide compounds.
Figure 10 is X-ray powder diffraction figure.Wherein (a) is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.
(b) be to leucine succinic diamide phenyl silicon oxide compounds.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Natural (L type) and racemize (DL type)-to the preparation of amino acid succinic diamide phenyl silicon oxide stratiform compound (A);
(1) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is: at first the sodium lauryl sulphate with 2.88mmol is dissolved in the deionized water of 250ml, the p-aminophenyl Trimethoxy silane that adds 2.74mmol then, then slowly drip the pH value to 2.07 of the hydrochloric acid adjusting mixing solutions of 0.5mol/L, and at room temperature magnetic agitation was carried out sol-gel process in 12 days; Last suction filtration, with deionized water, acetyl washing, vacuum-drying obtains p-aminophenyl silicon oxide-dodecyl sulphate lamellar structure compound respectively;
In order to prove the chemistry and the three-dimensional arrangement of p-aminophenyl silicon oxide-sodium lauryl sulfate rice straticulate structure compound, a series of analysis experiments have been carried out.At first use eight alkylsurfuric acid negatively charged ion, cl anion carries out anion exchange reaction with p-aminophenyl silicon oxide-dodecyl sulphate compound, obtains p-aminophenyl silicon oxide-eight alkylsurfuric acid and p-aminophenyl silicon oxide-chlorine compound.Carry out the X-ray powder diffraction analysis then.The result of X-ray powder diffraction shows, referring to Fig. 1, according to anionic difference, p-aminophenyl silicon oxide-dodecyl sulphate compound, p-aminophenyl silicon oxide-eight alkylsurfuric acid compound has shown the X-ray diffraction peak that the position is different with p-aminophenyl silicon oxide-chlorine compound.The structure pitch of its diffraction peak correspondence is respectively 4nm, 3.2nm, 1.6nm.As seen, the p-aminophenyl silicon oxide compounds has certain regular texture.And along with anionic difference, this regular texture is scalable, and this is the feature of typical laminate structure.In addition, these structure pitch values are with p-aminophenyl silicon oxide-dodecyl sulphate compound (shown in the specification sheets), and the theoretical pitch in p-aminophenyl silicon oxide-eight alkylsurfuric acid compound and the p-aminophenyl silicon oxide-chlorine compound structure between silicon oxide layer is consistent.
In order to confirm chemical structure, p-aminophenyl silicon oxide-dodecyl sulphate compound has also been carried out 13C CP/MAS nuclear magnetic resonance spectroscopy, as can be seen from Fig. 2,70-10ppm is the resonance peak of methyl and methylene radical in the dodecyl sulphate, 135 and 125ppm be the overlapping peaks of carbon on the phenyl ring.Prove that thus p-aminophenyl silicon oxide-dodecyl sulphate compound has very intact chemical structure.
P-aminophenyl silicon oxide-dodecyl sulphate compound is carried out 29Si HPDEC/MAS nuclear magnetic resonance spectroscopy referring to Fig. 3, is only observed two silicon peaks at 72.5ppm and 80ppm place, illustrates only to have two kinds of silicon oxide structures in p-aminophenyl silicon oxide-dodecyl sulphate compound, a kind of be RSi (OH) (OSi) 2, another kind is RSi (OSi) 3There is not unhydrolysed silylation to have silylation whole hydrolysis becoming silicon oxide structure.
P-aminophenyl silicon oxide-dodecyl sulphate compound is carried out transmission electron microscope observing.From transmission electron microscope picture as seen, referring to Fig. 4, p-aminophenyl silicon oxide-dodecyl sulphate compound is structure in the form of sheets, the restricted areas electron-diffraction diagram is regular regular hexagon, and the structure of silicon oxide is regular regular hexagon sheet structure in visible p-aminophenyl silicon oxide-dodecyl sulphate compound.
P-aminophenyl silicon oxide-dodecyl sulphate compound is carried out ultimate analysis show that N content is 0.0307g/g (about 2.2x10 -3Mol/g); S content is 0.0708g/g (about 2.2x10 -3Mol/g).As seen in p-aminophenyl silicon oxide-dodecyl sulphate compound structure, the p-aminophenyl silicon oxide is 1: 1 with the ratio of dodecyl sulphate.
P-aminophenyl Trimethoxy silane compound has only three hydrolysis tie points, so can only form two-dirnentional structure after its hydrolysis when silane hydrolyzate forms silicon oxide.Consider the molecular dimension of the phenyl that connects with silicon in addition, the phenyl that connects with silicon is very little in the arrangement possibility of silicon oxide layer single face.And,, should have the structure pitch peak of 2nm to occur among the X-ray powder diffraction figure of p-aminophenyl silicon oxide-dodecyl sulphate compound if the phenyl that connects with silicon only is arranged in the single face of silicon oxide layer.But in the X-ray powder diffraction figure of p-aminophenyl silicon oxide-dodecyl sulphate compound, only observe the structure pitch peak of 4nm.And good X-ray diffraction result shows that the two-dimensional layer structure of p-aminophenyl silicon oxide-dodecyl sulphate compound keeps good, and to arrange at interlayer with the aniline that silicon layer connects be comparison rule.Because if the aniline that connects with silicon layer will cause not having the appearance at X-ray diffraction peak in the interlayer fall into disarray.In sum, the chemistry of p-aminophenyl silicon oxide-dodecyl sulphate compound and three-dimensional arrangement are the two-dimensional layer compound with regular amido shown in the specification sheets model diagram.More specifically analyze and ask for an interview contriver's relevant paper: Ion-exchangeable LayeredAminophenylsilica Prepared with Anionic Surfactant Templates; (contriver: Yao builds (pseudonym: Yao Ken)) Chemistry Letters Vol.33, No.9 (2004).
(2) 0.1mol p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the 50ml THF, and then adds the Succinic anhydried of 0.5mol, be heated to 50 ℃, magnetic agitation 1 day; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound;
Product is carried out Infrared spectroscopy, referring to Fig. 5, for p-aminophenyl silicon oxide-dodecyl sulphate with to the infrared spectra comparison diagram of carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound.In p-aminophenyl silicon oxide-dodecyl sulphate compound of red external spectrum, the alkyl of dodecyl sulphate is 2700 to 3000cm as seen from the figure -1The peak, in infrared spectra, disappear to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.As seen, in to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, there is not the existence of dodecyl sulphate.Two new peak 1706and 1670cm have appearred in the infrared spectra to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds in addition -1, these two peaks are respectively the vibration peak of the carbonyl among amide group and the carboxylic acid group.Obviously, a carbonyl in the Succinic anhydried has generated acid amides with the reaction of the amino in p-aminophenyl silicon oxide-dodecyl sulphate, another carbonyl has changed into the carboxylic acid group in the Succinic anhydried simultaneously, thereby has formed carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.To the peak 1600cm in the infrared spectra of carboxylic acid group's propionic acid amide phenyl silicon oxide compounds -1And 1524cm -1Vibration peak for phenyl ring.
Product is carried out 13C CP/MAS nuclear magnetic resonance spectroscopy, referring to Fig. 6, contrast p-aminophenyl silicon oxide-dodecyl sulphate compound as seen, methyl and methylene radical complicated resonance peak between 70-10ppm in the dodecyl sulphate is to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds 13Disappear in the C CP/MAS nmr spectrum, generation be the resonance peak of two methylene radical in 29.3ppm occurs carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.As seen, in to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, there is not the existence of dodecyl sulphate.Two contour resonance peaks occurred at 177.8ppm and 172.6ppm in addition, these two peaks are respectively the resonance peak of the carbonyl among amide group and the carboxylic acid group.Obviously 13C CP/MAS nuclear magnetic resonance spectroscopy has proved that also a carbonyl in the Succinic anhydried has generated acid amides with the reaction of the amino in p-aminophenyl silicon oxide-dodecyl sulphate, another carbonyl has changed into the carboxylic acid group in the Succinic anhydried simultaneously, thereby has formed carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.
Product has also been carried out the X-ray powder diffraction analysis to carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound, p-aminophenyl silicon oxide-dodecyl sulphate compound and as can be known relatively to the X-ray powder diffraction peak of carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, referring to Fig. 7, the structure pitch of the diffraction peak correspondence of p-aminophenyl silicon oxide-dodecyl sulphate compound is 4nm, and is 2.3nm to the structure pitch of carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.These structure pitch values with p-aminophenyl silicon oxide-dodecyl sulphate compound with consistent to the spacing of silicon layer in the theoretical construct of carboxylic acid group's propionic acid amide phenyl silicon oxide compounds (shown in the specification sheets).This explanation is in to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, and two-dirnentional structure remains intact and with the model diagram unanimity.More specifically analyze and ask for an interview contriver's relevant paper: Two-Dimensional Molecular Space with Regular Molecular Structure; (contriver: Yao builds (pseudonym: Yao Ken)) Langmuir, 24 (2008) 302.
(3) 0.1mol is dispersed in the 30ml toluene carboxylic acid group's propionic acid amide phenyl silicon oxide, and then adds 0.5mol thionyl chloride or oxalyl chloride, be heated to 50 ℃, magnetic agitation 3 hours; Behind the cool to room temperature, residual thionyl chloride or oxalyl chloride are removed in decompression then, and last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides butyramide phenyl silicon oxide stratiform compound.
Product is carried out Infrared spectroscopy, referring to Fig. 8, as seen in carboxylic acid group's propionic acid amide phenyl silicon oxide compounds at 1670cm -1The vibration peak of carbonyl among the carboxylic acid group at place disappears in the infared spectrum to acyl chlorides butyramide phenyl silicon oxide stratiform compound, generation be to the 1777cm in the infared spectrum of acyl chlorides butyramide phenyl silicon oxide compounds -1The vibration peak of acyl chlorides has appearred in the place.Obviously, the carboxyl in carboxylic acid group's propionic acid amide phenyl silicon oxide compounds with thionyl chloride or oxalyl chloride reaction, has been generated acyl chlorides.More specifically analyze and ask for an interview contriver's relevant paper: Two-Dimensional MolecularSpace with Regular Molecular Structure; (contriver: Yao builds (pseudonym: Yao Ken)) Langmuir, 24 (2008) 302.
(4) 0.1mol is dispersed in the 20ml dry DMF acyl chlorides butyramide phenyl silicon oxide, add 0.15mol amino reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 2) in addition then, wherein carboxyl is protected with 2 bromobenzene oxygen carbonyls (BrZ) with the tert-butyl ester (tBu) protection, pendant hydroxyl group; Be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying; If amino reaction product with tertbutyloxycarbonyl (Boc) protection just is dispersed in the 20ml methylene dichloride that contains 0.2mol trifluoroacetic acid (TFA), room temperature magnetic force stirred skewer 3 hours, to remove amino protecting group tertbutyloxycarbonyl.If the reaction product of hydroxyl with 2-bromobenzene oxygen carbonyl (BrZ) protection arranged; just be dispersed in the 20ml methylene dichloride; add then and contain in 1ml methyl-phenoxide and the 8ml anhydrous hydrofluoric acid, 0 ℃ of magnetic agitation 3 hours is to remove 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl.Last product suction filtration is used washing with alcohol, vacuum-drying, and final product natural (L type) and racemize (DL type)-to amino acid succinic diamide phenyl silicon oxide stratiform compound.
Below with natural (L type) and racemize (DL type)-example that is prepared as of leucine succinic diamide phenyl silicon oxide stratiform compound is done and specified.0.1mol is dispersed in the 20ml dry DMF acyl chlorides butyramide phenyl silicon oxide, adds the 0.15mol L-leucine tert-butyl ester or racemize (DL type) the leucine tert-butyl ester then, be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying; Then product is dispersed in the 20ml methylene dichloride that contains 0.2mol trifluoroacetic acid (TFA), room temperature magnetic agitation 3 hours is to remove the protecting group tert-butyl ester base of amino acid whose carboxyl.Last product suction filtration is used washing with alcohol, vacuum-drying, final product natural (L type) or and racemize (DL type)-to leucine succinic diamide phenyl silicon oxide stratiform compound.
As seen product is carried out Infrared spectroscopy,, compare with infrared spectra to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds referring to Fig. 9, in infrared spectra to leucine tert-butyl ester succinic diamide phenyl silicon oxide compounds, 1670cm -1The vibration peak and the 2610cm of the carbonyl among the carboxylic acid group at place -1Hydroxyl vibration peak among the carboxylic acid group of place disappears, and in the infrared spectra to leucine succinic diamide phenyl silicon oxide compounds, 1670cm -1The vibration peak and the 2610cm of the carbonyl among the carboxylic acid group at place -1Hydroxyl vibration peak among the carboxylic acid group of place occurs again.The variation explanation of infrared spectra is reacted with the amino in the leucine tert-butyl ester the acyl chlorides in the acyl chlorides butyramide phenyl silicon oxide and has been formed amido linkage, the leucine tert-butyl ester has been grafted in the silicon oxide compounds, has formed leucine tert-butyl ester succinic diamide phenyl silicon oxide compounds.After utilizing the carboxylic acid group's protecting group in the trifluoroacetic acid removal leucine tert-butyl ester then, formed leucine succinic diamide phenyl silicon oxide compounds, the carboxylic acid group reappears in the compound.
As seen product is carried out the X-ray powder diffraction analysis, and referring to Figure 10, the two-dirnentional structure spacing becomes the 2.9nm to leucine succinic diamide phenyl silicon oxide compounds from the 2.3nm to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds.The variation of this two-dirnentional structure spacing theoretical value unanimity behind the two-dirnentional structure grafting leucine that coexists, thereby the formation to leucine succinic diamide phenyl silicon oxide compounds of further having confirmed to have laminate structure.
The amino acid of other in the table a kind also can obtain similarly infrared, the X-ray powder diffraction spectrogram.Proved formation to amino acid succinic diamide phenyl silicon oxide compounds with laminate structure.
Embodiment 2
Natural (L type) and racemize (DL type)-to the preparation of amino acid butylene diamide phenyl silicon oxide stratiform compound (C);
(1) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is with (1) step in the above embodiments 1;
(2) 0.1mol p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the 50ml THF, and then adds the maleic acid anhydride of 0.5mol, be heated to 50 ℃, magnetic agitation 1 day; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's acrylamide phenyl silicon oxide stratiform compound;
Product is carried out Infrared spectroscopy, and the alkyl of dodecyl sulphate is 2700 to 3000cm -1The peak, in infrared spectra, disappear to carboxylic acid group's acrylamide phenyl silicon oxide compounds.As seen, in to carboxylic acid group's propionic acid amide phenyl silicon oxide compounds, there is not the existence of dodecyl sulphate.Two new peak 1700and 1660cm have appearred in the infrared spectra to carboxylic acid group's acrylamide phenyl silicon oxide compounds in addition -1, these two peaks are respectively the vibration peak of the carbonyl among amide group and the carboxylic acid group.Obviously, a carbonyl in the maleic acid anhydride has generated acid amides with the reaction of the amino in p-aminophenyl silicon oxide-dodecyl sulphate, another carbonyl has changed into the carboxylic acid group in the maleic acid anhydride simultaneously, thereby has formed carboxylic acid group's acrylamide phenyl silicon oxide compounds.
Product is carried out 13C CP/MAS nuclear magnetic resonance spectroscopy two contour resonance peaks occurred at 177.8ppm and 172.6ppm, and these two peaks are respectively the resonance peak of the carbonyl among amide group and the carboxylic acid group.Observed the resonance peak of two carbon atoms of alkene respectively at 149ppm and 110.7ppm.Proved that a carbonyl in the maleic acid anhydride has generated acid amides with the reaction of the amino in p-aminophenyl silicon oxide-dodecyl sulphate, another carbonyl has changed into the carboxylic acid group in the maleic acid anhydride simultaneously, thereby has formed carboxylic acid group's acrylamide phenyl silicon oxide compounds.Product is carried out the X-ray powder diffraction analysis, obtained together the similar result of carboxylic acid group's propionic acid amide phenyl silicon oxide compounds (Fig. 7), thereby proof is in carboxylic acid group's acrylamide phenyl silicon oxide compounds, and two-dirnentional structure remains intact and with the model diagram unanimity.
(3) 0.1mol is dispersed in the 30ml toluene carboxylic acid group's third rare acid amides phenyl silicon oxide, and then adds 0.5mol thionyl chloride or oxalyl chloride, be heated to 50 ℃, magnetic agitation 3 hours; Behind the cool to room temperature, residual thionyl chloride or oxalyl chloride phosphorus are removed in decompression then, and last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides crotonamide phenyl silicon oxide stratiform compound.
Product is carried out Infrared spectroscopy, in carboxylic acid group's acrylamide phenyl silicon oxide compounds at 1660cm -1The vibration peak of carbonyl among the carboxylic acid group at place disappears in the infared spectrum to acyl chlorides crotonamide phenyl silicon oxide compounds, generation be to the 1770cm in the infared spectrum of acyl chlorides butyramide phenyl silicon oxide compounds -1The vibration peak of acyl chlorides has appearred in the place.Obviously, the carboxyl in the acyl chlorides crotonamide phenyl silicon oxide compounds with thionyl chloride or oxalyl chloride reaction, has been generated acyl chlorides.
(4) 0.1mol is dispersed in the 20ml dry DMF acyl chlorides crotonamide phenyl silicon oxide, add 0.15mol amino reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 2) in addition then, wherein carboxyl is protected with 2-bromobenzene oxygen carbonyl (BrZ) with the tert-butyl ester (tBu) protection, pendant hydroxyl group; Be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying; If amino reaction product with tertbutyloxycarbonyl (Boc) protection just is dispersed in the 20ml methylene dichloride that contains 0.2mol trifluoroacetic acid (TFA), room temperature magnetic agitation 3 hours is to remove amino protecting group tertbutyloxycarbonyl.If the reaction product of hydroxyl with 2-bromobenzene oxygen carbonyl (BrZ) protection arranged; just be dispersed in the 20ml methylene dichloride; add then and contain in 1ml methyl-phenoxide and the 8ml anhydrous hydrofluoric acid, 0 ℃ of magnetic agitation 3 hours is to remove 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl.Last product suction filtration is used washing with alcohol, vacuum-drying, and final product natural (L type) and racemize (DL type)-to amino acid butylene diamide phenyl silicon oxide stratiform compound.
Carry out infrared and the X-ray powder diffraction analysis to product, obtained being similar to infrared, the X-ray powder diffraction spectrogram of Fig. 9 and 10.Proved formation to amino acid butylene diamide phenyl silicon oxide stratiform compound with laminate structure.
Embodiment 3
Natural (L type) and racemize (DL type)-to the preparation of amino acid glutaramide phenyl silicon oxide stratiform compound (D);
(1) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is with (1) step in the above embodiments 1;
(2) 0.1mol p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the 50ml THF, and then adds the Pyroglutaric acid of 0.5mol, be heated to 50 ℃, magnetic agitation 1 day; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's butyramide phenyl silicon oxide stratiform compound;
To product carry out infrared and 13C CP/MAS nuclear magnetic resonance spectroscopy, obtained being similar to the infrared of Fig. 5 and 6 and 13The CCP/MAS nuclear magnetic resonance map, proved that a carbonyl in the Pyroglutaric acid has generated acid amides with the reaction of the amino in p-aminophenyl silicon oxide-dodecyl sulphate, another carbonyl has changed into the carboxylic acid group in the Pyroglutaric acid simultaneously, thereby has formed carboxylic acid group's butyramide phenyl silicon oxide compounds.Product is carried out the X-ray powder diffraction analysis, and obtaining the two-dirnentional structure spacing is 2.6nm.This structure pitch value is together to the silicon layer spacing unanimity in the theoretical construct of carboxylic acid group's butyramide phenyl silicon oxide stratiform compound.Proved that in two-dirnentional structure remains intact and with the model diagram unanimity to carboxylic acid group's butyramide phenyl silicon oxide compounds.
(3) 0.1mol is dispersed in the 30ml toluene carboxylic acid group's butyramide phenyl silicon oxide, and then adds thionyl chloride or the oxalyl chloride of 0.5mol, is heated to 50 ℃, magnetic agitation 3 hours; Behind the cool to room temperature, residual thionyl chloride or oxalyl chloride are removed in decompression then, and last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides valeramide phenyl silicon oxide stratiform compound.
Product is carried out Infrared spectroscopy, in carboxylic acid group's butyramide phenyl silicon oxide compounds at 1660cm -1The vibration peak of carbonyl among the carboxylic acid group at place disappears in the infared spectrum to acyl chlorides valeramide phenyl silicon oxide compounds, generation be to the 1775cm in the infared spectrum of acyl chlorides valeramide phenyl silicon oxide compounds -1The vibration peak of acyl chlorides has appearred in the place.Obviously, the carboxyl in the acyl chlorides valeramide phenyl silicon oxide compounds with thionyl chloride or oxalyl chloride reaction, has been generated acyl chlorides.
(4) 0.1mol is dispersed in the 20ml dry DMF acyl chlorides valeramide phenyl silicon oxide, add 0.15mol amino reactive group protected natural (L type) or racemize (DL type) amino acid (kind sees Table 3) in addition then, wherein carboxyl is protected with 2-bromobenzene oxygen carbonyl (BrZ) with the tert-butyl ester (tBu) protection, pendant hydroxyl group; Be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying; If amino reaction product with tertbutyloxycarbonyl (Boc) protection just is dispersed in the 20ml methylene dichloride that contains 0.2mol trifluoroacetic acid (TFA), room temperature magnetic agitation 3 hours is to remove amino protecting group tertbutyloxycarbonyl.If the reaction product of hydroxyl with 2-bromobenzene oxygen carbonyl (BrZ) protection arranged; just be dispersed in the 20ml methylene dichloride; add then and contain in 1ml methyl-phenoxide and the 8ml anhydrous hydrofluoric acid, 0 ℃ of magnetic agitation 3 hours is to remove 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl.Last product suction filtration is used washing with alcohol, vacuum-drying, and final product natural (L type) and racemize (DL type)-to amino acid glutaramide phenyl silicon oxide stratiform compound.
Product is carried out Infrared spectroscopy, obtained being similar to the infrared spectrogram of Fig. 9.Product is carried out the X-ray powder diffraction analysis, and obtaining the two-dimensional layer spacing is 3.2nm, has proved the formation to amino acid glutaramide phenyl silicon oxide stratiform compound with laminate structure.

Claims (2)

1. nano-laminal compound with regular arrays of amino acid includes (A) natural L type and racemize DL type-to amino acid succinic diamide phenyl silicon oxide stratiform compound, (B) natural L type and racemize DL type-to amino acid butylene diamide phenyl silicon oxide stratiform compound, (C) natural L type and racemize DL type-amino acid glutaramide phenyl silicon oxide stratiform compound, its chemical chemical formula and structural formula are respectively:
(A) natural L type and racemize DL type-to amino acid succinic diamide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 2H 4CONHCHCOOHR
Structure is:
Figure A2009101332160002C1
Table 1, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate 1 H Glycine To glycine succinic diamide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type 2 CH 3 L-Ala To L-Ala succinic diamide phenyl silicon oxide stratiform compound 3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan succinic diamide phenyl silicon oxide stratiform compound 4 CH 2CH(CH 3) 2 Leucine To leucine succinic diamide phenyl silicon oxide stratiform compound 5 CHCH 3C 2H 5 Isoleucine To Isoleucine succinic diamide phenyl silicon oxide stratiform compound 6 C 3H 6 Proline(Pro) To proline(Pro) succinic diamide phenyl oxygen The amino of proline(Pro) compares structural table
Change silicon layer shape compound Reach few hydrogen in the formula 7 CH 2C 6H 5 Phenylalanine To phenylalanine succinic diamide phenyl silicon oxide stratiform compound 8 CH 2C 6H 4OH Tyrosine To tyrosine succinic diamide phenyl silicon oxide stratiform compound 9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) succinic diamide phenyl silicon oxide stratiform compound 10 CH 2OH Serine To Serine succinic diamide phenyl silicon oxide stratiform compound 11 CHOHCH 3 Threonine To Threonine succinic diamide phenyl silicon oxide stratiform compound 12 CH 2COOH Aspartic acid To aspartic acid succinic diamide phenyl silicon oxide stratiform compound 13 C 2H 4COOH L-glutamic acid To L-glutamic acid succinic diamide phenyl silicon oxide stratiform compound
(B) natural L type and racemize DL type-to amino acid butylene diamide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 2H 2CONHCHCOOHR, structure is:
Figure A2009101332160003C1
Table 2, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate 1 H Glycine To glycine butylene diamide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type 2 CH 3 L-Ala To L-Ala butylene diamide phenyl silicon oxide stratiform compound
3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan butylene diamide phenyl silicon oxide stratiform compound 4 CH 2CH(CH 3) 2 Leucine To leucine butylene diamide phenyl silicon oxide stratiform compound 5 CHCH 3C 2H 5 Isoleucine To Isoleucine butylene diamide phenyl silicon oxide stratiform compound 6 C 3H 6 Proline(Pro) To proline(Pro) butylene diamide phenyl silicon oxide stratiform compound The amino of proline(Pro) is than the hydrogen that lacks in the structure expression 7 CH 2C 6H 5 Phenylalanine To phenylalanine butylene diamide phenyl silicon oxide stratiform compound 8 CH 2C 6H 4OH Tyrosine To tyrosine butylene diamide phenyl silicon oxide stratiform compound 9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) butylene diamide phenyl silicon oxide stratiform compound 10 CH 2OH Serine To Serine butylene diamide phenyl silicon oxide stratiform compound 11 CHOHCH 3 Threonine To Threonine butylene diamide phenyl silicon oxide stratiform compound 12 CH 2COOH Aspartic acid To aspartic acid butylene diamide phenyl silicon oxide stratiform compound 13 C 2H 4COOH L-glutamic acid To L-glutamic acid butylene diamide phenyl silicon oxide stratiform compound
(C) natural (L type) and racemize (DL type)-to amino acid glutaramide phenyl silicon oxide stratiform compound;
Chemical formula :-SiO 1.5C 6H 4NHCOC 3H 6CONHCHCOOHR, structure is:
Figure A2009101332160004C1
Table 3, the kind of R and the amino acid of correspondence and the title of compound
The kind of R Corresponding amino acid title Corresponding compound title Annotate 1 H Glycine To glycine glutaramide phenyl silicon oxide stratiform compound Glycine does not have chirality, is regardless of L type and DL type 2 CH 3 L-Ala To L-Ala glutaramide phenyl silicon oxide stratiform compound 3 CH(CH 3) 2 Xie Ansuan To Xie Ansuan glutaramide phenyl silicon oxide stratiform compound 4 CH 2CH(CH 3) 2 Leucine To leucine glutaramide phenyl silicon oxide stratiform compound 5 CHCH 3C 2H 5 Isoleucine To Isoleucine glutaramide phenyl silicon oxide stratiform compound 6 C 3H 6 Proline(Pro) To proline(Pro) glutaramide phenyl silicon oxide stratiform compound The amino of proline(Pro) is than the hydrogen that lacks in the structure expression 7 CH 2C 6H 5 Phenylalanine To phenylalanine glutaramide phenyl silicon oxide stratiform compound 8 CH 2C 6H 4OH Tyrosine To tyrosine glutaramide phenyl silicon oxide stratiform compound 9 C 2H 4SCH 3 Methionine(Met) To methionine(Met) glutaramide phenyl silicon oxide stratiform compound 10 CH 2OH Serine To Serine glutaramide phenyl silicon oxide stratiform compound 11 CHOHCH 3 Threonine To Threonine glutaramide phenyl silicon oxide stratiform compound 12 CH 2COOH Aspartic acid To aspartic acid glutaramide phenyl silicon oxide stratiform compound 13 C 2H 4COOH L-glutamic acid To L-glutamic acid glutaramide phenyl silicon oxide stratiform compound
2. one kind prepares the method with nano-laminal compound of regular arrays of amino acid according to claim 1, it is characterized in that to have the nano-laminal compound of regularly arranged acyl chloride, carry out the amidation graft reaction with protected natural L type of active group and racemize DL type amino acid beyond amino, utilize the protecting group remover to remove amino acid whose protecting group then, thereby obtain stablely, have the nano-laminal compound of regular arrays of amino acid; Nano-laminal compound (A), (B), (C) preparation process and reactions steps separately is as follows:
A. natural L type and racemize DL type-to the preparation of amino acid succinic diamide phenyl silicon oxide stratiform compound (A);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is: at first sodium lauryl sulphate is dissolved in the deionized water, add the p-aminophenyl Trimethoxy silane then, follow slow dripping hydrochloric acid solution and regulate pH value to 2～3 of mixing solutions, and at room temperature magnetic agitation was carried out sol-gel process in 12 days; Last suction filtration, with deionized water, acetyl washing, vacuum-drying obtains p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound respectively; Its chemical formula is:
-SiO 1.5C 6H 4NH 3C 12H 25OSO 3, structure is:
Figure A2009101332160006C1
(b) Succinic anhydried is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the THF, and then adds Succinic anhydried, be heated to 50 ℃, magnetic agitation 1 day; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 4COOH
Structure is:
Figure A2009101332160007C1
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's propionic acid amide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's propionic acid amide phenyl silicon oxide, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides butyramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 4COCl
Structure is:
Figure A2009101332160007C2
(d) with protected natural L type of reactive group or racemize DL type amino acid beyond the amino, kind sees Table 1, wherein carboxyl with the tert-butyl ester (tBu) protection, pendant hydroxyl group with 2-bromobenzene oxygen carbonyl (BrZ) protect, with above-mentioned acyl chlorides butyramide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester protecting group of carboxyl is removed with trifluoroacetic acid TFA then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides butyramide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 3 hours; last suction filtration; use washing with alcohol, vacuum-drying, final natural L type of product and racemize DL type-to amino acid succinic diamide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 2H 4The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 2H 4CONHCHCOOHR
The kind of R sees Table 1
B. natural L type and racemize DL type-to the preparation of amino acid butylene diamide phenyl silicon oxide stratiform compound (B);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is with (a) step among the above-mentioned A;
(b) maleic acid anhydride is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate is dispersed among the THF, and then adds maleic acid anhydride, be heated to 50 ℃, magnetic agitation 12 hours; Last suction filtration is used washing with alcohol, vacuum-drying, and the final product that gets is to carboxylic acid group's acrylamide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 2COOH
Structure is:
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's acrylamide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's acrylamide phenyl silicon oxide, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides crotonamide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 2H 2COCl
Structure is:
(d) with protected natural L type of reactive group or racemize DL type amino acid beyond the amino, kind sees Table 2, wherein carboxyl is protected with 2-bromobenzene oxygen carbonyl (BrZ) with tert-butyl ester protection, pendant hydroxyl group, with above-mentioned acyl chlorides crotonamide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester protecting group of carboxyl is removed with trifluoroacetic acid then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides crotonamide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 3 hours; last suction filtration; use washing with alcohol, vacuum-drying, final natural L type of product and racemize DL type-to amino acid butylene diamide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 2H 2The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 2H 2CONHCHCOOHR
The kind of R sees Table 2
C. natural L type and racemize DL type-to the preparation of amino acid glutaramide phenyl silicon oxide stratiform compound (C);
(a) the good p-aminophenyl silicon oxide of prepared beforehand-dodecyl sulphate lamellar compound; Its preparation method is with (a) step among the above-mentioned A;
(b) Pyroglutaric acid is reacted with above-mentioned p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound; Its reaction process and step are as follows: p-aminophenyl silicon oxide-dodecyl sulphate lamellar compound is dispersed among the THF, add Pyroglutaric acid then, be heated to 50 ℃, magnetic agitation 1 day, last suction filtration, use washing with alcohol, vacuum-drying, the final product that gets is to carboxylic acid group's butyramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 3H 6COOH
Structure is:
Figure A2009101332160010C1
(c) with thionyl chloride or oxalyl chloride with above-mentioned carboxylic acid group's butyramide phenyl silicon oxide stratiform compound is reacted; Its reaction process and step are as follows: will be dispersed in the toluene carboxylic acid group's butyramide phenyl silicon oxide stratiform compound, and then add thionyl chloride or oxalyl chloride, and be heated to 50 ℃, magnetic agitation 3 hours; Last suction filtration is used washed with dichloromethane, vacuum-drying, and the final product that gets is to acyl chlorides valeramide phenyl silicon oxide stratiform compound;
Its chemical formula is :-SiO 1.5C 6H 4NHCOC 3H 6COCl
Structure is:
Figure A2009101332160011C1
(d) with protected natural L type of reactive group or racemize DL type amino acid beyond the amino, kind sees Table 3, wherein carboxyl is with the tert-butyl ester (tBu) protection, pendant hydroxyl group 2-bromobenzene oxygen carbonyl-protection, with above-mentioned acyl chlorides valeramide phenyl silicon oxide stratiform compound is reacted; The tert-butyl ester protecting group of carboxyl is removed with trifluoroacetic acid then, and 2-bromobenzene oxygen carbonyl (BrZ) protecting group of hydroxyl is removed with the anhydrous hydrofluoric acid that contains methyl-phenoxide.Its reaction process and step are as follows: will be dispersed among the DMF acyl chlorides valeramide phenyl silicon oxide, and add the amino acid of band protecting group then, and be heated to 35 ℃, magnetic agitation 6 hours; Last suction filtration; use washed with dichloromethane; add TFA then or contain the anhydrous hydrofluoric acid of methyl-phenoxide; the room temperature magnetic agitation was removed protecting group in 2 hours; last suction filtration; use washing with alcohol, vacuum-drying, final natural L type of product and racemize DL type-to amino acid glutaramide phenyl silicon oxide stratiform compound.Its chemical reaction process is as follows:
-SiO 1.5C 6H 4NHCOC 3H 6The amino acid of COCl+ band protecting group-→
-SiO 1.5C 6H 4NHCOC 3H 6CONHCHCOOHR
The kind of R sees Table 3
CN200910133216A 2008-09-24 2009-03-25 Nano-layered compound with regular arrays of amino acid and preparation method thereof Pending CN101538276A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391300A (en) * 2011-08-30 2012-03-28 上海大学 Organic/ inorganic composite lamellar compound containing glutathione (GSH) and preparation method thereof
CN104311589A (en) * 2014-04-14 2015-01-28 上海大学 p-carboxyl propionamidophenyl silicon oxide, co-immobilized L-lactic dehydrogenase compound and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391300A (en) * 2011-08-30 2012-03-28 上海大学 Organic/ inorganic composite lamellar compound containing glutathione (GSH) and preparation method thereof
CN104311589A (en) * 2014-04-14 2015-01-28 上海大学 p-carboxyl propionamidophenyl silicon oxide, co-immobilized L-lactic dehydrogenase compound and preparation method thereof
CN104311589B (en) * 2014-04-14 2017-06-23 上海大学 To carboxylic acid group's propionamide phenyl silica, its co-immobilization L lactic dehydrogenase multienzyme complexs and preparation method thereof

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