CN1464001A - Chloro-silicane polyethylene derivative, process for synthesizing and use thereof - Google Patents
Chloro-silicane polyethylene derivative, process for synthesizing and use thereof Download PDFInfo
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- CN1464001A CN1464001A CN 02121354 CN02121354A CN1464001A CN 1464001 A CN1464001 A CN 1464001A CN 02121354 CN02121354 CN 02121354 CN 02121354 A CN02121354 A CN 02121354A CN 1464001 A CN1464001 A CN 1464001A
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- polyethylene glycol
- chlorosilane
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Abstract
The present invention relates to chlorsilane polyglycol derivative as one solid surface modifying compound. The derivative is prepared through condensation and addition reaction, and can inhibit the adsorption of protein molecule on the surface of solid. The derivative is suitable for application in biomedicine field.
Description
Technical Field
The invention relates to a surface modified compound, in particular to a compound for modifying a solid surface and inhibiting biological molecules from being adsorbed on the solid surface, a synthetic method and application thereof.
Background
Polyethylene glycol molecules have good biocompatibility and have been widely used in the biological field, particularly in material surface modification. The two ends of the polyethylene glycol molecule are hydroxyl groups, which are not easy to react with the solid surface to achieve the purpose of surface modification, sothe common method is to modify the terminal group of the polyethylene glycol molecule, so that the modified terminal group is easy to react with the solid surface. A research group at Harvard university in the United states (Joydeep Lahiri, Lyle Isaacs, Joe tien, George M. Whitesids, Analytical Chemistry, 1999, 71, 777-quick 790) uses a thiol group to modify the terminal groups of a polyethylene glycol molecule. The modified polyethylene glycol molecule can easily react with the gold surface, so as to be covalently immobilized on the gold surface. The polyethylene glycol molecule modified by sulfydryl can only react with the surfaces of metals such as gold, silver and the like, and the application range is narrow. Chlorosilane is a compound with extremely active chemical properties, can react with various surfaces of glass, plastics, metal oxides and the like, and has a wider application range.
Disclosure of Invention
The invention aims to overcome the defect of narrow application range of the traditional polyethylene glycol derivative as a surface modification material, and provides a chlorosilane polyethylene glycol derivative which is widely used for surface modification of a solid substrate.
The invention also aims to provide a synthesis method of the chlorosilane polyethylene glycol derivative.
The invention further aims to provide application of the chlorosilane polyethylene glycol derivative in solid surface modification.
The invention relates to a chlorosilane polyethylene glycol derivative which has the following molecular formula (I):
in the formula: m is any integer between 5 and 20;
n is any integer between 3 and 50;
x comprises methyl or ethyl;
r1 and R2 include Cl or methyl.
Chlorosilane polyethylene glycol derivatives according to the invention, where the radical X is preferably methyl, R1 and R2 are preferably Cl radicals.
The chlorosilane moiety in the chlorosilane polyethylene glycol derivative is susceptible to reacting with hydroxyl groups on the solid surface to form siloxane bonds, thereby covalently immobilizing the compound on the solid surface. The hydrophilicity, flexibility and electric neutrality of the polyethylene glycol molecules can effectively inhibit the physical adsorption of protein molecules on the surface of the solid substrate. The polymerization degree n of the polyethylene glycol can be changed according to needs, and the larger the n value in a certain range, the better the effect of inhibiting the adsorption of protein molecules on the solid surface.
The invention also relates to a method for preparing the chlorosilane polyethylene glycol derivative, which comprises the following steps: (1) condensation reaction Under alkaline environment, reacting H (OCH)2CH2)nOX and CH2＝CH(CH2)m-2Mixing Br in a molar ratio of 1: 2-1: 10; and carrying out oil bath at 70-150 ℃, and carrying out condensation reaction under the protection of reflux nitrogen, wherein the reaction time is about 16-24 hours. (2) Addition reaction Dissolving the product obtained in the step (1) in an alcohol organic solvent, and then adding 2-4 equivalents of chlorine hydrogen silicon and a photoinitiator; under the protection of reflux nitrogen, the reaction is carried out for 4 to 6 hours by 365nm ultraviolet radiation.
Wherein: m is any integer between 5 and 20;
n is any integer between 3 and 50;
x comprises methyl or ethyl;
r1 and R2 include Cl or methyl.
In the method for preparing the chlorosilane polyethylene glycol derivative, the alcohol organic solvent in the step (2) is preferably methanol; the photoinitiator is preferably benzoin dimethyl ether.
In addition, the invention also relates to the application of the chlorosilane polyethylene glycol derivative in solid surface modification.
The invention has the advantages that the modified solid surface can inhibit the adsorption of protein molecules, so the chlorosilane polyethylene glycol derivatives have wide application prospects in the material science in the field of biomedicine, such as the substrate surface modification for solid-phase immunoassay, the surface modification of biological materials (particularly materials implanted into organisms), the surface modification of appliances for protein purification and the like.
Detailed description example 1 Cl (CH)3)2Si(CH2)11(OCH2CH2)4OCH3Synthesis of (2)
Step 1: synthesis of CH2＝CH(CH2)9(OCH2CH2)4OCH3
1) 0.34ml of 50% NaOH was mixed with 4.0g H (OCH)2CH2)3OCH3Mixing, electromagnetically stirring, carrying out oil bath at 100 ℃ for 30 minutes, and taking reflux nitrogen as protective gas;
2) adding 1.0g of 11-bromo-1-ene-undecane into the reaction system, electromagnetically stirring, and carrying out oil bath at 100 ℃for 16 hours;
3) cooling the reactant, extracting for 6 times by using normal hexane, and combining the extract liquor;
4) concentrating the extract by rotary evaporation under reduced pressure to obtain yellow oily substance containing monoether and diether;
5) purifying the product;
step 2: synthesis of Cl (CH)3)2Si(CH2)11(OCH2CH2)4OCH3
1) Adding 4 equivalents of dimethyl chlorosilane and 10mg of benzoin dimethyl ether into 400mmol of the product solution (dissolved in methanol) obtained in the step 1, taking backflow nitrogen as protective gas, and placing the reaction system under 365nm ultraviolet, filtering and irradiating for 4 hours by hard glass;
2) concentrating the reaction product by rotary evaporation, dissolving the reaction product by using a small amount of ethyl acetate, and filtering out white insoluble precipitate;
3) the product was purified by distillation. Example 2 Cl2CH3Si(CH2)5(OCH2CH2)50OCH2CH3Synthesis of (2)
Step 1: synthesis of CH2＝CH(CH2)3(OCH2CH2)50OCH3
1) 0.34ml of 50% NaOH was mixed with 20.0g H (OCH)2CH2)50OCH3Mixing, electromagnetically stirring, carrying out oil bath at 150 ℃ for 30 minutes, and taking reflux nitrogen as protective gas;
2) adding 1.0g of 5-bromo-1-ene-pentadecane into the reaction system, electromagnetically stirring, and carrying out oil bath at 150 ℃ for 16 hours;
3) cooling the reactant, extracting for 6 times by using normal hexane, and combining the extract liquor;
4) concentrating the extract by rotary evaporation under reduced pressure to obtain yellow oily substance containing monoether and diether;
5) purifying the product;
step 2: synthesis of Cl2CH3Si(CH2)5(OCH2CH2)50OCH2CH3
1) Adding 4 equivalents of dichloromethyl hydrogen and 10mg of benzoin dimethyl ether into 400mmol of the product solution (dissolved in methanol) obtained in the step 1, taking backflow nitrogen as protective gas, and placing the reaction system under 365nm ultraviolet, filtering and irradiating for 6 hours by hard glass;
2) concentrating the reaction product by rotary evaporation, dissolving the reaction product by using a small amount of ethyl acetate, and filtering out white insoluble precipitate;
3) the product was purified by distillation. Example 3 Cl3Si(CH2)20(OCH2CH2)4OCH3Synthesis of (2)
Step 1: synthesis of CH2＝CH(CH2)18(OCH2CH2)4OCH3
1) 0.34ml of 50% NaOH was mixed with 5.0g H (OCH)2CH2)4OCH3Mixing, electromagnetically stirring, carrying out oil bath at 120 ℃ for 30 minutes, and taking reflux nitrogen as protective gas;
2) adding 1.0g of 20-bromo-1-ene-eicosane into the reaction system, electromagnetically stirring, and carrying out oil bath at 120 ℃ for 14 hours;
3) cooling the reactant, extracting for 6 times by using normal hexane, and combining the extract liquor;
4) concentrating the extract by rotary evaporation under reduced pressure to obtain yellow oily substance containing monoether and diether;
5) purifying the product;
step 2: synthesis of Cl3Si(CH2)20(OCH2CH2)4OCH3
1) Adding 4 equivalents of trichlorosilane and 10mg of benzoin dimethyl ether into 400mmol of the product solution (dissolved in methanol) obtained in the step 1, taking backflow nitrogen as protective gas, and placing the reaction system under 365nm ultraviolet to be filtered and irradiated by hard glass for 5 hours;
2) concentrating the reaction product by rotary evaporation, dissolving the reaction product by using a small amount of ethyl acetate, and filtering out white insoluble precipitate;
3) the product was purified by distillation.
Claims (8)
1. A chlorosilane polyethylene glycol derivative with the following molecular formula (I):
in the formula: m is any integer between 5 and 20;
n is any integer between 3 and 50;
x comprises methyl or ethyl;
r1 and R2 include Cl or methyl.
2. Chlorosilane polyethylene glycol derivatives according to claim 1, characterized in that the radical X is a methyl radical.
3. Chlorosilane polyethylene glycol derivatives according to claim 1, wherein R1 and R2 both comprise Cl.
4. A process for preparing a chlorosilane polyethylene glycol derivative of claim 1 comprising the steps of: (1) the condensation reaction has the following reaction formula: under alkaline environment, reacting H (OCH)2CH2)nOX and CH2＝CH(CH2)m-2Br is mixed, the molar ratio is 1: 2-1: 10, oil bath is carried out at 700-1500 ℃, and condensation reaction is carried out for 16-24 hours under the protection of reflux nitrogen; (2) the reaction formula of the addition reaction is as follows: dissolving the product obtained in the step (1) in an alcohol organic solvent, and then adding 2-4 equivalents of chlorine hydrogen silicon and a photoinitiator; under the protection of reflux nitrogen, 365nm ultraviolet rays are usedIrradiating for 4-6 hours;
wherein: m is any integer between 5 and 20;
n is any integer between 3 and 50;
x comprises methyl or ethyl;
r1 and R2 include Cl or methyl.
5. The process for preparing chlorosilane polyethylene glycol derivatives according to claim 4, wherein the alcoholic organic solvent in the step (2) is methanol.
6. The process for preparing chlorosilane polyethylene glycol derivatives according to claim 4, wherein the photoinitiator in the step (2) is benzoin dimethyl ether.
7. Chlorosilane polyethylene glycol derivatives according to claim 1, which can be used for modification of material surfaces inthe biomedical field.
8. Use of chlorosilane polyethylene glycol derivatives according to claim 6 as a material for modifying the surface of substrates for solid phase immunoassays, the surface of biomaterials and the surface of instruments for protein purification.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021213542A CN1180004C (en) | 2002-06-14 | 2002-06-14 | Chloro-silicane polyethylene derivative, process for synthesizing and use thereof |
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| CNB021213542A CN1180004C (en) | 2002-06-14 | 2002-06-14 | Chloro-silicane polyethylene derivative, process for synthesizing and use thereof |
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| CN1464001A true CN1464001A (en) | 2003-12-31 |
| CN1180004C CN1180004C (en) | 2004-12-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014143667A1 (en) * | 2013-03-15 | 2014-09-18 | Croda, Inc. | Alkoxylated fatty alcohol alkyl ethers and products containing same |
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2002
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014143667A1 (en) * | 2013-03-15 | 2014-09-18 | Croda, Inc. | Alkoxylated fatty alcohol alkyl ethers and products containing same |
| CN105050572A (en) * | 2013-03-15 | 2015-11-11 | 禾大公司 | Alkoxylated fatty alcohol alkyl ethers and products containing same |
| KR20150130468A (en) * | 2013-03-15 | 2015-11-23 | 크로다 인코포레이티드 | Alkoxylated fatty alcohol alkyl ethers and products containing same |
| JP2016513705A (en) * | 2013-03-15 | 2016-05-16 | クローダ，インコーポレイティド | Alkoxylated fatty alcohol alkyl ethers and products containing the same |
| KR102065629B1 (en) * | 2013-03-15 | 2020-02-11 | 크로다 인코포레이티드 | Alkoxylated fatty alcohol alkyl ethers and products containing same |
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| CN1180004C (en) | 2004-12-15 |
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Granted publication date: 20041215 Termination date: 20110614 |