CN1281611C - Mono-methoxy polyethylene glycol derivatives and their preparing process and use - Google Patents
Mono-methoxy polyethylene glycol derivatives and their preparing process and use Download PDFInfo
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- CN1281611C CN1281611C CN 200410009027 CN200410009027A CN1281611C CN 1281611 C CN1281611 C CN 1281611C CN 200410009027 CN200410009027 CN 200410009027 CN 200410009027 A CN200410009027 A CN 200410009027A CN 1281611 C CN1281611 C CN 1281611C
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- methoxy polyethylene
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Abstract
The present invention relates to a single methoxypolyethylene glycol silicane derivant, a preparation process and an application thereof. The single methoxypolyethylene glycol silicane derivant is shown as the structural formula I: (R<1>O)<z>R<(3-z)><2>Si(CH<2>)<n>A(CH<2>CH<2>O)<m>CH<3>, wherein R<1> and R<2> respectively and independently denote straight chain or branched alkyl with one to ten carbon atoms, aralkyl or aryl; A is an oxygen atom or a sulphur atom; z is 1, 2 or 3; n is a whole number between 1 to 12; m is a whole number between 1 to 50. In the preparation process of the single methoxypolyethylene glycol silicane derivant, firstly, single methoxypolyethylene glycol reacts with organic amine and p-tosyl chloride to obtain single methoxypolyethylene glycol p-toluenesulfonate; then, an alkoxy silane compound reacts with sodium alcoholate to obtain the single methoxypolyethylene glycol silicane derivant of the present invention. The single methoxypolyethylene glycol silicane derivant can be used as adsorption inhibitor to suppress the nonspecific adsorption of biomolecules on the surface of an inorganic material, use conditions are mild and processing processes are simple.
Description
Technical field
The present invention relates to a kind of mono methoxy polyethylene glycol silane derivative and its production and use.
Background technology
Concerning Biomedical Instruments, Biochemical processes and biological diagnosis, protein and other biomolecules are common problems in the non-specific adsorption of material surface, especially when relating to metal or glass material, because protein can adsorb into multilayer film at these material surfaces because of electrostatic adhesion with other biomolecules.The method that suppresses this absorption at present is to use the absorption inhibitor---long chain silane or polyoxyethylene glycol.The former forms a chain alkyl molecular film by the covalent effect of long chain silane and glass or oxidation on metal surface thing on the surface, has sheltered the electrostatic interaction between base material and the biomolecules, thereby has suppressed physical adsorption between the two.But, the surface free energy (γ that this is surperficial
SL=50mN/m) still higher relatively, still can adsorb an about rete that biomolecules is thick.Wetting ability, flexibility and the electric neutrality of latter's peg molecule (PEG) chain can effectively suppress the physical adsorption of biomolecules at inorganic material surface, are the means of the non-special absorption of a kind of effective inhibition biomolecules at surface bond PEG chain therefore.Usually, the method for bonding PEG chain comprises that the graft copolymerization of PEG and polymkeric substance and polyoxyethylene glycol are by linked reaction and surperficial coupling.Grafting copolymerization process makes the PEG chain become the polymer fragment of polymer materials, but is not suitable for on-macromolecular materials such as metallic substance, glass material.Though and with PEG chain and surface directly coupling be the effective ways of handling surface properties, this method usually needs could realize through complex process when coupling.
Summary of the invention
The objective of the invention is to overcome existing absorption inhibitor and suppress biomolecules when the non-specific adsorption of material surface, defectives such as restraining effect is not strong, complex disposal process, thereby provide a kind of to biomolecules the inhibition effect of material surface non-specific adsorption obviously, treating processes mono methoxy polyethylene glycol silane derivative simply and easily, and its production and use.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of mono methoxy polyethylene glycol silane derivative of representing by following structural formula I,
(R
1O)
zR
2 (3-z)Si (CH
2)
nA (CH
2CH
2O)
mCH
3(structural formula I)
Wherein, R
1, R
2Independent separately expression contains the straight or branched alkyl of 1～10 carbon atom, aralkyl or aryl; The straight chained alkyl of preferred 1～4 carbon atom; More preferably methyl or ethyl;
A is Sauerstoffatom or sulphur atom; Be preferably sulphur atom;
Z is 1,2 or 3; Preferably 3;
N is the integer between 1 to 12; Integer between preferred 3 to 10;
M is the integer between 1 to 50; Integer between preferred 1 to 18; The integer between 3 to 8 more preferably.
The invention provides a kind of preparation method of described mono methoxy polyethylene glycol silane derivative, it is with the terminal asymmetric functionalization of peg molecule, comprises the steps:
1) terminal hydroxyl of mono methoxy polyethylene glycol carries out functional group's conversion: react by following (reaction formula 1), bathe under the cooling at cryosel, mono methoxy polyethylene glycol molecule and organic amine are dissolved in the methylene dichloride, add Tosyl chloride again, the mono methoxy polyethylene glycol molecule that adds: organic amine: the mol ratio of Tosyl chloride is 10: 10～15: 10～15, then mixed solution was at room temperature reacted 20 hours at least, remove insolubles, after the mixed solution that obtains concentrated, with sherwood oil: ethyl acetate=1: 1 is an eluent, silica gel column chromatography separates, and obtains the mono methoxy polyethylene glycol p-toluenesulfonic esters shown in the structural formula II; Described organic amine is pyridine or triethylamine;
(structural formula II)
Wherein, m is the integer between 1 to 50; Integer between preferred 1 to 18; The integer between 3 to 8 more preferably;
2) with the organoalkoxysilane reaction: react by following (reaction formula 2), the alkoxysilane compound containing trialkylsilyl group in molecular structure with structural formula II I and sodium alkoxide back flow reaction 3 hours in the alcoholic solvent of correspondence, be cooled to room temperature, with aprotic solvent dissolving step 1) after the mono methoxy polyethylene glycol p-toluenesulfonic esters that obtains, join in the reaction system room temperature reaction two days; Described alkoxysilane compound containing trialkylsilyl group in molecular structure: sodium alkoxide: the mol ratio of mono methoxy polyethylene glycol p-toluenesulfonic esters is 10～13: 10～13: 10; Described aprotic solvent is tetrahydrofuran (THF) (THF) or N, dinethylformamide (DMF); Remove by filter insolubles, the mixed solution that obtains is concentrated, with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains the mono methoxy polyethylene glycol silane derivative shown in the structural formula I of the present invention.
(structure III) (structural formula I)
Wherein, in the organoalkoxysilane shown in the structural formula II I, R
1, R
2Independent separately expression contains the straight or branched alkyl of 1～10 carbon atom, aralkyl or aryl; The straight chained alkyl of preferred 1～4 carbon atom; More preferably methyl or ethyl;
A is Sauerstoffatom or sulphur atom; Be preferably sulphur atom;
Z is 1,2 or 3; Preferably 3;
N is the integer between 1 to 12; Integer between preferred 3 to 10.
Raw material used in whole synthesizing is all through purifying and not having water treatment, and solvent for use is all through no water treatment.Reaction in whole synthesizing all is to carry out under inert atmosphere, all is waterless operation.
The invention provides a kind of purposes of above-mentioned mono methoxy polyethylene glycol silane derivative, it suppresses the non-specific adsorption of biomolecules at inorganic material surface as the absorption inhibitor.
Mono methoxy polyethylene glycol silane derivative provided by the invention has been introduced the organoalkoxysilane fragment in molecule.Organoalkoxysilane forms hydrogen bond by the hydrolysis of OR group and the hydroxyl of material surface, through dehydration reaction, is connected with covalent linkage with material.Whole process condition gentleness, simple to operate quick.Polyoxyethylene glycol is combined use to the restraining effect of biomolecules and organoalkoxysilane to the covalently bound effect of material surface, solved problems such as the restraining effect that occurs when suppressing biomolecules absorption is strong, complex disposal process.This derivative can obviously suppress the non-specific adsorption of biomolecules at material surface, the working conditions gentleness, and treating processes is simple, is a kind of effective biomolecules absorption inhibitor.
Description of drawings
Fig. 1 is a protein in the absorption of the silicon chip surface of modifying through mono methoxy polyethylene glycol-800 silane derivative 4 of embodiment 4 preparations, and wherein, " ●-" representative is coupled at cytochrome c on the silicon chip (12KD, spherical, diameter 34 ); " ■-" representative is coupled at albumin on the silicon chip (68KD, spherical, diameter 72 ); "-▲-" representative is coupled at being on silicon chip scleroproein (500KD, bar-shaped, long 600 , wide 25 ).
Fig. 2 be protein in absorption through the hydride modified silicon chip surface of undecyl, wherein, " ▲-" representative is coupled at cytochrome c on the silicon chip (12KD, spherical, diameter 34 ); " ■-" representative is coupled at albumin on the silicon chip (68KD, spherical, diameter 72 ); "-●-" representative is coupled at being on silicon chip scleroproein (500KD, bar-shaped, long 600 , wide 25 ).
Embodiment
Raw material used in whole synthesizing is all through purifying and not having water treatment, and solvent for use is all through no water treatment.Reaction in whole synthesizing all is to carry out under inert atmosphere, all is waterless operation.
Embodiment 1, preparation mono methoxy polyethylene glycol silane derivative 1
Dissolving mono methoxy triglycol (CH in the 150ml methylene dichloride
3O (CH
2CH
2O)
3H) 6.560g (40mmol) and 4.444g (44mmol) triethylamine, cryosel is bathed cooling.In the 50ml methylene dichloride, dissolve 8.426g (44mmol) Tosyl chloride in addition.Following tolysulfonyl chloro-dichloromethane solution of induction stirring dropwise joins in the reaction solution.Remove cryosel afterwards and bathe, return to room temperature, continue to stir 24 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 9.540g (30mmol) mono methoxy triglycol p-toluenesulfonic esters, productive rate 75%.
In 6ml methyl alcohol, dissolve 897mg (39mmol) sodium Metal 99.5, obtain the 39mmol sodium methylate.Add 7.644g (39mmol) mercaptopropyl trimethoxysilane afterwards, induction stirring refluxed 3 hours.Be cooled to room temperature.In 50mlTHF, dissolve 9.540g (30mmol) mono methoxy triglycol p-toluenesulfonic esters, this solution is added in the reaction solution induction stirring 48 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 4.446g (13mmol) derivative 1, productive rate 43.3%.
Embodiment 2, preparation mono methoxy polyethylene glycol silane derivative 2
Use the method identical with embodiment 1.
In the 120ml methylene dichloride, dissolve 1.748g (23mmol) mono methoxy ethylene glycol (CH
3OCH
2CH
2OH) and 2.362g (30mmol) pyridine, cryosel is bathed cooling.In the 50ml methylene dichloride, dissolve 5.745g (30mmol) Tosyl chloride in addition.Following tolysulfonyl chloro-dichloromethane solution of induction stirring dropwise joins in the reaction solution.Remove cryosel afterwards and bathe, return to room temperature, continue to stir 24 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 3.45g (15mmol) mono methoxy ethylene glycol p-toluenesulfonic esters, productive rate 65.2%.
In 4ml methyl alcohol, dissolve 345mg (15mmol) sodium Metal 99.5, obtain the 15mmol sodium methylate.Add 2.7g (15mmol) methyl(3-mercaptopropyl) dimethoxysilane afterwards, induction stirring refluxed 3 hours.Be cooled to room temperature.In 50mlTHF, dissolve 3.45g (15mmol) mono methoxy ethylene glycol p-toluenesulfonic esters, this solution is added in the reaction solution induction stirring 48 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 1.286g (5.4mmol) derivative 2, productive rate 36%.
Embodiment 3, preparation mono methoxy polyethylene glycol silane derivative 3
Use the method identical with embodiment 1.
In the 200ml methylene dichloride, dissolve 1.92g (5mmol) mono methoxy eight glycol (CH
3O (CH
2CH
2O)
8H) and 5.925g (7.5mmol) pyridine, cryosel is bathed cooling.In the 50ml methylene dichloride, dissolve 1.436g (7.5mmol) Tosyl chloride in addition.Following tolysulfonyl chloro-dichloromethane solution of induction stirring dropwise joins in the reaction solution.Remove cryosel afterwards and bathe, return to room temperature, continue to stir 24 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 1.668g (3.1mmol) mono methoxy eight glycol p-toluenesulfonic esters, productive rate 62%.
In 4ml ethanol, dissolve 78mg (3.4mmol) sodium Metal 99.5, obtain the 3.4mmol sodium ethylate.Add 0.809g (3.4mmol) mercaptopropyltriethoxysilane afterwards, induction stirring refluxed 3 hours.Be cooled to room temperature.In 50mlDMF, dissolve 1.668g (3.1mmol) mono methoxy eight glycol p-toluenesulfonic esters, this solution is added in the reaction solution induction stirring 48 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 0.785g (1.3mmol) derivative 3, productive rate 41.9%.
Embodiment 4, preparation mono methoxy polyethylene glycol silane derivative 4
Use the method identical with embodiment 1.
In the 100ml methylene dichloride, dissolve 2.16g (2.6mmol) mono methoxy polyethylene glycol-800 (CH
3O (CH
2CH
2O)
18H) and 0.263g (2.6mmol) triethylamine, cryosel is bathed cooling.In the 50ml methylene dichloride, dissolve 0.498g (2.6mmol) Tosyl chloride in addition.Following tolysulfonyl chloro-dichloromethane solution of induction stirring dropwise joins in the reaction solution.Remove cryosel afterwards and bathe, return to room temperature, continue to stir 24 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 1.512g (1.6mmol) mono methoxy polyethylene glycol-800 p-toluenesulfonic esters, productive rate 63%.
In 4ml methyl alcohol, dissolve 44mg (1.9mmol) sodium Metal 99.5, obtain the 1.9mmol sodium methylate.Add 0.559g (1.9mmol) mercapto decyl Trimethoxy silane afterwards, induction stirring refluxed 3 hours.Be cooled to room temperature.In 50mlDMF, dissolve 1.512g (1.6mmol) mono methoxy polyethylene glycol-800 p-toluenesulfonic esters, this solution is added in the reaction solution induction stirring 48 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 0.538g (0.5mmol) derivative 4, productive rate 31.2%.
Embodiment 5, preparation mono methoxy polyethylene glycol silane derivative 5
Use the method identical with embodiment 1.
Dissolve 3.454g (1.7mmol) mono methoxy polyethylene glycol-2000 and 0.150g (1.9mmol) pyridine in the 200ml methylene dichloride, cryosel is bathed cooling.In the 50ml methylene dichloride, dissolve 0.364g (1.9mmol) Tosyl chloride in addition.Following tolysulfonyl chloro-dichloromethane solution of induction stirring dropwise joins in the reaction solution.Remove cryosel afterwards and bathe, return to room temperature, continue to stir 24 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 2.14g (1.0mmol) mono methoxy polyethylene glycol-2000 p-toluenesulfonic esters, productive rate 58.8%.
In 4ml methyl alcohol, dissolve 26mg (1.1mmol) sodium Metal 99.5, obtain the 1.1mmol sodium methylate.Add 0.337g (1.1mmol) hydroxyl dodecyl Trimethoxy silane afterwards, induction stirring refluxed 3 hours.Be cooled to room temperature.In 50mlDMF, dissolve 2.14g (1.0mmol) mono methoxy polyethylene glycol-2000 p-toluenesulfonic esters, this solution is added in the reaction solution induction stirring 48 hours.Filter, filtrate concentrates through rotary evaporation, and again with sherwood oil: ethyl acetate=1: 1 be an eluent, and the silica gel column chromatography separation obtains 0.7g (0.3mmol) derivative 5, productive rate 30%.
The infrared absorption peak value of the mono methoxy polyethylene glycol silane derivative 1～5 of embodiment 1～5 preparation is listed in table 1.
The IR peak of table 1, mono methoxy polyethylene glycol silane derivative 1～5
| Derivative | IR peak (cm -1) |
| 1 | 2930，2925，2891，2860，2819，1460，1415，1213，1151，1112，1100， 1090，1102，963，947，842，729，690 |
| 2 | 2959，2925，2891，2860，2815，1740，1460，1421，1413，1365，1260， 1250，1254，1210，1151，1112，1090，1102，1100，963，947，842， 765，729，690 |
| 3 | 2930，2927，2891，2860，2822，1460，1420，1231，1151，1112，1110， 1102，1095，963，947，842，729，690 |
| 4 | 3500，3400，2946，2930，2891，2860，2828，1678，1460，1430，1267， 1151，1112，1110，1102，963，947，842，724，690 |
| 5 | 2948，2891，2830，1740，1460，1433，1254，1270，1210，1151，1112， 1110，1102，963，947，842，722 |
The Application Example of embodiment 6, mono methoxy polyethylene glycol silane derivative absorption inhibitor
After silicon chip washed with tap water, scrubbing powder water logging bubble spent the night, and uses tap water, distilled water, acetone, distilled water and second distillation water wash more respectively, oven dry back Pirahan solution (V ((H
2SO
4): V (H
2O
2), 70: 30) under 100 ℃, handle 1h, after a large amount of second distillation water washings, 150 ℃ of thermal treatment 5min, vacuum-drying.The activatory silicon chip is immersed rapidly in the silane derivative solution of mono methoxy polyethylene glycol-800 of fresh embodiment 4 preparations, under the room temperature in nitrogen gas stream standing over night (15-20h).Take out silicon chip, it is immersed in the methylene dichloride, then jog in a large amount of Virahols.Use chloroform, ethanol drip washing afterwards successively, the nitrogen gas stream drying obtains the silicon chip that the mono methoxy polyethylene glycol silane derivative 4 of embodiment 4 preparation is modified.
Other gets silicon chip, after above-mentioned identical cleaning, immerse rapidly in the trimethoxy undecyl solution of silane, under the room temperature in nitrogen gas stream standing over night (15-20h).Take out silicon chip, it is immersed in the methylene dichloride, then jog in a large amount of Virahols.Use chloroform, ethanol drip washing afterwards successively, the nitrogen gas stream drying obtains the hydride modified silicon chip of undecyl (in contrast).
With protein be made into 1-5 μ M phosphate buffer solution (EDTA that contains 1mM, PH=7.8-8.0).The silicon chip of above-mentioned fresh processing is immersed, leave standstill 4-5h under the room temperature.Take out silicon chip,, use phosphate buffer solution and deionized water drip washing repeatedly its KCl solution that immerses 10mM, dry in the nitrogen gas stream.
Measure the adsorbent layer thickness δ of protein on the silicon chip of modifying through mono methoxy polyethylene glycol-800 silane derivative 4 of embodiment 4 preparations.The δ of the silicon chip correspondence after relatively the different concns derivative is handled, its result as shown in Figure 1.
Measure protein at the adsorbent layer thickness δ on the hydride modified silicon chip of undecyl.The δ of the silicon chip correspondence after the comparison different concns undecyl silane treatment, its result as shown in Figure 2.
Compare with the silicon chip that undecyl is hydride modified, the silicon chip of modifying through mono methoxy polyethylene glycol-800 silane derivative 4 of embodiment 4 preparations can suppress this three kinds of absorption of proteins better.When derivatives concentration is 10%, very obvious to three kinds of absorption of proteins restraining effect.Because the size and the shape of these three kinds of protein moleculars have contained most of proteinic scope, therefore can think that derivative all has tangible absorption restraining effect to most protein.
Claims (8)
1, a kind of mono methoxy polyethylene glycol silane derivative of representing by following structural formula I,
(R
1O)
zR
2 (3-z)Si (CH
2)
nA (CH
2CH
2O)
mCH
3(structural formula I)
Wherein, R
1, R
2The straight chained alkyl of 1～4 carbon atom of independent separately expression;
A is Sauerstoffatom or sulphur atom;
Z is 1,2 or 3;
N is the integer between 1 to 12;
M is the integer between 1 to 50.
2, mono methoxy polyethylene glycol silane derivative as claimed in claim 1 is characterized in that, described n is the integer between 3 to 10.
3, mono methoxy polyethylene glycol silane derivative as claimed in claim 1 is characterized in that, described m is the integer between 1 to 18.
4, the preparation method of the described mono methoxy polyethylene glycol silane derivative of a kind of claim 1, it is with the terminal asymmetric functionalization of peg molecule, comprises the steps:
1) terminal hydroxyl of mono methoxy polyethylene glycol carries out functional group's conversion: react by reaction formula 1, bathe under the cooling at cryosel, mono methoxy polyethylene glycol molecule and organic amine are dissolved in the methylene dichloride, add Tosyl chloride again, the mono methoxy polyethylene glycol molecule that adds: organic amine: the mol ratio of Tosyl chloride is 10: 10～15: 10～15, then mixed solution was at room temperature reacted 20 hours at least, remove insolubles, after the mixed solution that obtains concentrated, with 1: 1 sherwood oil of volume ratio: ethyl acetate is an eluent, silica gel column chromatography separates, and obtains the mono methoxy polyethylene glycol p-toluenesulfonic esters TsO (CH shown in the structural formula II
2CH
2O)
mCH
3Described organic amine is pyridine or triethylamine;
(structural formula II)
Wherein, m is the integer between 1 to 50;
2) with the organoalkoxysilane reaction: react by reaction formula 2, alkoxysilane compound containing trialkylsilyl group in molecular structure (R with structural formula II I
1O)
zR
2 (3-z)Si (CH
2)
nAH and sodium alkoxide back flow reaction 3 hours in the alcoholic solvent of correspondence is cooled to room temperature, with aprotic solvent dissolving step 1) after the mono methoxy polyethylene glycol p-toluenesulfonic esters that obtains, join in the reaction system room temperature reaction two days; Described alkoxysilane compound containing trialkylsilyl group in molecular structure: sodium alkoxide: the mol ratio of mono methoxy polyethylene glycol p-toluenesulfonic esters is 10～13: 10～13: 10; Described aprotic solvent is tetrahydrofuran (THF) or N, dinethylformamide; Remove by filter insolubles, the mixed solution that obtains is concentrated, with 1: 1 sherwood oil of volume ratio: ethyl acetate is an eluent, and silica gel column chromatography separates, and obtains the mono methoxy polyethylene glycol silane derivative shown in the structural formula I as claimed in claim 1;
(structural formula II) (structural formula II I) (structural formula I)
Wherein, in the organoalkoxysilane shown in the structural formula II I, R
1, R
2The straight chained alkyl of 1～4 carbon atom of independent separately expression;
A is Sauerstoffatom or sulphur atom;
Z is 1,2 or 3;
N is the integer between 1 to 12.
5, the preparation method of mono methoxy polyethylene glycol silane derivative as claimed in claim 4 is characterized in that, m is the integer between 1 to 18 in the described step 1).
6, the preparation method of mono methoxy polyethylene glycol silane derivative as claimed in claim 4 is characterized in that, described step 2) in A be sulphur atom.
7, the preparation method of mono methoxy polyethylene glycol silane derivative as claimed in claim 4 is characterized in that, described step 2) in n be integer between 3 to 10.
8, the described mono methoxy polyethylene glycol silane derivative of a kind of claim 1 is as the purposes of absorption inhibitor.
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|---|---|---|---|
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410009027 CN1281611C (en) | 2004-04-19 | 2004-04-19 | Mono-methoxy polyethylene glycol derivatives and their preparing process and use |
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|---|---|
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| CN1281611C true CN1281611C (en) | 2006-10-25 |
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| KR100668045B1 (en) * | 2005-08-17 | 2007-01-16 | 한국과학기술연구원 | omega;-[2-(POLYALKYLENEOXY)ETHYLTHIO]ALKYLALKOXYSILANES AND THEIR PREPARATION METHODS |
| JP5910530B2 (en) * | 2013-02-15 | 2016-04-27 | 信越化学工業株式会社 | Method for producing hydrophilic treatment substrate |
| WO2019049734A1 (en) * | 2017-09-11 | 2019-03-14 | 日油株式会社 | Novel poly(ethylene glycol) derivative and protein-adsorption inhibitor |
| CN114524943B (en) * | 2022-04-22 | 2022-09-16 | 天津凯莱英制药有限公司 | Process for preparing polyethylene glycol-glycerol derivatives and intermediates thereof |
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