CN106158197A - A kind of phenylboric acid functional magnetic nano-particle with blocking group and its preparation method and application - Google Patents
A kind of phenylboric acid functional magnetic nano-particle with blocking group and its preparation method and application Download PDFInfo
- Publication number
- CN106158197A CN106158197A CN201510209285.4A CN201510209285A CN106158197A CN 106158197 A CN106158197 A CN 106158197A CN 201510209285 A CN201510209285 A CN 201510209285A CN 106158197 A CN106158197 A CN 106158197A
- Authority
- CN
- China
- Prior art keywords
- blocking group
- magnetic
- group
- particle
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of phenylboric acid functional magnetic nano-particle with blocking group, and its preparation method and application.The described phenylboric acid functional magnetic nano-particle with blocking group includes that surface is modified with the magnetic nanoparticle doped with silicon dioxide of active function groups and the phenylboronic acid derivant modified on its surface and the end protection molecule with hydroxyl.Described surface is modified with the phenylboric acid functional magnetic nano-particle of blocking group can specific adsorption to glucide; the non-specific adsorption of other chaff interferences can be eliminated; effectively remove the nonspecific interference thing such as albumen therein and polypeptide, rapid sensitive low-abundance saccharide sample is analyzed.
Description
Technical field
The present invention relates to phenylboric acid functional magnetic nano-particle with blocking group and preparation method thereof,
And the described phenylboric acid functional magnetic nano-particle with blocking group is at specific adsorption saccharide thing
Application in matter, the especially application in the purity analysis method of glucide.
Background technology
Glycosylation is one of most common and most important post translational modification process in eukaryotic cell, at organism
The performance of various functions plays important role.Increasing evidence shows, protein glycosylation
And correct performance of the function of the unconventionality expression of glucide and various diseases and protein has closely
Contact, such as inflammation, immunological diseases, tumor and metabolism syndrome etc..Additionally, glucose is with poly-
Saccharide compound is also the important energy source of human and animal.Therefore, the analysis to glucide is
Very important, but it is full of challenge, because the analysis of glucide relates to a series of loaded down with trivial details and complicated
Biochemical steps.The separation method of traditional saccharide is mainly affinity chromatograph, and this method not only separated
Journey is complicated, is the most also easy to lose sample, therefore, the affinity chromatograph analysis to low abundance saccharide sample
There is certain limitation.
At present, magnetic nano-particle is big because of its specific surface area, is easily isolated and waits spy under additional magnetic field condition
Point, be widely used in biological sample isolated and purified in.But due to glucide is general and albumen or
Polypeptides matter is also deposited, and in the purge process to pure glucide, albumen or polypeptide can be to a great extent
The purity analysis of the pure glucide of upper impact and research.Therefore, existing method still can not be quick, sensitive
Ground saccharide sample pure to low abundance is effectively analyzed.In order to analyze and be enriched with pure glucide, we
Need the nonspecific interference things such as the polypeptide and the albumen that contain in removing sample as much as possible.
Summary of the invention
It is an object of the invention to be to overcome drawbacks described above, it is provided that one can remove largely
The nonspecific interference things such as the polypeptide contained in glucide sample and albumen, and can be enzyme rapidly and sensitively
The phenylboric acid functional magnetic with blocking group that saccharide sample pure to low abundance is effectively analyzed is received
Rice grain and preparation method thereof, and the described phenylboric acid functional magnetic nano-particle with blocking group
Application in specific adsorption glucide, especially answering in the purity analysis method of glucide
With.
First aspect, the invention provides a kind of phenylboric acid functional magnetic nanometer with blocking group
Grain, wherein, the described phenylboric acid functional magnetic nano-particle with blocking group includes magnetic Nano
Grain and the phenylboric acid functional group modified on its surface and blocking group；
Wherein, described magnetic nanoparticle is the magnetic doped with silicon dioxide that surface is modified with active group
Property nano-particle；
Described blocking group is the end protection molecule with hydroxyl.
Second aspect, the invention provides and a kind of prepare the phenylboric acid functional magnetic with blocking group and receive
The method of rice grain, wherein, the method includes:
(1) contact magnetic nanoparticle with tetraethyl orthosilicate to obtain and receive doped with the magnetic of silicon dioxide
Rice grain；
(2) the described magnetic nanoparticle doped with silicon dioxide is even with the silane with active group
Connection agent contact obtains surface and is modified with the magnetic nanoparticle doped with silicon dioxide of active group；
(3) described surface is modified with the magnetic nanoparticle doped with silicon dioxide of active group with
Phenylboronic acid derivant contacts with blocking group, it is thus achieved that the phenylboric acid functional magnetic with blocking group is received
Rice grain；Wherein, described blocking group is the end protection molecule with hydroxyl.
The third aspect, the invention provides the phenylboric acid functional magnetic as above with blocking group
Phenylboric acid functional magnetic nanometer with blocking group prepared by nano-particle or method as above
Granule application in specific adsorption glucide.
Fourth aspect, the invention provides a kind of purity analysis method of glucide, wherein, the method
Including: magnetic nanoparticle is contacted with testing sample material after acquisition contacts, and uses mass spectrometric analysis method
Dock material after touch to be analyzed；
Wherein, containing glucide in described testing sample；Described magnetic nanoparticle is as above
With the phenylboric acid functional magnetic nano-particle of blocking group or method as above prepare with
The phenylboric acid functional magnetic nano-particle of blocking group.
The phenylboric acid functional magnetic nano-particle with blocking group that the present invention provides can be to saccharide
Material carries out specific binding, effectively removes the nonspecific interference thing such as albumen therein and polypeptide, quickly
Sensitive is analyzed low-abundance glucide sample.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1: B-H loop, wherein, curve a is SPIO magnetic prepared by preparation example
The B-H loop of property nano-particle；Curve b is the phenylboric acid merit with blocking group of embodiment 1 preparation
The B-H loop of magnetic nanoparticle can be changed.
The phenylboric acid functional magnetic nano-particle with blocking group of Fig. 2: embodiment 1 preparation is to chicken
The purity analysis mass spectrum of N sugar chain in oralbumin.
The phenylboric acid functional magnetic nano-particle pair without blocking group of Fig. 3: comparative example 1 preparation
The purity analysis mass spectrum of N sugar chain in chicken ovalbumin.
The phenylboric acid functional magnetic nano-particle of the band blocking group of Fig. 4: embodiment 1 preparation is to human milk
In the purity analysis mass spectrum of free oligosaccharide.Wherein, the embedded figure of Fig. 4 be Fig. 5 from charge-mass ratio 400 to
The partial enlargement of 1800.
The phenylboric acid functionalization superparamagnetic nano particle without blocking group of Fig. 5: comparative example 1 preparation
Purity analysis mass spectrum to oligosaccharide free in human milk.
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.Should be appreciated that herein
Described detailed description of the invention is merely to illustrate and explains the present invention, is not limited to the present invention.
First aspect, the invention provides a kind of phenylboric acid functional magnetic nanometer with blocking group
Grain, wherein, the described phenylboric acid functional magnetic nano-particle with blocking group includes magnetic Nano
Grain and the phenylboric acid functional group modified on its surface and blocking group；
Wherein, described magnetic nanoparticle is the magnetic doped with silicon dioxide that surface is modified with active group
Property nano-particle；
Described blocking group is the end protection molecule with hydroxyl.
In the present invention, described magnetic nanoparticle is preferably SPIO magnetic nanoparticle.
In the present invention, described phenylboric acid functional group is provided by phenylboronic acid derivant, described phenylboronic acid
Derivant can select in wider scope, for example, it is possible to for active can the benzene boron of modification group
Acid, it is preferred that described band active can the phenylboric acid of modification group selected from Carboxybenzeneboronic acid, aminobenzene boron
One or more in acid or mercaptophenyl boronic acid, can the benzene of modification group it is furthermore preferred that described band is active
Boric acid is selected from 2-aminobenzene boric acid, 2-Carboxybenzeneboronic acid, 3-mercaptophenyl boronic acid, 3-aminobenzene boric acid, 3-
Hydroxy benzenes boric acid, 3-Carboxybenzeneboronic acid, 4-mercaptophenyl boronic acid, 4-aminobenzene boric acid, 4-hydroxy benzenes boric acid,
One or more in 4-Carboxybenzeneboronic acid and 4-(trans-2-carboxy vinyl) phenylboric acid.
In the present invention, described end can select with the protection molecule of hydroxyl in wider scope,
Be preferably, with the hydrophilic chain molecule of hydroxyl, such as, with can the Polyethylene Glycol of modification activities group,
2-(2-amino ethoxy) ethanol, 2-(2-methoxy ethoxy) ethyl mercaptan, 2-[2-(2-amino ethoxy)
Ethyoxyl] ethanol, 3-[2-(2-hydroxy ethoxy) ethyoxyl] propanoic acid, 2-(2-methoxy ethoxy) ethyl mercaptan,
1-amino-3,6,9-tri--11-undecyl alcohols, 1-sulfydryl-3,6,9-tri--11-undecyl alcohols and 2-[2-(3-aminopropan
Epoxide) ethyoxyl] one or more in ethanol.Wherein, described Polyethylene Glycol is preferably the poly-second of short chain two
Alcohol, described short chain polyalkylene glycol refers to the Polyethylene Glycol being polymerized by 2-5 glycol molecule.
According to the present invention, although being modified with phenylboric acid functional group and protection on the surface of magnetic nanoparticle
Group i.e. can realize the purpose of the present invention, but it was found by the inventors of the present invention that when magnetic nanoparticle table
When phenylboric acid functional group that face is modified and the scope that mol ratio is 1:1-3 of blocking group, it is possible to enter one
Step realizes the purpose of the present invention.
Second aspect, present invention also offers a kind of phenylboric acid functional magnetic nanometer with blocking group
The preparation method of granule, wherein, the method includes:
(1) contact magnetic nanoparticle with tetraethyl orthosilicate to obtain and receive doped with the magnetic of silicon dioxide
Rice grain；
(2) the described magnetic nanoparticle doped with silicon dioxide is even with the silane with active group
Connection agent contact obtains surface and is modified with the magnetic nanoparticle doped with silicon dioxide of active group；
(3) described surface is modified with the magnetic nanoparticle doped with silicon dioxide of active group with
Phenylboronic acid derivant contacts with blocking group, it is thus achieved that the phenylboric acid functional magnetic with blocking group is received
Rice grain；Wherein, described blocking group is the end protection molecule with hydroxyl.
According to the present invention, described magnetic nanoparticle, phenylboronic acid derivant and end are with the guarantor of hydroxyl
The selection protecting molecule is referred to category as enumerated above, but is not limited to this, and this is the most detailed again for the present invention
Carefully repeat.
Following exemplary method as above is discussed in detail, but the present invention is not limited thereto, in this area
In the cognitive range of technical staff, it is possible to carry out equivalent modifications and realize the preparation method of identical purpose and all exist
In protection scope of the present invention.
According to the present invention, in step (1), described magnetic nanoparticle contacts with tetraethyl orthosilicate
Can be carried out by following steps:
Magnetic nanoparticle is suspended in ethanol acquisition alcohol suspension 1, then by described ethanol suspension
Liquid 1 contacts with ammonia, water and tetraethyl orthosilicate, it is thus achieved that doped with the magnetic nanoparticle of silicon dioxide；
Wherein, relative to the described magnetic nanoparticle of 100mg, the consumption of described ethanol is 30-50ml,
The consumption of described ammonia is 3-5ml, and the consumption of described water is 3-5ml, the consumption of described tetraethyl orthosilicate
For 0.04-0.06mL.
In step (2), the described magnetic nanoparticle doped with silicon dioxide with active group
The contact of silane coupler can be carried out by following steps:
The described magnetic nanoparticle doped with silicon dioxide is suspended in ethanol acquisition alcohol suspension 2
(wherein, the magnetic nanoparticle raw material relative to 100mg, the consumption of ethanol can be 20-30mL),
Then, by described alcohol suspension 2, silane coupler with ammonia with active group connects successively
Touch, it is thus achieved that surface is modified with the magnetic nanoparticle doped with silicon dioxide of active group；Wherein, phase
For the described alcohol suspension 2 of 1ml, the consumption of described ammonia is 0.04-0.06ml, with active group
The consumption of the silane coupler of group is 0.001-0.002mL.
Wherein, what described active group can be known in the art can modify on silane coupler and repair
Can have the group of targeted activity after decorations, such as, described active group can be selected from amino, carboxyl,
Hydroxyl and sulfydryl one or more.Based on this, the described silane coupler with active group is preferably selected from
3-aminopropyl triethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl trimethoxysilane,
3-(2-aminoethylamino) propyl trimethoxy silicane one or more.
In step (3), illustrate described as a example by (2-amino ethoxy) ethanol as 2-with blocking group
Surface is modified with the magnetic nanoparticle doped with silicon dioxide and the phenylboronic acid derivant of active group
Contact with blocking group:
The magnetic nanoparticle doped with silicon dioxide that described surface is modified with active group is suspended in
Dimethyl formamide solution obtains suspension 3, by described suspension 3 and 2-(7-azo benzo three nitrogen
File)-N, N, N ', N '-tetramethylurea hexafluoro sulfuric ester (HATU), phenylboronic acid derivant and N, N '-two
Wopropyl ethyl amine (DIEA) contact obtains mixture 1, and described mixture 1 contacts acquisition with malonic acid
Mixture 2, more described mixture 2 is contacted with blocking group the described magnetic nanoparticle of acquisition；Institute
Stating in suspension 3, described surface is modified with the magnetic nanoparticle doped with silicon dioxide of active group
Concentration be 4-6mg/mL weight %, relative to suspension described in 3ml 3, described 2-(7-diphenyl diimide
And three nitrogen file)-N, N, N ', the consumption of N '-tetramethylurea hexafluoro sulfuric ester is 0.2-0.3mmol, described benzene
The consumption of boric acid analog derivative is 1-3mmol, and the consumption of described N, N '-diisopropylethylamine is 4-6
Mmol, the consumption of described malonic acid is 21-3mmol, and the amount of described blocking group is 1-3mmol.
Wherein, the consumption of described phenylboronic acid derivant and blocking group enable to preparation described with
The phenylboric acid functional group of the phenylboric acid functional magnetic nano grain surface of blocking group and blocking group
Ratio can be 1:1-3.
The third aspect, the invention provides the phenylboric acid functional magnetic as above with blocking group
Phenylboric acid functional magnetic nanometer with blocking group prepared by nano-particle or method as above
Granule application in specific adsorption glucide.
Based on use above, fourth aspect, the invention provides a kind of purity analysis method of glucide,
Wherein, the method includes: magnetic nanoparticle contacts with testing sample material after acquisition contact, and uses
Mass spectrometric analysis method docks material after touch and is analyzed；Wherein, containing glucide in described testing sample；
Described magnetic nanoparticle is the phenylboric acid functional magnetic nanometer with blocking group as above
Phenylboric acid functional magnetic nano-particle with blocking group prepared by grain or method as above.
Described purity analysis method can be carried out by following steps: (1) is by the benzene boron with blocking group
Acid functionalization magnetic nanoparticle solution obtains described with blocking group in the alkaline buffer of pH 8-9
The dispersion soln of phenylboric acid functional magnetic nano-particle, be called for short dispersion soln A, relative to 1mg
Described dispersion soln A, the consumption of described alkaline buffer is 100 μ L；(2) by described dispersion soln
A contacts material after acquisition contact with testing sample；(3) connect described in the alkaline buffer flushing of pH 8-9
Material 4-5 time after touch；(4) with tri-distilled water by material suspended acquisition suspension after the contact through rinsing,
Relative to phenylboric acid functional magnetic nano-particle with blocking group described in 1mg, described tri-distilled water
Consumption be 10 μ L；(5) suspension described in 1 μ L and the 2,5-dihydroxy benzenes first of 1 μ L 0.13M are taken
Acid mixing obtains detection liquid；(6) described detection liquid is carried out mass spectral analysis.
Wherein, described alkaline buffer is the ammonia spirit of pH 8-9, ammonium hydrogen carbonate, sodium hydroxide,
One in the aqueous solutions such as potassium hydroxide.
Wherein, glucide has implication well known in the art.Typically, glucide is to polyhydroxy
Aldehyde or polyhydroxyketone and condensation polymer thereof and the general name of some derivant, typically by carbon, hydrogen and three kinds of elements of oxygen
Formed, blazoned nature.
Mass spectrum used in the present invention is Matrix Assisted Laser Desorption ionization time of flight mass spectrometry, this instrument
There is high sensitivity, it is easy to operation, can high-throughout analysis trace biological sample.B-H loop is logical
Cross property tester at a temperature of 300K from-20000Oe to 20000Oe with blocking group
The magnetic parameter test data of phenylboric acid functional magnetic nano-particle.
Present invention also offers SPIO magnetic nanoparticle, wherein, the method includes
Following steps: Iron dichloride tetrahydrate and ferric chloride hexahydrate are dissolved in hydrochloric acid by (1), then carry out play
Strong stirring, after it is dissolved completely in hydrochloric acid, is added dropwise over ammonia spirit in reaction system, continues
Stirring 20-40min, obtains SPIO magnetic nanoparticle.In whipping process,
In reaction system, constantly it is passed through nitrogen, prevents the SPIO magnetic nanoparticle prepared
Oxidized.
Below in conjunction with embodiment, embodiment of the present invention are described in detail.
Experimental technique in following embodiment, if no special instructions, is conventional method；Experiment used
Material, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Further describe the present invention by the following examples.
Preparation example 1
The preparation of SPIO magnetic nanoparticle
In 250mL there-necked flask, add the hydrochloric acid solution of 25mL 2M, then 2g tetra-is hydrated chlorine
Change ferrous (FeCl2·4H2And 5.4g ferric chloride hexahydrate (FeCl O)3·6H2O) biased sample adds
Enter in hydrochloric acid, and be passed through nitrogen and protect.Reaction system is stirred vigorously at ambient temperature, treats
FeCl2·4H2O and FeCl3·6H2After O is completely dissolved, in reaction system, it is added dropwise over 30mL ammonia
Solution (28～30 weight %), after dropping, continues to be stirred vigorously reaction system at ambient temperature
30 minutes, obtain SPIO magnetic nanoparticle.Prepared superparamagnetism four is aoxidized
Three ferromagnetic nanoparticle 50mL tri-distilled water washs three times, is finally saved into the degassing of 50mL
Tri-distilled water in, concentration is set to 40mg/mL.
Comparative example 1
Preparation without the phenylboric acid magnetic nanoparticle of blocking group
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, removes undoped p two
The SPIO magnetic nanoparticle of silicon oxide.Finally gained granule is suspended from 50mL second
In alcohol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-aminopropyl triethoxysilane (3-aminopropyl) of 1mL ammonia spirit and 0.03mL
Triethoxysilane, APS), under room temperature condition, stir 24h, magnetic particle surface is by sulfhydrylation.Will
The tri-distilled water of the amidized magnetic nanoparticle 30mL of gained washs three times, removes undoped p dioxy
The magnetic nanoparticle of SiClx.Finally gained granule is suspended from 30mL dimethylformamide (Dimethyl
Formamide, DMF) in.
(3) taking the magnetic particle of 3mL surface amination, ultrasonic 30min makes it fully dispersed.To
Reaction system successively adds the DMF solution (0.5M) of 5mL HATU, 2.5mmol 4-carboxyl benzene
Boric acid and 5mmol DIEA.24h reaction is stirred under the conditions of 4 DEG C.After completion of the reaction, by obtained
Without blocking group 4-Carboxybenzeneboronic acid functional magnetic particle with 5mL tri-distilled water wash 5 times,
Its concentration is set to 1.0mg/mL.
According to the selection of following phenylboric acid and blocking group, embodiment is set
| Embodiment | Phenylboric acid | Blocking group |
| 1 | 4-Carboxybenzeneboronic acid | 2-(2-amino ethoxy) ethanol |
| 2 | 4-mercaptophenyl boronic acid | 2-(2-methoxy ethoxy) ethyl mercaptan |
| 3 | 3-Carboxybenzeneboronic acid | 3-[2-(2-hydroxy ethoxy) ethyoxyl] propanoic acid |
| 4 | 3-Carboxybenzeneboronic acid | 1-amino-3,6,9-three-11-undecyl alcohol |
| 5 | 4-mercaptophenyl boronic acid | 1-sulfydryl-3,6,9-three-11-undecyl alcohol |
| 6 | 4-aminobenzene boric acid | 1-amino-3,6,9-three-11-undecyl alcohol |
Embodiment 1
Phenylboric acid functional magnetic nano-particle with blocking group (2-(2-amino ethoxy) ethanol)
Preparation
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, remove not with magnetic
The material of Fe2O3 doping.Finally gained granule is suspended from 50mL ethanol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-aminopropyl triethoxysilane (3-aminopropyl) of 1mL ammonia spirit and 0.03mL
Triethoxysilane, APS), under room temperature condition, stir 24h, magnetic particle surface is by amination.Will
The tri-distilled water of the amidized magnetic nanoparticle 30mL of gained washs three times, removes and does not reacts
Material.Finally gained granule is suspended from 30mL dimethylformamide (Dimethyl Formamide,
DMF) in.
(3) taking the magnetic particle of 3mL surface amination, ultrasonic 30min makes it fully dispersed.To
Reaction system successively adds the DMF solution (0.5M) of 5mL HATU, 1.25mmol 4-carboxyl
Phenylboric acid and 5mmol DIEA.After being stirred vigorously 0.5h under room temperature, then in reaction system, add 1.25
Mmol malonic acid, stirs 24h reaction under the conditions of 4 DEG C.Then in reaction system, add 1.25
The DMF solution of mmol 2-(2-amino ethoxy) ethanol, continues 4 DEG C and is stirred vigorously 24h.React
Bi Hou, by the phenylboric acid functional magnetic grain of obtained band 2-(2-amino ethoxy) Alcohol Protection group
Son 5mL tri-distilled water washs 5 times, washes away the unmodified material to Armco magnetic iron, its concentration is arranged
For 1.0mg/mL.
Embodiment 2
Phenylboric acid functional magnetic nanometer with blocking group (2-(2-methoxy ethoxy) ethyl mercaptan)
The preparation of granule
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, remove not with magnetic
The material of Fe2O3 doping.Finally gained granule is suspended from 50mL ethanol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-mercaptopropyltriethoxysilane of 1mL ammonia spirit and 0.03mL
(3-Mercaptopropyltriethoxysilane, MPS), stirs 24h, magnetic grain under room temperature condition
Sub-surface is by sulfhydrylation.The tri-distilled water of the magnetic nanoparticle 30mL of the sulfhydrylation of gained is washed three
Secondary, remove the material not reacted.Finally gained granule is suspended from 30mL dimethylformamide
In (Dimethyl Formamide, DMF).
(3) taking the magnetic particle of 3mL surface sulfhydrylation, ultrasonic 30min makes it fully dispersed.To
Reaction system adds 1.0mmol 4-mercaptophenyl boronic acid.In the case of stirring, drip in reaction system
Add bromine water as oxidant, until reaction system does not has hydrogen bromide gas to release, continue at stirring at normal temperature
4h.Then in reaction system, add 1.5mmol 2-(2-methoxy ethoxy) ethyl mercaptan, continue dropping
Bromine water aoxidizes, until releasing without hydrogen bromide gas.After completion of the reaction, by obtained with 2-(2-
Methoxy ethoxy) ethyl mercaptan blocking group phenylboric acid functional magnetic particle with 5mL tri-distilled water wash
5 times, wash away the unmodified material to Armco magnetic iron, its concentration is set to 1.0mg/mL.
Embodiment 3
Phenylboric acid functional magnetic with blocking group (3-[2-(2-hydroxy ethoxy) ethyoxyl] propanoic acid) is received
The preparation of rice grain
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, removes and does not occurs instead
The material answered.Finally gained granule is suspended from 50mL ethanol.
2) the SPIO magnetic doped with silicon dioxide that 20mL step (1) obtains is taken
Property nanoparticles solution, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over 1mL
3-aminopropyl triethoxysilane (3-aminopropyl) triethoxysilane of ammonia spirit and 0.03mL,
APS), stirring 24h under room temperature condition, magnetic particle surface is by amination.By the amination of gained
Magnetic nanoparticle 30mL tri-distilled water wash three times, remove undoped silicon dioxide magnetic receive
Rice grain.Finally gained granule is suspended from 30mL dimethylformamide (Dimethyl Formamide,
DMF) in.
(3) taking the magnetic particle of 3mL surface amination, ultrasonic 30min makes it fully dispersed.To
The DMF solution (0.5M) of priority addition 5mL HATU in reaction system, 1.5mmol 3-carboxyl-
Phenylboric acid, 3-[2-(2-hydroxy ethoxy) ethyoxyl] propanoic acid of 1mmol and the DIEA of 5mmol, then
In 4 DEG C of stirring 24h reactions.After completion of the reaction, by obtained band 3-[2-(2-hydroxy ethoxy) ethyoxyl]
The phenylboric acid functional magnetic particle of propanoic acid blocking group 5mL tri-distilled water washs 5 times, washes away and does not repaiies
Adorn the material on Armco magnetic iron, its concentration is set to 1.0mg/mL.
Embodiment 4
Phenylboric acid functional magnetic nanometer with blocking group (1-amino-3,6,9-three-11-undecyl alcohol)
The preparation of granule
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, remove not with magnetic
The material of Fe2O3 doping.Finally gained granule is suspended from 50mL ethanol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-aminopropyl triethoxysilane (3-aminopropyl) of 1mL ammonia spirit and 0.03mL
Triethoxysilane, APS), under room temperature condition, stir 24h, magnetic particle surface is by amination.Will
The tri-distilled water of the amidized magnetic nanoparticle 30mL of gained washs three times, removes and does not reacts
Material.Finally gained granule is suspended from 30mL dimethylformamide (Dimethyl Formamide,
DMF) in.
(3) taking the magnetic particle of 3mL surface amination, ultrasonic 30min makes it fully dispersed.To
The DMF solution (0.5M) of priority addition 5mL HATU in reaction system, 1.0mmol 3-carboxyl-
Phenylboric acid and 5mmol DIEA.After being stirred vigorously 0.5h under room temperature, in reaction system, add 1.5
Mmol malonic acid, stirs 24h reaction under the conditions of 4 DEG C.Then in reaction system, add 1.5mmol
1-amino-3, the DMF solution of 6,9-tri--11-undecyl alcohols, continues 4 DEG C and is stirred vigorously 24h.React
Bi Hou, by obtained band 1-amino-3, the phenylboric acid functionalization of 6,9-tri--11-undecyl alcohol blocking groups
Magnetic particle 5mL tri-distilled water washs 5 times, washes away the unmodified material to Armco magnetic iron, and it is dense
Degree is set to 1.0mg/mL.
Embodiment 5
Phenylboric acid functional magnetic nanometer with blocking group (1-sulfydryl-3,6,9-three-11-undecyl alcohol)
The preparation of granule
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, remove not with magnetic
The material of Fe2O3 doping.Finally gained granule is suspended from 50mL ethanol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-mercaptopropyltriethoxysilane of 1mL ammonia spirit and 0.03mL
(3-Mercaptopropyltriethoxysilane, MPS), stirs 24h, magnetic grain under room temperature condition
Sub-surface is by sulfhydrylation.The tri-distilled water of the magnetic nanoparticle 30mL of the sulfhydrylation of gained is washed three
Secondary, remove the material not reacted.Finally gained granule is suspended from 30mL dimethylformamide
In (Dimethyl Formamide, DMF).
(3) taking the magnetic particle of 3mL surface sulfhydrylation, ultrasonic 30min makes it fully dispersed.To
Reaction system adds the 1-sulfydryl-3,6,9-three-11-undecyl alcohol of 1mmol.In the case of stirring,
In reaction system, dropping bromine water is as oxidant, until reaction system does not has hydrogen bromide gas to release,
Continue at stirring at normal temperature 4h.The 4-mercaptophenyl boronic acid of 1.5mmol is added the most again in reaction system,
And continue in reaction system, drip bromine water and aoxidize, until do not have hydrogen bromide to release.After completion of the reaction,
By the obtained phenylboric acid functional magnetic with 1-sulfydryl-3,6,9-three-11-undecyl alcohol blocking group
Particle 5mL tri-distilled water washs 5 times, washes away the unmodified material to Armco magnetic iron, its concentration is set
It is set to 1.0mg/mL.
Embodiment 6
Preparation with the phenylboric acid functional magnetic nano-particle of blocking group
(1) the SPIO magnetic particle solution of 5mL preparation example gained is resuspended in
The ethanol of 80mL, is placed in 250mL there-necked flask, ultrasonic 10 minutes so that it is be completely dispersed.So
After wherein will successively add the ammonia spirit of 8mL, the tri-distilled water of 7.5mL and the positive silicic acid of 0.1mL
Ethyl ester (tetraethyl orthosilicate, TEOS), is stirred vigorously 4h in 40 DEG C, obtains doped with two
The SPIO magnetic nanoparticle of silicon oxide.By the surpassing doped with silicon dioxide of gained
The tri-distilled water of paramagnetism ferroferric oxide magnetic nanoparticle 50mL washs three times, remove not with magnetic
The material of Fe2O3 doping.Finally gained granule is suspended from 50mL ethanol.
(2) SPIO doped with silicon dioxide that 20mL step (1) obtains is taken
Solution of magnetic nanoparticles, is placed in 100mL there-necked flask, ultrasonic 30min, is then added dropwise over
The 3-aminopropyl triethoxysilane (3-aminopropyl) of 1mL ammonia spirit and 0.03mL
Triethoxysilane, APS), under room temperature condition, stir 24h, magnetic particle surface is by amination.Will
The tri-distilled water of the amidized magnetic nanoparticle 30mL of gained washs three times, removes and does not reacts
Material.Finally gained granule is suspended from 30mL dimethylformamide (Dimethyl Formamide,
DMF) in.
(3) taking the magnetic particle of 3mL surface amination, ultrasonic 30min makes it fully dispersed.To
Reaction system successively adds the DMF solution (0.5M) of 10mL HATU, 2.5mmol malonic acid
With 10mmol DIEA.After being stirred vigorously 4h at 4 DEG C, in reaction system, add 1.5mmol 4-ammonia
Base phenylboric acid and 1.0mmol 1-amino-3,6,9-tri--11-undecyl alcohols, stir 24h under the conditions of 4 DEG C
Reaction.After completion of the reaction, by obtained band 1-amino-3,6,9-tri--11-undecyl alcohol blocking groups
Phenylboric acid functional magnetic particle 5mL tri-distilled water washs 5 times, washes away unmodified to Armco magnetic iron
Material, is set to 1.0mg/mL by its concentration.
Test case 1
By the property tester of Quantum Design company according to the method in its description, to system
Band prepared by the SPIO magnetic nanoparticle prepared for example and embodiment 1-6 is protected
The phenylboric acid functional magnetic nano-particle of group carries out B-H loop mensuration.Result shows, preparation example system
Standby ferroferric oxide magnetic nanoparticle has the strongest magnetic responsiveness, has superparamagnetism (figure simultaneously
1 curve a), embodiment 1 prepared phenylboric acid functionalization and the magnetic of 2-(2-amino ethoxy) Alcohol Protection
Property nano-particle, still there is more ferromagnetism, and keep superparamagnetism (Fig. 1 curve b) (embodiment 2-6
The prepared phenylboric acid functional magnetic nano-particle with blocking group carries out B-H loop and enforcement
Example 1 is similar to).The phenylboric acid functionalization prepared by result explanation of Fig. 1 and 2-(2-amino ethoxy) ethanol
The magnetic nanoparticle of protection has higher magnetic responsiveness, has superparamagnetism, for sharp separation simultaneously
Saccharide sample provides guarantee.
Test case 2
The magnetic nanoparticle that this test case provides for the present invention the is described N sugar to chicken ovalbumin
Chain is analyzed.
Take the phenylboric acid functionalization magnetic with blocking group prepared by 100mg (100 μ L) embodiment 1-6
Property nano-particle, is separated from the water out by Magnet, is then resuspended in 100 μ L pH's 8.5
In ammonia spirit, ultrasonic 10min so that it is fully dispersed.Then in described magnetic nanoparticle suspension
Add 10mg by the PNGase F enzymolysis (mark that enzyme solution provides with reference to New England Lab
Quasi-method perform) after chicken ovalbumin, room temperature concussion 30min.Then molten with the ammonia of pH 8.5
Magnetic nanoparticle is washed 4-5 time by liquid, washes away the albumen and polypeptide not identified in sample with it, by it
It is suspended from tri-distilled water, and takes out DHB (DHB) mixing of 1 μ L and 1 μ L, mixed
The sample of MALDI _ TOFMS instrument (MALDI-TOF) is directly dripped to after conjunction
On product plate, it is not necessary to adsorbed sugar chain is disintegrated down from magnetic nanoparticle, then carry out mass spectrum and divide
Analysis test.The phenylboric acid functional magnetic nano-particle result with blocking group of embodiment 1 preparation is such as
Shown in Fig. 2.The phenylboric acid functional magnetic nanometer with blocking group prepared by result explanation of Fig. 2
Granule can well be purified into N sugar chain, it is possible to is analyzed by Mass Spectrometer Method.Embodiment 2-6 is made
The standby phenylboric acid functional magnetic nano-particle with the blocking group N sugar chain to chicken ovalbumin
The result being analyzed is similar with embodiment 1.
Contrast test example 2
The phenylboric acid function without blocking group will prepared in comparative example 1 according to the method for test case 2
Change the magnetic nanoparticle detection analysis for the N sugar chain of chicken ovalbumin.Gained mass spectrum such as Fig. 3
Shown in.
Fig. 3 result explanation prepared by the magnetic nanoparticle without blocking group can not isolated and purified go out
The N sugar chain of chicken ovalbumin, it has the absorption of nonspecific proteins while absorption N sugar chain,
Have influence on the detection of glucide.
Test case 3
This test case is for illustrating that the oligonucleotide chain in human milk is carried out by the magnetic nanoparticle that the present invention provides
Analyze.
The phenylboric acid function with blocking group will prepared in embodiment 1-6 according to the method for test case 2
Change magnetic nanoparticle oligonucleotide chain in human milk and carry out enriching and purifying, and detect with mass spectrum, real
Execute the phenylboric acid functional magnetic nano-particle result with blocking group of example 1 preparation as shown in Figure 4.
Fig. 4 result explanation prepared by magnetic nanoparticle can well by isolated and purified for oligonucleotide chain in human milk,
And can be analyzed in conjunction with mass spectrum.The phenylboric acid function with blocking group prepared by embodiment 2-6
The result that oligonucleotide chain in human milk is analyzed by change magnetic nanoparticle is similar with embodiment 1.
Contrast test example 3
The phenylboric acid function without blocking group will prepared in embodiment 1 according to the method for test case 2
Change magnetic nanoparticle oligonucleotide chain in human milk and carry out enriching and purifying, and detect with mass spectrum, knot
Fruit is as shown in Figure 5.The magnetic nanoparticle without blocking group prepared by result explanation of Fig. 5 can
The oligosaccharide kind material that can not be effectively purified in human milk.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention,
In the case of reconcilable, can be combined by any suitable means.In order to avoid unnecessary
Repeating, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the phenylboric acid functional magnetic nano-particle with blocking group, it is characterised in that institute
State the phenylboric acid functional magnetic nano-particle with blocking group and include magnetic nanoparticle and at it
The phenylboric acid functional group of surface modification and blocking group；
Wherein, described magnetic nanoparticle is the magnetic doped with silicon dioxide that surface is modified with active group
Property nano-particle；
Described blocking group is the end protection molecule with hydroxyl.
2. the method preparing the phenylboric acid functional magnetic nano-particle with blocking group, it is special
Levying and be, the method includes:
(1) contact magnetic nanoparticle with tetraethyl orthosilicate to obtain and receive doped with the magnetic of silicon dioxide
Rice grain；
(2) the described magnetic nanoparticle doped with silicon dioxide is even with the silane with active group
Connection agent contact obtains surface and is modified with the magnetic nanoparticle doped with silicon dioxide of active group；
(3) described surface is modified with the magnetic nanoparticle doped with silicon dioxide of active group with
Phenylboronic acid derivant contacts with blocking group, it is thus achieved that the phenylboric acid functional magnetic with blocking group is received
Rice grain；Wherein, described blocking group is the end protection molecule with hydroxyl.
Method the most according to claim 2, wherein, in step (1), connects with tetraethyl orthosilicate
The described magnetic nanoparticle touched is SPIO magnetic nanoparticle.
Method the most according to claim 2, wherein, in step (2), described active group selects
One or more in amino, carboxyl, hydroxyl and sulfydryl；Preferably, described with active group
Silane coupler is selected from 3-aminopropyl triethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercapto propyl group
One or more in trimethoxy silane and 3-(2-aminoethylamino) propyl trimethoxy silicane.
Method the most according to claim 2, wherein, in step (3), described phenylboronic acid is spread out
Biological for active can the phenylboric acid of modification group, it is preferred that described band is active can modification group
One or more in Carboxybenzeneboronic acid, aminobenzene boric acid or mercaptophenyl boronic acid of phenylboric acid, more preferably
Choosing, described band active can the phenylboric acid of modification group selected from 2-aminobenzene boric acid, 2-Carboxybenzeneboronic acid,
3-mercaptophenyl boronic acid, 3-aminobenzene boric acid, 3-hydroxy benzenes boric acid, 3-Carboxybenzeneboronic acid, 4-mercaptophenyl boronic acid,
4-aminobenzene boric acid, 4-hydroxy benzenes boric acid, 4-Carboxybenzeneboronic acid and 4-(trans-2-carboxy vinyl) phenyl
One or more in boric acid；
Described end is the end hydrophilic chain molecule with hydroxyl with the protection molecule of hydroxyl, preferably selects
From with can the Polyethylene Glycol of modification activities group, 2-(2-amino ethoxy) ethanol, 2-(2-methoxyl group second
Epoxide) ethyl mercaptan, 2-[2-(2-amino ethoxy) ethyoxyl] ethanol, 3-[2-(2-hydroxy ethoxy) ethyoxyl]
Propanoic acid, 2-(2-methoxy ethoxy) ethyl mercaptan, 1-amino-3,6,9-tri--11-undecyl alcohols, 1-sulfydryl-3,6,9-
One or more in three-11-undecyl alcohols and 2-[2-(3-aminopropan epoxide) ethyoxyl] ethanol.
6. according to the method described in claim 2 or 5, wherein, in step (3), described benzene boron
The consumption of acid derivative and blocking group makes the described phenylboric acid function with blocking group of preparation
Change the phenylboric acid functional group on magnetic nanoparticle surface and the ratio of blocking group can be 1:1-3.
7. the phenylboric acid functional magnetic nano-particle with blocking group described in claim 1 or power
Profit requires in 2-6 the phenylboric acid functional magnetic with blocking group prepared by the method described in any one
Nano-particle application in specific adsorption glucide.
8. the purity analysis method of a glucide, it is characterised in that the method includes: by magnetic
Nano-particle contacts material after acquisition contact with testing sample, and docks material after touch with mass spectrometric analysis method
It is analyzed；
Wherein, containing glucide in described testing sample；Described magnetic nanoparticle is claim 1
In the described phenylboric acid functional magnetic nano-particle with blocking group or claim 2-6 any one
Phenylboric acid functional magnetic nano-particle with blocking group prepared by the method described in Xiang.
Method the most according to claim 8, wherein, the condition of described contact includes: temperature is
20-40 DEG C, pH value is 8-9, and the time is 20-40min；
Relative to the glucide of 1 μ g, the consumption of described magnetic nanoparticle is 20-100 μ g.
Method the most according to claim 8 or claim 9, wherein, described glucide be glycoprotein or
Person's sugar and the pure sugar chain in albumen or lipid mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510209285.4A CN106158197B (en) | 2015-04-28 | 2015-04-28 | A kind of phenyl boric acid functional magnetic nano particle and its preparation method and application with blocking group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510209285.4A CN106158197B (en) | 2015-04-28 | 2015-04-28 | A kind of phenyl boric acid functional magnetic nano particle and its preparation method and application with blocking group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106158197A true CN106158197A (en) | 2016-11-23 |
| CN106158197B CN106158197B (en) | 2019-03-08 |
Family
ID=57347671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510209285.4A Expired - Fee Related CN106158197B (en) | 2015-04-28 | 2015-04-28 | A kind of phenyl boric acid functional magnetic nano particle and its preparation method and application with blocking group |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106158197B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN108499601A (en) * | 2018-01-17 | 2018-09-07 | 天津大学 | A kind of boric acid modified silica solid-carrying type platinum catalyst and its preparation and application |
| CN109046275A (en) * | 2018-07-05 | 2018-12-21 | 华侨大学 | It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead |
| CN109966504A (en) * | 2019-02-26 | 2019-07-05 | 中国科学院化学研究所 | A kind of albumin nanoparticle and the preparation method and application thereof that cell quickly absorbs |
| CN113975855A (en) * | 2021-11-17 | 2022-01-28 | 浙江树人学院（浙江树人大学） | Phenolic compound molecularly imprinted nanoenzyme solid-phase extraction column based on aminophenylboronic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287721A1 (en) * | 2007-05-17 | 2008-11-20 | Chevron Phillips Chemical Company | Catalysts for olefin polymerization |
| CN101684005A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Nano magnetic material of surface modified boric acid base group, preparation method and application thereof |
-
2015
- 2015-04-28 CN CN201510209285.4A patent/CN106158197B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287721A1 (en) * | 2007-05-17 | 2008-11-20 | Chevron Phillips Chemical Company | Catalysts for olefin polymerization |
| CN101684005A (en) * | 2008-09-28 | 2010-03-31 | 复旦大学 | Nano magnetic material of surface modified boric acid base group, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张希浩: "硼酸功能化磁性材料的制备及其对目标糖蛋白的分离和富集", 《中国博士学位论文全文数据库 工程科技II辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN106693909B (en) * | 2017-01-19 | 2019-06-28 | 江苏大学 | A kind of magnetic nano-particle and its preparation method and application of phenyl boric acid modification |
| CN108499601A (en) * | 2018-01-17 | 2018-09-07 | 天津大学 | A kind of boric acid modified silica solid-carrying type platinum catalyst and its preparation and application |
| CN109046275A (en) * | 2018-07-05 | 2018-12-21 | 华侨大学 | It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead |
| CN109966504A (en) * | 2019-02-26 | 2019-07-05 | 中国科学院化学研究所 | A kind of albumin nanoparticle and the preparation method and application thereof that cell quickly absorbs |
| CN113975855A (en) * | 2021-11-17 | 2022-01-28 | 浙江树人学院（浙江树人大学） | Phenolic compound molecularly imprinted nanoenzyme solid-phase extraction column based on aminophenylboronic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106158197B (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Immobilization of trypsin on superparamagnetic nanoparticles for rapid and effective proteolysis | |
| CN106158197A (en) | A kind of phenylboric acid functional magnetic nano-particle with blocking group and its preparation method and application | |
| CN107413313B (en) | A kind of Magnetic solid phases extractant and its preparation method and application based on covalent organic framework material | |
| Li et al. | Ultrasensitive amperometric immunosensor for PSA detection based on Cu2O@ CeO2-Au nanocomposites as integrated triple signal amplification strategy | |
| Li et al. | Nitrilotriacetic acid-coated magnetic nanoparticles as affinity probes for enrichment of histidine-tagged proteins and phosphorylated peptides | |
| Go et al. | Desorption/ionization on silicon time-of-flight/time-of-flight mass spectrometry | |
| Qu et al. | Ultrasensitive ELISA using enzyme-loaded nanospherical brushes as labels | |
| Shen et al. | Engineering an enzymatic cascade catalytic smartphone-based sensor for onsite visual ratiometric fluorescence–colorimetric dual-mode detection of methyl mercaptan | |
| Bhaisare et al. | Rapid and direct MALDI-MS identification of pathogenic bacteria from blood using ionic liquid-modified magnetic nanoparticles (Fe 3 O 4@ SiO 2) | |
| CN108262019A (en) | A kind of magnetism sulfonic functional COFs materials and its preparation method and application | |
| Liu et al. | On-chip enzymatic microreactor using trypsin-immobilized superparamagnetic nanoparticles for highly efficient proteolysis | |
| CN110687182A (en) | Preparation method of electrochemical immunosensor for detecting prostate specific antigen | |
| Yuan et al. | Disassembly mediated fluorescence recovery of gold nanodots for selective sulfide sensing | |
| KR102021663B1 (en) | Method of detecting a target material using magnetic bead based enzyme-mimic nanozyme | |
| CN102796824B (en) | Detection reagent and detection kit of thrombin and application | |
| CN110865061B (en) | Simultaneous detection of nitrite ions and Hg2+Dual emission fluorescent probe and method thereof | |
| Zhai et al. | Facile synthesis of magnetic metal organic frameworks for highly efficient proteolytic digestion used in mass spectrometry-based proteomics | |
| CN104531669A (en) | Magnetic graphene nanocomposite material cladded with hydrophilic polydopamine and preparing method and application thereof | |
| Qian et al. | A smart glycol‐directed nanodevice from rationally designed macroporous materials | |
| KR20120128440A (en) | Kit and method for detecting target material | |
| CN105891189A (en) | Copper ion detecting kit and application thereof | |
| Song et al. | Efficient ABEI–Dissolved O2–Ce (III, IV)-MOF Ternary Electrochemiluminescent System Combined with Self-Assembled Microfluidic Chips for Bioanalysis | |
| Liu et al. | Quantum dot enhancement of peptide detection by matrix-assisted laser desorption/ionization mass spectrometry | |
| Li et al. | A simple gold nanoplasmonic SERS method for trace Hg2+ based on aptamer‐regulating graphene oxide catalysis | |
| Yang et al. | Fluorosurfactant-capped gold nanoparticles-based label-free colorimetric assay for Au3+ with tunable dynamic range via a redox strategy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190308 Termination date: 20200428 |