CN104177453B - A kind of synthetic method of nano grain surface dressing agent - Google Patents
A kind of synthetic method of nano grain surface dressing agent Download PDFInfo
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- CN104177453B CN104177453B CN201410346448.9A CN201410346448A CN104177453B CN 104177453 B CN104177453 B CN 104177453B CN 201410346448 A CN201410346448 A CN 201410346448A CN 104177453 B CN104177453 B CN 104177453B
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Abstract
The invention provides a kind of synthetic method of nano grain surface dressing agent.Water miscible two sulphur glycols and mannose are combined by chemical synthesis process, two sulphur glycols mannose derivatives are obtained;The product can carry out functional modification by the effect of sulfydryl covalent bond to the metals such as Au, Ag, Cd and semiconductor material surface, and the exposed mannose structures of the other end can be with canavaline(ConA)Specific binding;The process of this mannose derivative modification/silver nano-grain and ConA and mannose specific recognition process, in dark field microscope(DFM)The significant changes that can occur by the SPR color of image of individual particle nano particle down(Usually red shift)Real-time characterization comes out.The sugared nano particle hypotoxicity that is obtained by the surface modification of the functional molecular and stablize in the solution, not only with good biocompatibility and stability, be provided simultaneously with the efficient targets identification ability to trace canavaline.
Description
Technical field
Present invention relates particularly to a kind of synthetic method of nano grain surface dressing agent, belong to field of nanometer material technology.
Background technology
Albumen-sugar is reacted to the base of in terms of cell recognition is a lot (including cell adherence, transmission and immune response)
Plinth.These specific reactions are by glycoprotein, glycolipid, and cell surface polysaccharide and phytolectin, with sugared binding site
Protein occur.Phytolectin generally has the combination room of very weak sudden and violent leakage in a solvent.Therefore sugar and protein it
Between reaction it is typically all weaker.In order to provide the specificity of response intensity and reaction, the albumen being combined with sugar of much having the ability
Matter is that, by multiple similar or identical monomer composition oligomer, each monomer can be combined with a glycan molecule.It is right
In participating in for multiple simultaneous association reaction phytolectins are closed or formed to multivalence bond, there is provided an obvious knot
(feature adhesion) ability of conjunction, and to be much stronger than the summation of the binding ability of single reaction.
For studying the method for-protein-sugar reaction for obtaining to biological function and these reactions in pathology production at initial stage
Raw important function is necessary.Ordinary bond protein-glycan molecule is weaker with reference to often adhesion is belonged in solution
Reaction, so that with as the usually classical analysis based on solution of research protein or nucleic acid reaction before those
Method becomes highly difficult to analyze association reaction.Sugared array based on surface can for promoting phytolectin identification,
These will turn into a valuable instrument in blood glucose field.Sugared appearance provides one and seen simultaneously in array format
Survey multiple fixations sugar and solution in protein between binding events method.In addition, the sugar for being fixed on surface is many valence links
What form occurred.The association reaction of phytolectin combination multivalence key array contrast ordinary bond component is stronger and higher spy
The opposite sex.Therefore, it is phase that the fixation array of group, which helps phytolectin binding analysis and there is site for cell surface,
Close.
So far, lack for sugar strong, common and array can be controlled to assemble type, realize sugar
The report of molecular array arrangement.In addition for sugared array making, with reference to sugared array protein without using fluorescence, radioactivity
Element, or the analysis of enzyme transmission group are required, are avoided when also requiring that observation using second of binding constituents;In face of current a variety of analyses
Defect and deficiency in method, it is necessary to we have tried using Applications of surface plasmon resonance, one kind can and plasma
The incident light that body nano-material surface conduction band electron resonates occurs resonance in nano grain surface and electronics and triggers electromagnetic wave
A kind of optical phenomena of field-effect studies the reaction of sugar-protein.The present invention is exactly by hydrophilic two sulphur glycols chemical combination
Thing glycan molecule and nano particle to combine, and obtaining a glycan molecule medium chain can together soak with the CTAC nano particles coated
Culture, can thus occur base exchange reaction to form the nano particle of glycan molecule capped derivatives modification.By this
Sugar-nano particle that individual process is obtained be it is water miscible, it is non-toxic and stablize in the solution.
The content of the invention
Water miscible 2,2 '-two sulphur diethanols and full acetylated mannose are combined by chemical synthesis process, obtained
Product turns into 2,2 '-two sulphur diethanol mannose derivatives that can be with canavaline specific recognition after being deprotected, then
Bio-compatible sex modification is carried out to nano particle Au Ag with this compound, 2,2 '-two sulphur diethanol mannoses are to nano particle
Au Ag carry out biocompatibility modification can be by the SPR of individual particle Au Ag core shell structures under dark field microscope (DFM)
The change of spectrum is characterized, and is comprised the following steps that:
At room temperature, powdered mannose (MW180.16) is dissolved in NaSO to step 1.4In dried pyridine, excessive second is added
Acid anhydrides, stirring certain time length (being more than 2h) is rotated afterwards, with pyridine in removing system;It is extracted with ethyl acetate, saturation NaHCO3It is molten
Liquid, constant temperature is rotated after saturated aqueous common salt cleaning, vacuum drying;Obtain full acetylated mannose:
Step 2. is by BF3·Et2O is added dropwise to 0 DEG C, does not stop the cystine linkage glycols carbohydrate and step 1 of stirring
The CH of obtained full acetylated mannose2Cl2(through drying process) in solution, then mixed liquor can at room temperature react and be more than
12h (does not stop stirring);Use CH2Cl2Extraction, is washed out twice, then use NaSO4Dry;Ethyl acetate is used again:Petroleum ether according to
Certain proportioning is purified, and obtains the mannose derivative of acetylation protection:
The purified product that step 2 is obtained is dissolved in methanol by step 3. in a round-bottomed flask, adds NaOMe in room temperature
Lower stirring, solvent is steamed and EtOAc is used:MeOH is purified according to a certain ratio, is obtained two sulphur glycols mannoses and is spread out
Biologic:
The processing procedure of step 4.ITO substrates.With detergent, acetone, ethanol, ultra-pure water soaks ITO egative films successively, immersion
Egative film, which is positioned in Ultrasound Instrument, handles 1-2h, uses ultrapure water after replacing solution every time;Dried up and preserved with nitrogen after 4h;
Au@Ag core-shell nanocube are fixed on the treated ITO surfaces of step 4 by step 5., are obtained with step 3
The aqueous solution soaking of the product arrived fixes Au@Ag NC ITO substrate, carries out surface modification to Au@Ag NC, obtains surface exposure
Mannose group nano particle, can be used as the bioprobe for detecting canavaline.With various concentrations (10-8-10-2M mannose)
ITO substrate to fixed Au@Ag core-shell nanocube carries out surface immersion modification.
Beneficial effect
The present invention obtains 2,2 '-two sulphur diethanol mannose derivatives that can be with canavaline specific recognition,
Then bio-compatible sex modification is carried out to nano particle Au Ag with this compound, it is naked that Au Ag NC just turn into surface by modification
Reveal mannose group nano particle, surface exposure mannose group can just be carried out to micro canavaline (ConA) present in solution
Specific detection, the specific biological probe of canavaline (ConA) can be detected by just becoming one.Pass through this process
Obtained sugar-nano particle be it is water miscible, it is non-toxic and stablize in the solution.
Brief description of the drawings
Fig. 1 is the H of the full acetylated mannose of product of step 1 in the present invention1NMR spectra.
Fig. 2 is the H of the full acetylated mannose of sulphur diethanol of product 2,2 '-two of step 2 in the present invention1NMR spectra.
Fig. 3 is the H of the sulphur diethanol mannose of product 2,2 '-two of step 3 in the present invention1NMR spectra.
Fig. 4 is that 2,2 '-two sulphur diethanol mannoses of step 4 in the present invention carry out modification difference to nano particle Au@Ag
The process of time, is characterized by the change of the SPR spectroscopy of individual particle Au Ag core shell structures under dark field microscope (DFM)
As a result.
Embodiment
Embodiment 1
1. at room temperature, 2.5g, at room temperature, 2.5g, 0.0139mol (1eq) powdered mannose (MW180.16) are dissolved in
In pyridine dried 20mL NaSO4,70 DEG C of revolvings after 10mL, 0.083mol (1.5eq) acetic anhydride, stirring 16h are added, are used
Ethyl acetate is extracted, 2 × 100mL saturation NaHCO3 solution, and 40 DEG C of revolvings after the cleaning of 2 × 100mL saturated aqueous common salts, vacuum is done
It is dry;Obtain full acetylated mannose.
2.6.4mL BF3.Et2O (7.2g, 5eq, 51.2mmol) is added dropwise to 0 DEG C, does not stop the cystine linkage diethyl of stirring
Alcohol 1.09g (1.4eq, 7mmol) and the product (4g, 1eq, 10.2mmol) of step 1 CH2Cl2In solution (20mL is dried), so
Mixed liquor can react 24h (not stopping stirring) at room temperature afterwards.Use 30mL CH2Cl2Extraction, 20mL NaHCO3Wash twice,
Na2SO4Dry.Crude product can use ethyl acetate:Petroleum ether=1:1 is separated, the product purified.
3. the product of (0.2g, 0.37mmol) step 2 is dissolved in 5mL methanol in a round-bottomed flask, add
(0.03g, 0.55mmol) NaOMe is stirred at room temperature 30min and steams solvent and use EtOAc:MeOH=10:0.2 purifying.
Obtain 2,2 '-two sulphur diethanol mannoses.
The processing procedure of 4.ITO substrates.With detergent, acetone, ethanol, ultra-pure water soaks ITO egative films successively, soaks egative film
It is positioned in Ultrasound Instrument and handles 1-2h, uses ultrapure water after replacing solution every time;Dried up and preserved with nitrogen after 4h.
5. Au@Ag core-shell nanocube are fixed on into the treated ITO surfaces of step 4, obtained with step 3
The aqueous solution soaking of product fixes the ITO substrate that Au Ag NC step 4 is treated, with 10-2M carries out surface to Au@Ag NC and repaiied
Decorations, modification is as follows:ITO substrate is soaked with the Au@Ag NC solution purified, Au@Ag is absorbed and fixed at ITO surfaces;So
After be fixed on dark field microscope (DFM) objective table, adjust focal length, obtain clearly Au@Ag NC colored CCD picture;At random
Several individual particle Au@Ag NC are chosen, 200uL 10 is then added in substrate-2The product of M step 3, to selected particle table
The modification in face carries out real-time monitored 0.5h.It can be seen that the absorption of 2,2 '-two sulphur diethanol mannose derivatives is in Au@Ag
Red shift will occur for NC surface process, Au@Ag NC SPR spectroscopy.Such as Fig. 4 square dotted line.
Embodiment 2
1. at room temperature, 2.5g, at room temperature, 2.5g, 0.0139mol (1eq) powdered mannose (MW180.16) are dissolved in
In pyridine dried 20mL NaSO4,70 DEG C of revolvings after 10mL, 0.083mol (1.5eq) acetic anhydride, stirring 16h are added, are used
Ethyl acetate is extracted, 2 × 100mL saturation NaHCO3 solution, and 40 DEG C of revolvings after the cleaning of 2 × 100mL saturated aqueous common salts, vacuum is done
It is dry, obtain full acetylated mannose.
2.6.4mL BF3.Et2O (7.2g, 5eq, 51.2mmol) is added dropwise to 0 DEG C, does not stop the cystine linkage diethyl of stirring
Alcohol 1.09g (1.4eq, 7mmol) and the product (4g, 1eq, 10.2mmol) of step 1 CH2Cl2In solution (20mL is dried), so
Mixed liquor can react 24h (not stopping stirring) at room temperature afterwards.Use 30mL CH2Cl2Extraction, 20mL NaHCO3Wash twice,
Na2SO4Dry.Crude product can use ethyl acetate:Petroleum ether=1:1 is separated, the product purified.
3. the product of (0.2g, 0.37mmol) step 2 is dissolved in 5mL methanol in a round-bottomed flask, add
(0.03g, 0.55mmol) NaOMe is stirred at room temperature 30min and steams solvent and use EtOAc:MeOH=10:0.2 purifying.
Obtain 2,2 '-two sulphur diethanol mannoses.
The processing procedure of 4.ITO substrates.With detergent, acetone, ethanol, ultra-pure water soaks ITO egative films successively, soaks egative film
It is positioned in Ultrasound Instrument and handles 1-2h, uses ultrapure water after replacing solution every time;Dried up and preserved with nitrogen after 4h.
5. Au@Ag core-shell nanocube are fixed on into the treated ITO surfaces of step 4, obtained with step 3
The aqueous solution soaking of product fixes the ITO substrate that Au Ag NC step 4 is treated, with 10-2M carries out surface to Au@Ag NC and repaiied
Decorations, modification is as follows:ITO substrate is soaked with the Au@Ag NC solution purified, Au@Ag is absorbed and fixed at ITO surfaces;So
After be fixed on dark field microscope (DFM) objective table, adjust focal length, obtain clearly Au@Ag NC colored CCD picture;At random
Several individual particle Au@Ag NC are chosen, 200uL 10 is then added in substrate-2The product of M step 3, to selected particle table
The modification in face carries out real-time monitored 1.0h.It can be seen that the absorption of 2,2 '-two sulphur diethanol mannose derivatives is in Au@Ag
Red shift will occur for NC surface process, Au@Ag NC SPR spectroscopy.Such as Fig. 4 ball dotted line.
Embodiment 3
1. at room temperature, 2.5g, at room temperature, 2.5g, 0.0139mol (1eq) powdered mannose (MW180.16) are dissolved in
In pyridine dried 20mL NaSO4,70 DEG C of revolvings after 10mL, 0.083mol (1.5eq) acetic anhydride, stirring 16h are added, are used
Ethyl acetate is extracted, 2 × 100mL saturation NaHCO3 solution, and 40 DEG C of revolvings after the cleaning of 2 × 100mL saturated aqueous common salts, vacuum is done
It is dry;Obtain full acetylated mannose.
2.6.4mL BF3.Et2O (7.2g, 5eq, 51.2mmol) is added dropwise to 0 DEG C, does not stop the cystine linkage diethyl of stirring
Alcohol 1.09g (1.4eq, 7mmol) and the product (4g, 1eq, 10.2mmol) of step 1 CH2Cl2In solution (20mL is dried), so
Mixed liquor can react 24h (not stopping stirring) at room temperature afterwards.Use 30mL CH2Cl2Extraction, 20mL NaHCO3Wash twice,
Na2SO4Dry.Crude product can use ethyl acetate:Petroleum ether=1:1 is separated, the product purified.
3. the product of (0.2g, 0.37mmol) step 2 is dissolved in 5mL methanol in a round-bottomed flask, add
(0.03g, 0.55mmol) NaOMe is stirred at room temperature 30min and steams solvent and use EtOAc:MeOH=10:0.2 purifying.
Obtain 2,2 '-two sulphur diethanol mannoses.
The processing procedure of 4.ITO substrates.With detergent, acetone, ethanol, ultra-pure water soaks ITO egative films successively, soaks egative film
It is positioned in Ultrasound Instrument and handles 1-2h, uses ultrapure water after replacing solution every time;Dried up and preserved with nitrogen after 4h.
5. Au@Ag core-shell nanocube are fixed on into the treated ITO surfaces of step 4, obtained with step 3
The aqueous solution soaking of product fixes the ITO substrate that Au Ag NC step 4 is treated, with 10-2M carries out surface to Au@Ag NC and repaiied
Decorations, modification is as follows:ITO substrate is soaked with the Au@Ag NC solution purified, Au@Ag is absorbed and fixed at ITO surfaces;So
After be fixed on dark field microscope (DFM) objective table, adjust focal length, obtain clearly Au@Ag NC colored CCD picture;At random
Several individual particle Au@Ag NC are chosen, 200uL 10 is then added in substrate-2The product of M step 3, to selected particle table
The modification in face carries out real-time monitored 2.0h.It can be seen that the absorption of 2,2 '-two sulphur diethanol mannose derivatives is in Au@Ag
Red shift will occur for NC surface process, Au@Ag NC SPR spectroscopy.Such as Fig. 4 inverted triangle dotted line.
Claims (1)
1. a kind of synthetic method based on nano grain surface dressing agent, it is characterised in that:
The synthesis of the full acetylated mannose of step 1.:
At room temperature, powdered mannose MW180.16 is dissolved in Na2 SO4In dried pyridine, excessive acetic acid acid anhydride is added, during stirring
It is long to be more than revolving after 2h, with pyridine in removing system;It is extracted with ethyl acetate, saturation NaHCO3Solution, saturated aqueous common salt cleaning
Constant temperature is rotated afterwards, vacuum drying;Obtain full acetylated mannose;
Step 2. is by BF3·Et2O is added dropwise to 0 DEG C, do not stop stirring two sulphur diethanols and step 1 obtain it is full acetylated sweet
Reveal the CH of sugar2Cl2In solution, then mixed liquor can react more than 12h at room temperature;Use CH2Cl2Extraction, is washed out two
It is secondary, then use Na2 SO4Dry;Ethyl acetate is used again:Petroleum ether is purified according to a certain ratio, obtains the sweet of acetylation protection
Reveal sugar derivatives;
Step 3. prepares two sulphur diethanol mannose derivatives:
The purified product that step 2 is obtained is dissolved in methanol in a round-bottomed flask, NaOMe is added and is stirred at room temperature, will
Solvent steams and uses EtOAc:MeOH is purified according to a certain ratio, obtains product;
The nano particle of Au, Ag, Cd metal or its semi-conducting material is fixed on conductive glass surface by step 4., is obtained with step 3
The aqueous solution soaking of the product arrived fixes the electro-conductive glass substrate of Au, Ag, Cd metal or the nano particle of its semi-conducting material, right
The nano particle of Au, Ag, Cd metal or its semi-conducting material carries out surface modification, obtains surface exposure mannose group nanometer
Grain;
The electro-conductive glass is a series of transparent conducting glass for including ITO, FTO or TCO, surface by processing can with Au,
The nano particle absorption of Ag, Cd metal or its semi-conducting material is combined.
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