CN109999770A - One species specificity is affine porous polymer MOF chromatographic material and its preparation method and application - Google Patents
One species specificity is affine porous polymer MOF chromatographic material and its preparation method and application Download PDFInfo
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- CN109999770A CN109999770A CN201910220646.3A CN201910220646A CN109999770A CN 109999770 A CN109999770 A CN 109999770A CN 201910220646 A CN201910220646 A CN 201910220646A CN 109999770 A CN109999770 A CN 109999770A
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Abstract
The invention discloses affine porous polymer MOF chromatographic materials of a species specificity and its preparation method and application, under the conditions of the preparation method includes: existing for the strong basicity initiator, by sulphamide, three (2,3- glycidyl) isocyanates and MIL-101-NH2It is mixed in the first organic solvent, carries out copolyreaction.The preparation method is for the first time by MIL-101-NH2As matrix, thiophilic reagent sulphamide is introduced into MIL-101-NH2Surface, be made porous polymer MOF material, which has good specific enrichment and separating capacity to compound containing disulfide bond.The present invention provides the synthetic methods of the MOF of feasibility, and as new chromatographic material, impart the new application function of MOF, theory and practice value with higher.
Description
Technical field
The present invention relates to specific affinity chromatography materials, and in particular, to a species specificity is affine porous polymer MOF color
Compose material and its preparation method and application.
Background technique
Metal-organic framework materials (MOFs) are a kind of coordination polymers quickly grown in recent years, generally with metal ion
Or metal cluster is tie point, is self-assembly of three-dimensional porous structure by organic ligand, is after zeolite and carbon nanotube
Another class novel porous materials, be all widely used in catalysis, energy storage and separation.Currently, MOF have become inorganic chemistry,
The important research direction of multiple chemical branches such as organic chemistry.
As a kind of novel porous materials, MOFs has the physicochemical properties of highly significant (referring to " Science " 2005
The 309th phase page 204 in year), such as large specific surface area, thermal stability is high and porosity is persistently (referring to " Nature
Chemistry " the 2nd phase page 944 in 2010), it is being catalyzed it, drug conveying and sensing or identification aspect etc. have very well
Application prospect (referring to " Chemical Communications " the 47th phase page 3351 in 2011).In addition, based on MOFs's
High-specific surface area and Different porosities, MOFs can also be used as on gas is stored and separated a kind of ideal selection (referring to
" Angewandte Chemie International Edition " the 45th phase page 8227 in 2006).In addition, nearest function
The synthesis for changing MOF is also receive a lot of attention, however, the MOFs of synthesis functionalization but has very big challenge, because having perhaps
More chemical functional groups are incompatible with the synthesis condition of MOF, so can not be obtained by traditional synthetic route (referring to
" Chemical Communications " 2009 page 3720).
Therefore it provides the synthetic method of the MOF of feasibility and new MOF material and assign new application function be research
Target and direction.
Summary of the invention
The object of the present invention is to provide a kind of MOF materials and preparation method thereof, and the preparation method is for the first time by MIL-101-NH2
As matrix, thiophilic reagent sulphamide is introduced into MIL-101-NH2Surface, porous polymer MOF material, the material has been made
Material has good specific enrichment and separating capacity to compound containing disulfide bond.The present invention provides the conjunctions of the MOF of feasibility
At method, and as new chromatographic material, the new application function of MOF, theory and practice value with higher are imparted.
To achieve the goals above, the present invention provides the systems of the affine porous polymer MOF chromatographic material of a species specificity
Preparation Method, under the conditions of the preparation method includes: existing for the strong basicity initiator, by sulphamide, three (2,3- glycidyl)
Isocyanates and MIL-101-NH2It is mixed in the first organic solvent, carries out copolyreaction, obtain MIL-101-NH2@P
(TEPIC-co-SFA)。
The present invention also provides a kind of affine porous polymer MOF colors of specificity according to made from previously described preparation method
Compose material.
Moreover, the present invention also provides a kind of according to the affine porous polymer MOF chromatography material of previously described specificity
Expect to the specific enrichment of the compound containing disulfide bond with separate.
Through the above technical solutions, the present invention is for the first time by MIL-101-NH2As matrix, thiophilic reagent sulphamide is introduced
To MIL-101-NH2Surface, porous polymer MOF material MIL-101-NH has been made2@P (TEPIC-co-SFA), the material
There is good specific enrichment and separating capacity to compound containing disulfide bond, in conjunction with porous MOF chromatographic material specific surface itself
Product is big, the high advantage of stability, so that porous polymer MOF material is stablized with chemical property, thermal stability is high, is easy to store up
It deposits, the characteristics of good dispersion.Through the above technical solutions, realizing under the conditions of high salt concentration, affine porous MOF polymerization is looked for
Compose material with containing disulfide bond compound occur specificity interaction, its is immobilized, and with without disulfide bond compound into
Row separation；The compound containing disulfide bond is eluted under the conditions of low concentration of salt, obtains pure compound containing disulfide bond, at
Function realize to the enrichment containing disulfide bond compound with separate.The present invention provides the synthetic methods of the MOF of feasibility, and by its
As new chromatographic material, the new application function of MOF, theory and practice value with higher are imparted.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is reaction principle schematic diagram of the invention；
Fig. 2 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity obtained in embodiment 12@P
(TEPIC-co-SFA) Fourier Transform Infrared Spectroscopy figure；
Fig. 3 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity obtained in embodiment 12@P
(TEPIC-co-SFA) X-ray diffractogram；
Fig. 4 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity obtained in embodiment 12@P
(TEPIC-co-SFA) thermogravimetric analysis figure；
Fig. 5 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity obtained in embodiment 12@P
(TEPIC-co-SFA) scanning electron microscope (SEM) photograph, (a) are MIL-101-NH2Material amplifies 7.0K times of scanning electron microscope (SEM) photograph；(b) it is
MIL-101-NH2@P (TEPIC-co-SFA) material amplifies 50.0K times of scanning electron microscope (SEM) photograph；
Fig. 6 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity obtained in embodiment 12@P
(TEPIC-co-SFA) transmission electron microscope picture, (a) are MIL-101-NH obtained in embodiment 12The transmission electron microscope of 15K times of amplification
Figure；It (b) is the affine porous MOF polymer material MIL-101-NH of specificity obtained in embodiment 22@P(TEPIC-co-SFA)
The transmission electron microscope picture of 8K times of amplification；
Fig. 7 is the affine porous MOF polymer chromatography material MIL-101-NH of specificity provided in application examples2@P
(TEPIC-co-SFA) electrophoretogram with enrichment is separated to compound specificity containing disulfide bond.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides the preparation method of the affine porous polymer MOF chromatographic material of a species specificity, the preparation sides
Under the conditions of method includes: existing for the strong basicity initiator, by sulphamide, three (2,3- glycidyl) isocyanates and MIL-101-
NH2It is mixed in the first organic solvent, carries out copolyreaction.
Through the above technical solutions, the present invention is for the first time by MIL-101-NH2As matrix, thiophilic reagent sulphamide is introduced
To MIL-101-NH2Surface, be made porous polymer MOF material, which has compound containing disulfide bond good
Specific enrichment and separating capacity, in conjunction with porous MOF chromatographic material large specific surface area itself, the high advantage of stability, so that should
The characteristics of porous polymer MOF material is stablized with chemical property, and thermal stability is high, easily stored, good dispersion.By above-mentioned
Technical solution realizes under the conditions of high salt concentration, affine porous MOF polymer chromatography material and the compound containing disulfide bond
Specificity interaction occurs, its is immobilized, and separated with without disulfide bond compound；To containing under the conditions of low concentration of salt
There is the compound of disulfide bond to be eluted, obtain pure compound containing disulfide bond, successfully realizes to containing disulfide bond compound
It is enriched with and separates.The present invention provides the synthetic methods of the MOF of feasibility, and as new chromatographic material, impart MOF
New application function, theory and practice value with higher.
In the above-mentioned technical solutions, in order to further increase the yield of porous polymer MOF material, of the invention a kind of excellent
In the embodiment of choosing, relative to the sulphamide of 1 parts by weight, the dosage of three (2,3- glycidyl) isocyanates is 1-10 weight
Part, the dosage of MIL-101-NH2 is 0.5-10 parts by weight, and the dosage of strong basicity initiator is 0.01-0.5 parts by weight, and first has
The dosage of solvent is 400-600 parts by weight.
In order to further increase the yield of porous polymer MOF material, in a kind of preferred embodiment of the present invention, add
Heat condition includes: that temperature is 55-75 DEG C.
And the time of heating can be adjusted in a wider range, in a kind of preferred embodiment of the present invention,
Heating time is 8-16h.
To obtained porous MOF polymer chromatography material MIL-101-NH2@P (TEPIC-co-SFA) can use ability
The conventional post-processing step in domain is cleaned, to achieve the purpose that removal for reactant or other impurities, of the invention a kind of
In preferred embodiment, the preparation method further include: obtained copolymeric material is extracted with the second organic solvent
Or the step of elution.
Wherein, the second organic solvent selects one of methanol, ethyl alcohol, acetone and n-hexane or a variety of.Preferably, described
Second organic solvent is methanol.
MIL-101 series material is to combine computer simulation design to synthesize in the Ferey group by France in 2005 earliest.
As a kind of metal-organic framework materials, MIL-101 series material has a high specific surface area, large hole hold and aperture and compared with
Big window size, it is often more important that can it is stable in the air presence and keep its structural integrity not collapse, so
More MOFs material is studied through becoming.Herein, we select MIL-101 (Cr) as MIL-101-NH2The synthesis of material
Basis, i.e., with metal salt chromic nitrate and organic ligand 1,2- terephthalic acid (TPA) synthesizes under hydrothermal conditions.
In the above-mentioned technical solutions, MIL-101-NH2I.e. amidized MIL-101 be the prior art, 2012, Lin Yichao
Seminar's design has directly synthesized amidized MIL-101 (referring to " RSC Advances " the 2nd phase 6417-6419 in 2012
Page).We can synthesize MIL-101-NH using the synthetic method in the document2, can also adopt with other methods.
MIL-101-NH in the present invention2The MIL-101-NH of different morphologies can be selected2, such as sheet, spherical shape, stick
One of shape, polyhedral are a variety of, in order to improve the affine area of chromatographic material, it is preferable that select the MIL- of spherical shape
101-NH2。
In the present invention, we are to MIL-101-NH2Synthetic method be optimized, the preparation method include: with
As solvent, Chromium nitrate (Cr(NO3)3),nonahydrate and 2- amino terephthalic acid (TPA) as reactant, sodium hydroxide turns deionized water as intermediate
Agent, in 140-160 DEG C of reaction 8-16h, product is continuously washed repeatedly with solvent, is dried for standby, is obtained MIL-101-NH2。
Further, MIL-101-NH2The preparation method comprises the following steps: by the Chromium nitrate (Cr(NO3)3),nonahydrate of 0.4-0.6g, 0.14-0.22g
2- amino terephthalic acid (TPA) and 40mL deionized water be placed in 50mL beaker, through magnetic agitation, ultrasonic degassing, uniformly mixed
Solution is closed, solution is transferred in 50mL reaction kettle, reacts 8-14h in 140-160 DEG C of baking oven.After reaction, DMF is used
It is continuously washed with ethyl alcohol repeatedly, oven drying obtains MIL-101-NH2.The MIL-101-NH of available spherical shape2。
Again in above-mentioned technical proposal, sodium hydroxide, potassium hydroxide and calcium hydroxide are selected for the strong basicity initiator
One of or it is a variety of.Preferably, the strong basicity initiator selects sodium hydroxide.
First organic solvent selects methanol, ethyl alcohol, polyethylene glycol, dimethyl sulfoxide etc., it is preferable that described first has
Solvent selects dimethyl sulfoxide.
In the present invention, ring opening copolymer reaction reaction vessel can be glass container conventional in the art, as flask,
Test tube and chromatographic column, but the better affine porous MOF polymer material MIL-101-NH of specificity in order to obtain2@P
(TEPIC-co-SFA) chromatographic material, it is preferable that copolyreaction carries out in beaker.
The affine porous MOF polymer MIL-101-NH of specificity in this way in beaker2@P (TEPIC-co-SFA) chromatography
Material reaction is as abundant as possible, and then by extraction and elution, removal unreacted reactant obtains the affine porous MOF polymer of specificity
Chromatographic material MIL-101-NH2@P (TEPIC-co-SFA), the specificity is affine porous MOF polymer chromatography material MIL-101-
NH2@P (TEPIC-co-SFA) can also be perfused into chromatographic column, thus be applied to mixing sample enrichment with separate.
The present invention also provides a kind of affine porous polymer MOF colors of specificity according to made from previously described preparation method
Compose material.
Moreover, the present invention also provides a kind of according to the affine porous polymer MOF chromatography material of previously described specificity
Expect to the specific enrichment of the compound containing disulfide bond with separate.
Through the above technical solutions, the present invention is for the first time by MIL-101-NH2As matrix, thiophilic reagent sulphamide is introduced
To MIL-101-NH2Surface, be made porous polymer MOF material, which has compound containing disulfide bond good
Specific enrichment and separating capacity, in conjunction with porous MOF chromatographic material large specific surface area itself, the high advantage of stability, so that should
The characteristics of porous polymer MOF material is stablized with chemical property, and thermal stability is high, easily stored, good dispersion.By above-mentioned
Technical solution realizes under the conditions of high salt concentration, affine porous MOF polymer chromatography material and the compound containing disulfide bond
Specificity interaction occurs, its is immobilized, and separated with without disulfide bond compound；To containing under the conditions of low concentration of salt
There is the compound of disulfide bond to be eluted, obtain pure compound containing disulfide bond, successfully realizes to containing disulfide bond compound
It is enriched with and separates.The present invention provides the synthetic methods of the MOF of feasibility, and as new chromatographic material, impart MOF
New application function, theory and practice value with higher.
The present invention will be described in detail by way of examples below.In following embodiment, infared spectrum parameter passes through Fu
Li Ye-infrared spectrometer (FT-IR-21, Japanese Shimadzu Corporation) is measured, and scanning electron microscope (SEM) photograph and transmission electron microscope picture are to pass through Flied emission
Scanning electron microscope and transmission electron microscope (S-4800, Hitachi, Japan Hitachi) measure, and X ray diffracting spectrum is by XRD instrument
(BRUKER D8ADVANCE, German) is measured, and (DTG-60A, Japanese Shimadzu are public by thermogravimetric analyzer for thermogravimetric analysis map
Department) it measures, electrophoretic parameters pass through capillary electrophoresis (P/ACEtmMDQ, U.S. Bake Mann) it measures.
Preparation example 1
The Chromium nitrate (Cr(NO3)3),nonahydrate of 0.400g, the 2- amino terephthalic acid (TPA) of 0.180g and 40mL deionized water are placed in
It in 50mL beaker, through magnetic agitation, ultrasonic degassing, gets a uniform mixture, solution is transferred in 50mL reaction kettle,
12h is reacted in 150 DEG C of baking oven.After reaction, it is continuously washed three times with DMF and ethyl alcohol, oven drying 12h, obtains at 80 DEG C
To MIL-101-NH2。
Embodiment 1
(1) by MIL-101-NH obtained in the preparation example of 0.1506g 12It is mixed in 60mL DMSO, sequentially adds
0.0061g NaOH, 0.2216g crosslinking agent TEPIC and 0.1500g sulphamide is vortexed, oscillation is sufficiently dissolved, ultrasonic degassing
10.0min obtains uniformly mixed polymer fluid, is transferred to beaker, continues in an oven that reaction 12h is made blocky affine at 75 DEG C
Chromatographic material M1.
(2) bulk material M1 is continuously washed 3 times with methanol, washes away solvent DMSO and unreacting substance, obtains block-shaped material
Expect M2.
(3) bulk material M2 being placed in a vacuum drying oven, dry 12h, can be obtained affinity chromatography material at 60 DEG C,
That is copolymer MIL-101-NH2@P(TEPIC-co-SFA)。
Embodiment 2
It is prepared by the method in embodiment 1, unlike, 0.15g sulphamide is taken, the sulfonyl relative to 1 parts by weight
Amine, the dosage of three (2,3- glycidyl) isocyanates are 1 parts by weight, and the dosage of MIL-101-NH2 is 0.5 parts by weight, highly basic
Property initiator dosage be 0.01 parts by weight, the dosage of the first organic solvent is 400 parts by weight.
Embodiment 3
It is prepared by the method in embodiment 1, unlike, 0.15g sulphamide is taken, the sulfonyl relative to 1 parts by weight
Amine, the dosage of three (2,3- glycidyl) isocyanates are 10 parts by weight, and the dosage of MIL-101-NH2 is 10 parts by weight, highly basic
Property initiator dosage be 0.5 parts by weight, the dosage of the first organic solvent is 600 parts by weight.
Embodiment 4
It is prepared by the method in embodiment 1, unlike, reaction time 12h is changed to 8h respectively in step 1,
10h, 14h, 16h respectively obtain copolymer MIL-101-NH2@P(TEPIC-co-SFA)。
Embodiment 5
It is prepared by the method in embodiment 1, unlike, it is changed to 55 DEG C respectively by 75 DEG C of reaction temperature in step 1,
65 DEG C, 85 DEG C, 95 DEG C, respectively obtain copolymer MIL-101-NH2@P(TEPIC-co-SFA)。
Embodiment 6
It is prepared according to the method for embodiment 1, unlike, in step 1 into NaOH is changed to KOH, Ca (OH) respectively2,
The affine porous MOF polymer material of specificity is prepared respectively.
Embodiment 7
It is prepared according to the method for embodiment 1, unlike, change the second organic reagent methanol into ethyl alcohol, dimethyl
Sulfoxide.
Detect example 1
Porous MOF polymer chromatography material MIL-101-NH affine to specificity obtained2@P (TEPIC-co-SFA) material
Material carries out infrared detection, as a result sees Fig. 2, and in conjunction with the figure and relevant knowledge, make a concrete analysis of as follows: curve a is MIL-101-NH2
Infrared spectrogram, amino group is in 3300-2500cm-1Between there are two weak and sharp bimodal, curve c is the infrared suction of sulphamide
Spectrogram is received, the infrared signature absorption peak position of sulfuryl is in 1350-1300cm-1(1338cm-1) and 1160-1120cm-1
(1156cm-1).Curve b is the affine porous MOF polymer chromatography material MIL-101-NH of specificity of synthesis2@P(TEPIC-co-
SFA infrared spectrogram) can obviously observe sulfuryl characteristic absorption peak (1246cm in figure-1, 1128cm-1) presence, and b
Middle amino characteristic absorption peak disappears, this is because amino participates in ring-opening reaction.
The results show sulphamide and MIL-101-NH2It successfully reacts, it is poly- that the affine porous MOF of specificity is made
Close object chromatographic material MIL-101-NH2@P(TEPIC-co-SFA).According to it is presumed that, reaction mechanism of the invention is as shown in Figure 1.
Similarly, to the polymer MIL-101-NH in embodiment 2-72@P (TEPIC-co-SFA) is analyzed, and is obtained
Infrared spectrogram it is similar to the product in embodiment 1, it was demonstrated that sulphamide and MIL-101-NH2It successfully reacts, is made
Specific affine porous MOF polymer chromatography material MIL-101-NH2@P (TEPIC-co-SFA), but, the production in embodiment 1
Rate is better than embodiment 2,3.
Detect example 2
The structure of the porous organic-inorganic polymer material in polymerization front and back in embodiment 1 is observed using the method for XRD.
As a result see Fig. 3, can significantly see the MIL-101-NH synthesized with the first step2(Fig. 3 a) is compared, the affine material finally synthesized
Expect MIL-101-NH2Characteristic strong peak is remained on@P (TEPIC-co-SFA) (Fig. 3 b), only intensity is weakened, this illustrates its knot
Structure and MIL-101-NH before2Structure be consistent substantially.
Detect example 3
The thermal stability of the porous MOF polymer material in polymerization front and back in embodiment 1 is carried out using the method for thermogravimetric analysis
It investigates.As a result see Fig. 4, can significantly see that synthetic material there are three step weightlessness processes, the first step is solvent visitor in material duct
The burning of body molecule, second step may be the burning of organic moiety in material, and 500 DEG C of third step or so of weightlessness is material skeleton
Collapse completely, so the decomposition temperature of synthetic material close to 500 DEG C, illustrate synthesis affine porous MOF polymer material
Good thermal stability.
Detect example 4
The pattern of the porous MOF polymer material of polymerization front and back in embodiment 1 is seen using the method for scanning electron microscope
It examines.A is MIL-101-NH in Fig. 52It is amplified to 7K times of scanning electron microscope (SEM) photograph；The porous MOF polymer affinitive material amplification of b synthesis
To 50K times of scanning electron microscope (SEM) photograph, the MIL-101-NH of spherical shape can be clearly observed2It is still able to maintain shape after polymerization
Looks it is relatively stable.
Detect example 5
The dispersibility of the porous MOF polymer material of polymerization front and back is observed using the method for transmission electron microscope.In Fig. 6
A is MIL-101-NH2It is amplified to 15K times of transmission electron microscope picture；B is synthetic material MIL-101-NH2@P (TEPIC-co-SFA) is put
Greatly to 8K times of transmission electron microscope picture, the affinitive material favorable dispersibility synthesized as shown in Figure 6.
Application examples 1
The preparation of solution
1) preparation of bis- (4- hydroxy phenyls) disulfide (2S-OH) standard solution of 0.1mg/mL:, will at 25 DEG C
The 2S-OH of 1.0mg is dissolved in the 0.5M Klorvess Liquid (acetonitrile containing 5%) of 10.0mL, and the 2S-OH mark of 0.1mg/mL is made
Quasi- solution.
2) preparation of bis- (4- hydroxy phenyls) methane (2-OH) standard solution of 0.1mg/mL: at 25 DEG C, by 1.0mg's
Bis- (4- hydroxy phenyl) methane are dissolved in the 0.5M potassium chloride solution (acetonitrile containing 5%) of 10mL, are made 0.1mg/mL's
2-OH standard solution.
3) preparation of the 2S-OH and 2-OH mixed solution of 0.1mg/mL: at 25 DEG C, 1.0mg2S-OH and 2-OH is distinguished
It is dissolved in the 0.5M potassium chloride solution (acetonitrile containing 5%) of 10.0mL, 2S-OH and the 2-OH mixing that 0.1mg/mL is made are molten
Liquid.
4) preparation of sample solution: at 25 DEG C, 0.7162g disodium hydrogen phosphate and 0.186 1g potassium chloride are dissolved in about
In the distilled water of 45.0mL, being then adjusted to pH with the aqueous citric acid solution of 1M is 6.20, is then settled to 50.0mL and obtains
Sample liquid.
5) preparation of eluent: at 25 DEG C, by the distilled water of 0.7162g disodium hydrogen phosphate about 45mL, 1M is then used
Aqueous citric acid solution be adjusted to pH be 6.20, be then settled to 50.0mL and obtain eluent.
The preparation of background buffer solution
The preparation of Capillary Electrophoresis background buffer: the disodium hydrogen phosphate of 1.791g is dissolved in about 95.0mL distilled water
In, adjusting solution to pH with the aqueous citric acid solution of 1M is 8.50, is settled to 100.0mL, Capillary Electrophoresis background buffer is made
Solution.
2S-OH be enriched with affinity chromatography integral material and is detected for CE.
1) sample solution and eluent are prepared using method described above.
2) after the sample solution of 600 μ L and 800 μ L being mixed by 0.1mg/mL 2S-OH and 0.1mg/mL2-OH standard sample
Sample be added in the centrifuge tube of the affine porous MOF polymer material M2 containing specificity, shock balance 20min, to allow 2S-OH
It is fully immobilized on affine porous MOF polymer material M2.
3) sample solution of 300 μ L is added in the above-mentioned immobilized affine porous MOF polymer chromatography material M2 of 2S-OH,
It will not rinsed sufficiently, remove by immobilized 2S-OH, washing is three times.
4) eluent of 15 μ L is added in the centrifuge tube containing the affine porous MOF chromatographic material M2 of specificity, concussion is clear
10min is washed, the 2S-OH being immobilized on affine porous MOF polymer material is eluted, 2S-OH pregnant solution is obtained, it is to be measured；
5) pass through capillary electrophoresis (P/ACEtmMDQ, U.S. Bake Mann) electrophoresis inspection is carried out to 2S-OH pregnant solution
It surveys, specific testing conditions are as follows: (total length 56.5cm, effective length are the vitreous silica capillary for being 75 μm in internal diameter
It is carried out in 50cm)；Ultraviolet detection wavelength is 214nm, and sample volume is 8s × 0.5psi.
A curve is the electrophoretogram (blank) of buffer solution in Fig. 7, and b curve is the electrophoretogram (control) of eluent, c curve
It is the electrophoretogram using the mixed solution of 0.1mg/mL 2S-OH and 0.1mg/mL 2-OH as sample, d curve is 0.1mg/mL
Electrophoretogram of the 2-OH solution as sample, e curve are electrophoretogram of the 0.1mg/mL 2S-OH as sample, and f curve is aggregate sample
The electrophoretogram for the component that product elute after material is enriched with.Under the same conditions, 2-OH can not be by under the conditions of high salt concentration
Affine porous MOF polymer chromatography material-specific retains, and 2S-OH can be retained by specificity, after eluent is added, Ke Yishun
2S-OH is eluted by benefit, and the affinitive material synthesized reaches 0.8mg/g to the maximum adsorption capacity of 2S-OH, average richness
Integrate concentration as 0.1mg/ml, is the isoconcentration absorption to standard specimen.Data result shows the affine porous MOF polymerization of specificity obtained
Object chromatographic material MIL-101-NH2@P (TEPIC-co-SFA) imitates the compound containing disulfide bond with good specific enrichment
Fruit.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. the preparation method of a species specificity is affine porous polymer MOF chromatographic material, which is characterized in that the preparation method packet
It includes: under the conditions of existing for the strong basicity initiator, by sulphamide, three (2,3- glycidyl) isocyanates and MIL-101-NH2
It is mixed in the first organic solvent, carries out copolyreaction.
2. preparation method according to claim 1, wherein the mixed process are as follows:
1) by MIL-101-NH2Mixed once is carried out with the first organic solvent, sequentially adds strong basicity initiator, three (2,3- rings
Oxygen propyl group) isocyanates, the secondary mixing of sulphamide progress, ultrasonic degassing is then carried out, prepolymerization liquid is obtained；
2) the prepolymerization liquid is performed under heating conditions copolyreaction.
3. preparation method according to claim 1 or 2, wherein relative to the sulphamide of 1 parts by weight, three (2,3- epoxies third
Base) isocyanates dosage be 1-10 parts by weight, MIL-101-NH2Dosage be 0.5-10 parts by weight, strong basicity initiator
Dosage is 0.01-0.5 parts by weight, and the dosage of the first organic solvent is 400-600 parts by weight.
4. preparation method according to claim 3, wherein heating condition includes: that heating temperature is 55-75 DEG C, when heating
Between be 8-16h.
5. preparation method according to claim 1-4, wherein the preparation method further include: organic with second
The step of solvent is extracted or is eluted to obtained copolymeric material.
6. preparation method according to claim 1-4, wherein the strong basicity initiator selection sodium hydroxide,
One of potassium hydroxide and calcium hydroxide are a variety of.
7. preparation method according to claim 1-4, wherein first organic solvent select methanol, ethyl alcohol,
One of polyethylene glycol and dimethyl sulfoxide are a variety of；
With or, the second organic solvent selects one of methanol, ethyl alcohol, acetone and n-hexane or a variety of.
8. preparation method according to claim 1-4, wherein MIL-101-NH2Select the MIL-101- of spherical shape
NH2。
9. the affine porous polymer of specificity made from a kind of preparation method described in any one of -8 according to claim 1
MOF chromatographic material.
10. a kind of affine porous polymer MOF chromatographic material of specificity according to claim 9 is to compound containing disulfide bond
Specific enrichment with separate.
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