CN105181910B - A kind of method measuring monosaccharide enantiomeric excess value - Google Patents
A kind of method measuring monosaccharide enantiomeric excess value Download PDFInfo
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Abstract
The present invention provides a kind of method measuring monosaccharide enantiomeric excess value：1) using the method for Electrostatic Absorption, dipeptides polyethyleneimine polymers are grafted to microcrystalline quartz body balance chip surface, form thin polymer film；2) it is utilized respectively the monosaccharide solutions soaking step 1 of different known enantiomeric excess values) the microcrystalline quartz body balance chip that obtains；3) the Young's moduluss size of the thin polymer film after being soaked using the monosaccharide solutions that the mechanical mode of atomic force microscope measures above-mentioned different known enantiomeric excess value respectively, obtains the linear relationship curve that thin polymer film Young's moduluss are with respect to enantiomeric excess value；4) monosaccharide solutions of unknown enantiomeric excess value, repeat step 2 are provided) and 3) obtaining Young's moduluss value, the enantiomeric excess value on this Young's moduluss value corresponding linear relationship curve is test result.The method measurement accurate, simple to operate, repeat, be expected to glucide Enantiomeric excess detection field acquisition be widely applied.
Description
Technical field
The invention belongs to materials chemistry and organic chemistry filed are and in particular to a kind of side of mensure monosaccharide enantiomeric excess value
Method.
Background technology
For asymmetric synthesis, its target is to obtain a kind of high enantiomerism of purity by chiral catalyst
Body.This method, it can be avoided that time-consuming chiral separation, saves production cost.And for the assessment of asymmetric synthesis, right
Reflect body excessive value (common first names：Ee value) mensure most important.With being continuously increased of chiral drug on market, need to develop and
Exploitation is new, the assay method of efficient enantiomeric excess value.
At present, the mensure of enantiomeric excess mainly uses liquid and gas chromatograph and carries out, by design with prepare different
Chiral chromatogram column packing, according to the difference of chiral species to be determined retention time on a column, by comparing L-, D- type
The chromatographic peak area of species, to measure the enantiomeric excess value of chiral material.However, these methods all to there is the consuming time long
The shortcomings of with spending big, particularly chiral chromatographic column price is very expensive, easily 20,000 yuan of every analytical columns；And chromatograph packing material
Very enervated it is impossible to bear some harsh separation conditions (such as to avoid introducing in a solvent dimethyl sulfoxide, N as far as possible, N '-
Dimethylformamide, chloroform, dichloromethane, toluene, oxolane, dioxane etc. common are machine solvent, in order to avoid causing color
The spectrum irreversible damage of filler).For chiral chromatography, it is right to some chiral materials (as chiral monosaccharide) that it cannot be realized
Reflect the excessive mensure of isomer.
Monosaccharide and oligosaccharide are widely used in the synthesis of chiral drug, serve as initial optics pure raw material or anti-
The intermediate answered.Naturally occurring monosaccharide great majority are all D- type sugar, only arabinose and fucose in the form of L-type sugar
Exist.The biological function of D- type sugar is fully disclosed, and has carried out in-depth study exploration；But the life of L-type sugar
Reason function is but seldom found, and such as L-arabinose has the sweet taste the same with D- type arabinose, but but can not be people
The metabolism of body institute, is therefore widely used as a kind of diet food (" left-handed arabinose ").D- type deoxyribose is DNA
Core construction unit, and L-type deoxyribose is used to synthesize a kind of anti-AIDS drug.Therefore study non-natural chiral single
Sugar has significant scientific meaning and potential economic worth.But L-type monosaccharide is difficult to extract from nature biotechnology obtain,
Generally require the asymmetric catalysis carrying out multistep, the product obtaining is often presented in racemic modification, therefore has
The necessary enantiomeric purity to monosaccharide is accurately measured, as the basis of subsequent development.
At present, chiral chromatographic column cannot realize the enantiomer differentiation to monosaccharide, therefore cannot be carried out enantiomeric excess
The mensure of value；Polarimetry and circular dichroism detector, because precision is not high, batch reproducibility is poor, also cannot be carried out quantitative determining.Cause
This is it is necessary to develop a kind of new method of energy Accurate Determining monosaccharide enantiomeric excess.
Content of the invention
It is an object of the invention to provide a kind of assay method of accuracy monosaccharide enantiomeric excess value high, easy and simple to handle.
The present invention by solving the scheme that adopted of above-mentioned technical problem is：
A kind of method measuring monosaccharide enantiomeric excess, it comprises the steps：
1) using the method for Electrostatic Absorption, dipeptides polyethyleneimine polymers are grafted to microcrystalline quartz body balance chip table
Face, forms thin polymer film；
Described dipeptides polyethyleneimine polymers areWherein, n is polymerization
Degree, in the range from 5 to 200000；
2) it is utilized respectively the monosaccharide solutions soaking step 1 of different known enantiomeric excess values) the microcrystalline quartz body that obtains
Balance chip；
3) monosaccharide of above-mentioned different known enantiomeric excess value is measured respectively using the mechanical mode of atomic force microscope
The Young's moduluss size of the thin polymer film after solution soaking, obtains thin polymer film Young's moduluss with respect to enantiomeric excess value
Linear relationship curve；
4) monosaccharide solutions of unknown enantiomeric excess value are provided, the monosaccharide solutions of described unknown enantiomeric excess value are soaked
Step 1) the microcrystalline quartz body balance chip that obtains, the mechanical mode using atomic force microscope measures described unknown enantiomer mistake
The Young's moduluss of the thin polymer film after the monosaccharide solutions immersion of value, this Young's modulus is worth on corresponding linear relationship curve
Enantiomeric excess value is test result.
In such scheme, described step 2) in monosaccharide solutions be ribose, deoxyribose, glucose, xylose, lyxose,
Arabinose or mannose.
In such scheme, described dipeptides polyethyleneimine polymers are by substitution reaction, by the dipeptides of chloracetyl chlorination
It is grafted on the side chain of the polyethyleneimine that the degree of polymerization is 5 to 200000, obtain described dipeptides polyethyleneimine polymers, its
In, described dipeptides isThe dipeptides of described chloroacetylation is
In such scheme, the preparation method of described dipeptides polyethyleneimine polymers comprises the steps：
1) described dipeptides and triethylamine are dissolved among anhydrous chloroform solution, under stirring condition, by chloracetyl chloride dropwise
It is added drop-wise in above-mentioned solution, after completion of dropwise addition, react 10-14 hour under room temperature, obtain the dipeptides 1 of chloroacetylation；
2) under room temperature condition, by polyethyleneimine, it is molten that sodium iodide and potassium carbonate are dissolved into anhydrous DMF
In liquid, under stirring condition, the DMF solution Deca dissolved with 1 is dropwise added drop-wise among above-mentioned solution, lucifuge
React 22-26 hour under nitrogen protective condition, can get dipeptides polyethyleneimine polymers PEI-g-D-DF through purification；
Beneficial effects of the present invention are：
1. the present invention develops a kind of brand-new, and the change using detection polymer Young's moduluss measures monosaccharide enantiomer
Excessive new method.In the research of early stage, inventor finds dipeptides (for example：D-Asp-D-Phe, abridge D-DF) for difference
Monosaccharide enantiomer, there is good stereo selectivity.On this basis, inventor by the method for chemical graft by two
Peptide unit is grafted to a kind of polyelectrolyte of flexibility (for example：Polyethyleneimine, english abbreviation：PEI) on segment, that is, obtained one
Plant the polymeric material (PEI-g-D-DF) to monosaccharide enantiomer with chiral selectivity interaction.By QCM-D's
Research shows, this chiral polymer is to variety classes monosaccharide (for example：Ribose, deoxyribose, glucose, xylose, lyxose,
Arabinose, mannose) show good chiral selectivity and chemo-selective absorption, wherein L/D- ribose and L/D- deoxidation
Ribose shows the chiral diversity of maximum.Simultaneously, after absorption monosaccharide, two kinds of macroscopic properties of thin polymer film, that is,
Hardness and viscoelasticity occur significantly to change, and in the degree simultaneously changing and solution, the Enantiomeric excess ratio of monosaccharide is in good
Linear relationship.Based on this, it is possible to use to the change in this polymer machinery performance, to measure the enantiomeric excess value of monosaccharide；
2. the polymer of present invention preparation is polyelectrolyte, both can be bonded to various differences by way of Electrostatic Absorption
Metal substrate surface, construct have sugar response function interface material；By substitution reaction, polymer can be grafted again
Modify Silica Surface, develop as sugar from chromatograph packing material；
3. the present invention passes through to measure the change that thin polymer film adsorbs Young's moduluss before and after monosaccharide, you can obtain the right of monosaccharide
Reflect isomer excessive value, solve the insurmountable difficult problem of chiral chromatography methods of routine.The method has certainty of measurement simultaneously
High, time-consuming short, low cost, the advantages of easily promote, there is provided a kind of method of brand-new chiral species determination of enantiomer excess.
Brief description
The syntheti c route of the polyethyleneimine functional polymer that Fig. 1 modifies for dipeptides.
Fig. 2 is compound 1, the nucleus magnetic hydrogen spectrum of PEI and polymeric material PEI-g-D-DF.
Fig. 3 is compound 1, the ultraviolet spectra of PEI and PEI-g-D-DF.
Fig. 4 is compound 1, the infrared spectrum of PEI and PEI-g-D-DF.
Fig. 5 is compound 1, the C. D. spectrum spectrum of PEI and PEI-g-D-DF.
Fig. 6 is the chip polymer thickness test after bare chip and PEI-g-D-DF modification.
The chip XPS elementary analysiss that Fig. 7 modifies for PEI-g-D-DF, carbon forms.
The chip XPS elementary analysiss that Fig. 8 modifies for PEI-g-D-DF, oxygen element forms.
The chip XPS elementary analysiss that Fig. 9 modifies for PEI-g-D-DF, nitrogen forms.
Figure 10 is the change causing PEI-g-D-DF polymer chip frequency after seven groups of monosaccharide enantiomers are adsorbed.
Figure 11 changes for the frequency that ribose enantiomer produces in PEI-g-D-DF polymer chip surface adsorption.
Figure 12 is original polymer surfaces hardness distribution (A), and after L-type (B) or D- type (C) ribose are processed
Case hardness distribution.
Figure 13 is L/D- ribose mixture enantiomeric excess value and polymer Young's moduluss linear relationship chart.
Figure 14 is L/D- deoxyribose mixture enantiomeric excess value and polymer Young's moduluss linear relationship chart.
Specific embodiment
For making present disclosure, technical scheme and advantage become more apparent, below in conjunction with specific embodiments and the drawings
The present invention is expanded on further, these embodiments are merely to illustrate the present invention, and the present invention is not limited only to following examples.
Raw materials used and equipment in embodiment:
Polyethyleneimine (molecular weight 10000,100000,500000) is by Shanghai Aladdin biochemical technology limited company
Buy, D-Asp-D-Phe is buied by Shanghai Xi Shi bio tech ltd.Chloracetyl chloride, triethylamine and chromatographically pure DMF by
TCI company buys.Other reagent are all pure using commercially available analysis.1H and13C NMR spectra is in Bruker
ARX300spectrometer detection obtains.
Embodiment 1
The preparation of PEI-g-D-DF
Detailed syntheti c route is as shown in Figure 1.Under condition of ice bath, by D-Asp-D-Phe and 0.24g of 0.62g (2mmol)
(2mmol) triethylamine is dissolved among 30mL anhydrous chloroform solution, under stirring condition, by the chloracetyl of 0.27g (2.4mmol)
Chlorine is dropwise added drop-wise in above-mentioned solution, after completion of dropwise addition, reacts 12 hours under room temperature.Reaction terminates rear 30mL salt and washes 4 times,
Take organic phase solution, rotary evaporation is crossed silicagel column after falling organic solvent and be can get reactant 1 (0.51g, yield 65%).
Under room temperature condition, by 1.5g polyethyleneimine (molecular weight be 10000), 0.04g sodium iodide (0.26mmol) and
The potassium carbonate (2.6mmol) of 0.36g is dissolved in the anhydrous DFM solution of 50mL, under stirring condition, by 10mL dissolved with 0.5g chemical combination
The DMF solution Deca of thing 1 is dropwise added drop-wise among above-mentioned solution, reacts 24 hours under lucifuge nitrogen protective condition.Then will be upper
State solution and transfer to bag filter (molecular cut off：3000), in, dialyse 5 days under the conditions of methanol and ultra-pure water.Reduce pressure bar afterwards
Solvent is removed, you can obtain PEI-g-D-DF under part.The characterize data of two materials is as follows.
The characterize data of compound 1：
Nucleus magnetic hydrogen spectrum (300MHz, deuterochloroform):Chemical shift (ppm):2.65(d,d,J1=J2=4.2Hz, 1H, C-
CH2),2.97(d,d,J1=J2=2.4Hz, 1H, C-CH2),3.06(d,d,J1=J2=3.9Hz, 1H, C-CH2),3.16(d,
d,J1=J2=4.2Hz, 1H, C-CH2),3.71(s,3H,OCH3),3.73(s,3H,OCH3),3.92-4.02(d,d,J1=J2
=9.0Hz, 2H, C-CH2), Cl 4.78-4.82 (m, 2H, C*H), 6.97 (d, J=7.5Hz, 1H, CONH), 7.12-7.32 (m,
5H, Ph-H), 7.86 (d, J=4.8Hz, 1H, CONH). nuclear-magnetism carbon composes (600MHz, deuterochloroform):Chemical shift (ppm):
35.1,37.5,42.3,49.3,52.3,52.4,53.4,127.2,128.4,128.6,129.0,129.2,135.6,166.3,
169.4,171.4,172.3；Infrared (wave number):3290,2956,1755,1732,1668,1646,1530,1436,1413,
1367,1311,1292,1207,1173,1068,1031,989,952,930,900.Elementary analysiss, C17H21N2O6Cl predictive value
(%):C,53.06；H,5.50；N,7.28；Actual measured value C, 53.00；H,5.58,N,7.36；High resolution mass spectrum:Charge-mass ratio
C17H21N2O6Cl value of calculation：384.1；Measured value:385.0[M+H]+.
Shown in the characterize data as Fig. 2 to Fig. 5 of PEI-g-D-DF.
Embodiment 2
Using the method described in embodiment 1, the dipeptides of chloroacetylation is grafted to the polyvinyl Asia of different polymerization degree
On amine, the scope of the degree of polymerization is 5 to 200000.
Embodiment 3
PEI-g-D-DF functional polymer self-assembling method on a gold surface：
Using the QCM-D cleaning up chip (chip surface has been deposited with the thick gold of one layer of 30-40nm as metal sensor)
It is immersed in the PEI-g-D-DF aqueous solution of 20mg/mL, take out after half an hour, use ultrapure water chip, blown with nitrogen afterwards
Dry chip can obtain being grafted with the chip of PEI-g-D-DF.Chip after polymer-modified characterizes as shown in Figures 6 to 9.
Fig. 6 is chip (right figure) the polymer thickness test after bare chip (left figure) and PEI-g-D-DF modification, can by figure
Know that polymer thickness is 7-8nm.
Embodiment 4
QCM-D adsorption experiment
Inventor passes through QCM-D, measures the dynamic adsorption behavior to six groups of monosaccharide enantiomers for the PEI-g-D-DF, according to
Chip frequency and dissipation data learn that PEI-g-D-DF has chiral diversity absorption behavior (as shown in Figure 10) to six groups, simultaneously
There is the change of diversity in the viscoelasticity of polymer.Taking ribose as a example, as shown in figure 11.Adsorption experiment is later stage surface Young mould
The basis of measurement, only adsorption experiment confirm to create the chiral species pair of Adsorption in polymer surfaces, are possible to
Measured by Young's moduluss and obtain enantiomeric excess value.
Embodiment 5
The excessive mensure of enantiomer
By the absorption frequency measurement in embodiment 4, chirality to be measured can be distinguished with rapid evaluation polymer surfaces
Species pair.The absorption of chiral monosaccharide causes the notable change of polymer surfaces hardness (carrying out quantitative analyses using Young's moduluss)
Change, L-type and the firmness change caused by D- type monosaccharide are completely different simultaneously., the absorption of L-type ribose leads to gather taking ribose as a example
Compound case hardness significantly reduces, and the absorption of D- type ribose makes the hardness of material surface dramatically increase, as shown in figure 12.Figure
12 is that original polymer surfaces hardness is distributed (A), and the case hardness after L-type (B) or D- type (C) ribose are processed
Distribution.
On this basis, polymer surfaces Young's moduluss and chiral species are set up to the linear pass between enantiomeric excess value
System, wherein surface Young's moduluss are given automatically by AFM software statistics.Taking ribose as a example, using different enantiomeric excesses (-
100%, -50,0,50,100) ribose solution soaks the QCM chip that PEI-g-D-DF modifies, and then shows by using atomic force
The mechanical mode of micro mirror determines the Young's moduluss of polymeric film.By data analysiss, the enantiomeric excess value of ribose with
Linear relationship (as shown in figure 13) is there is between corresponding polymeric film Young's moduluss.Therefore, establishing polymer Young
After modulus and corresponding monosaccharide enantiomeric excess linear relationship, only need to measure the Young's moduluss of unknown polymeric film
Know the enantiomeric excess value of its ribose.
As shown in Figure 13, through five groups of different known ribose enantiomeric mixture, (enantiomeric excess value is：-
100%, -50%, 0,50%, 100%) the PEI-g-D-DF Young's moduluss after processing, the enantiomeric excess value set up out with poly-
Compound Young's moduluss linear relationship chart.On this basis, we determine three groups of " unknown " ribose samples, and the result obtaining can be very
The good Linear Quasi zygonema obtaining before of coincideing, illustrates that this enantiomeric excess assay method is very accurate.
Embodiment 6
Using similar method in embodiment 5, by the measurement of surface of polymer material Young's moduluss, obtain Young mould
Linear relationship between amount and deoxyribose enantiomeric excess value.Equally adopt three groups of unknown deoxyribose blend sample,
Examine the accuracy of method.As shown in figure 14.
In Figure 14, by measuring, through five groups of different deoxyribose enantiomeric mixture (enantiomeric excess values
For：- 100%, -50%, 0,50%, 100%) the PEI-g-D-DF Young's moduluss after processing, the enantiomeric excess value set up out
With polymer Young's moduluss linear relationship chart.On this basis, we determine three groups of " unknown " deoxyribose samples, obtain
Result can be coincide the Linear Quasi zygonema obtaining before well, illustrates that this enantiomeric excess assay method is very accurate.
It is understood that glucose, xylose, lyxose, arabinose or mannose can also measure with reference to the method
Enantiomeric excess value.
Claims (4)
1. a kind of method measuring monosaccharide enantiomeric excess value, it comprises the steps：
1) using the method for Electrostatic Absorption, dipeptides polyethyleneimine polymers are grafted to microcrystalline quartz body balance chip surface, shape
Become thin polymer film；
Described dipeptides polyethyleneimine polymers areWherein, n is the degree of polymerization,
In the range from 5 to 200000；
2) it is utilized respectively the monosaccharide solutions soaking step 1 of different known enantiomeric excess values) the microcrystalline quartz body balance that obtains
Chip；
3) monosaccharide solutions of above-mentioned different known enantiomeric excess value are measured respectively using the mechanical mode of atomic force microscope
The Young's moduluss size of the thin polymer film after immersion, obtains the line that thin polymer film Young's moduluss are with respect to enantiomeric excess value
Sexual intercourse curve；
4) monosaccharide solutions of unknown enantiomeric excess value are provided, by the monosaccharide solutions soaking step of described unknown enantiomeric excess value
1) the microcrystalline quartz body balance chip obtaining, the mechanical mode using atomic force microscope measures described unknown enantiomeric excess value
Monosaccharide solutions soak after thin polymer film Young's moduluss, this Young's modulus be worth corresponding linear relationship curve on mapping
Body excessive value is test result.
2. the method for claim 1 is it is characterised in that described step 2) in monosaccharide solutions be ribose, deoxyribose,
Glucose, xylose, lyxose, arabinose or mannose.
3. the method for claim 1 is it is characterised in that described dipeptides polyethyleneimine polymers are anti-by replacing
Should, the dipeptides of chloracetyl chlorination is grafted on the side chain of the polyethyleneimine that the degree of polymerization is 5 to 200000, obtains described dipeptides
Polyethyleneimine polymers, wherein, described dipeptides isThe dipeptides of described chloroacetylation is
4. method as claimed in claim 3 is it is characterised in that the preparation method bag of described dipeptides polyethyleneimine polymers
Include following steps：
1) described dipeptides and triethylamine are dissolved among anhydrous chloroform solution, under stirring condition, by chloracetyl chloride dropwise Deca
To in above-mentioned solution, after completion of dropwise addition, react 10-14 hour under room temperature, obtain the dipeptides 1 of chloroacetylation；
2) under room temperature condition, by polyethyleneimine, sodium iodide and potassium carbonate are dissolved in anhydrous DMF solution,
Under stirring condition, the DMF solution Deca dissolved with 1 is dropwise added drop-wise among above-mentioned solution, lucifuge nitrogen is protected
React 22-26 hour under the conditions of shield, can get dipeptides polyethyleneimine polymers PEI-g-D-DF through purification；
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| US6270640B1 (en) * | 1998-04-29 | 2001-08-07 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Polymerized oligopeptide-surfactant chiral micelles |
| CN101921376B (en) * | 2010-07-06 | 2012-04-04 | 武汉理工大学 | Chiral three-component polymer with recognition capability, preparation and application thereof |
| CN103558325A (en) * | 2013-10-31 | 2014-02-05 | 中南大学 | Method for directly determining enantiomer excess of chiral compound in mixed sample |
| CN104215680B (en) * | 2014-09-02 | 2016-09-07 | 天津大学 | Capillary Electrophoresis speed difference pattern measures the device of compound Enantiomer excess value |
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