CN102806070B - Material and method for separating heavy metals from traditional Chinese medicine extract and food - Google Patents
Material and method for separating heavy metals from traditional Chinese medicine extract and food Download PDFInfo
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Abstract
The invention relates to a material and method for separating heavy metals from traditional Chinese medicine extract and food. The material is prepared by covalent bonding of surface-modified functionalization radical (amino) of mesoporous silicon dioxide nano particles with a compound shown in Formula I. The material can be used for removing trace lead, mercury cadmium and other harmful heavy metals from the traditional Chinese medicine extract and has no effect on active ingredients of the traditional Chinese medicine extract. The material has the advantages of wide application scope, high removing ability, high selectivity, reproduction and the like.
Description
Technical field
The invention belongs to heavy metal separation field.Specifically, the present invention relates to a kind of material for separating of heavy metal in Chinese medicine extract, food and method.
Technical background
Heavy metal is one of the important pollutant of Chinese medicine, food, the large key factor that it is restriction Chinese medicine that content of beary metal exceeds standard, food product strides forward to international market, due to exceeding standard of traditional Chinese medicine heavy metal content, cause Chinese medicine to export and be subject to serious obstruction, this problem has more and more been subject to concern and the attention of people.The content of current countries in the world to the heavy metal in Chinese medicine and Chinese patent drug is proposed strict requirement, 2005 version " Chinese Pharmacopoeia " also to add in Chinese medicine plumbous (Pb), cadmium (Cd), arsenic (As), mercury (Hg), the assay method of copper (Cu) 5 kinds of harmful elements and limit standard, this is for raising Chinese medicine quality, uphold one's heritage medicine reputation in the world, Chinese medicine is gone to the world, promotes the well-being of mankind and have great importance.
The heavy metal pollution of trace, can produce enrichment by biological chain effect.As people because drink or the edible medicine by heavy metal pollution, when in-vivo heavy metal content is too high, just various disease can be caused.If cadmium poisoning is by causing the pathology of liver, kidney and bone, cause anaemia or neuralgia, the Itai-itai diseases that Japan is popular in one's early years, be exactly for a long time edible " cadmium rice " cause.It can suppress liver cell mitochondria oxidative phosphorylation process, makes tissue metabolism that obstacle occur, has teratogenesis, carcinogenic, mutagenesis to people; Lead is that it all has harm to nervous system, hemopoietic function of bone marrow, digestive system, male reproductive system etc. to the great heavy metal species of harm.Particularly brain is in the children of nervous system sensitive periods, has special sensitiveness to lead.Research shows that the feeblemindedness incidence of disease of children raises with the increasing of lead contamination degree.
Remove the method for heavy metal in Chinese medicine, generally adopt UF membrane, solvent extraction is separated with macroporous absorbent resin.UF membrane is separated to use in traditional Chinese medicine heavy metal and fouling membrane can occurs and be separated the decay of flux, and then limits it and apply further; Solvent extraction in processes medicine heavy metal time have employed a large amount of organic solvents, determine the method and be not suitable for being applied to the separation of heavy metal in Chinese medicine; Macroporous absorbent resin partition method is comparatively large on Effective Component of Chinese Medicine impact, and is difficult to reach effective separation to the heavy metal of trace in Chinese medicine.Therefore, still need the material for separating of heavy metal in Chinese medicine extract, food and method, to overcome the deficiency of above-mentioned separation method.
Summary of the invention
The invention provides a kind of parting material, it is obtained by covalent bonding containing amino carrier by R1 and surface by compound shown in formula I:
formula I
In formula,
Ring A is 5-14 unit aromatic ring, hetero-aromatic ring, heterocycle or carbocyclic ring;
R
1for-R
8-C (O) H;
R
2and R
3independently be selected from-NR separately
4r
5;
R
4and R
5independently be selected from-R separately
6-C (O)-NH-R
7-OH; With
R
6-R
7independently be selected from C1-C4 alkyl separately;
R
8for not existing or being selected from C1-C4 alkyl;
Wherein, R
2and R
3be connected with the adjacent carbon atom of ring A.
In one embodiment, ring A is selected from phenyl ring and C6-C8 cycloalkyl.
In one embodiment, R
1for C1-C2 alkyl-CHO.
In one embodiment, R
2and R
3for identical or different group.
In one embodiment, R
6for methyl, R
7for ethyl.
In one embodiment, formula I is as follows:
In one embodiment, described carriers selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), wherein, described carrier is through surface-functionalized and have the active group being selected from amino and halogen.
The present invention relates to parting material of the present invention or the purposes of formula I in separation of heavy metal ions.
In one embodiment, described compound removing for harmful heavy metal ions in Chinese medicine extract or food.
The invention provides the method for the heavy metal ion in a kind of sample separation, described method comprises use parting material processing sample of the present invention, thus isolates described heavy metal ion.
Accompanying drawing explanation
Fig. 1 shows scanning electron microscope (SEM) photograph (a:SEM) and the transmission electron microscope picture (b:TEM) of SM.
Fig. 2 shows little angle X-ray powder diffraction pattern (functional silica gel particle, parting material SM).
The mesoporous silica gel particle of Fig. 3 Presentation Function and the N of SM
2absorption-desorption thermoisopleth.
Fig. 4 shows the infrared spectrogram of compound 4-3.
The infrared spectrogram of Fig. 5 Presentation Function mesoporous silica gel particle.
Fig. 6 shows the infrared spectrogram of parting material SM.
Fig. 7 shows fluorescence chemical sensor S3 at the aqueous solution (H
2o, pH=6.56) in Hg
2+the titration fluorescence utilizing emitted light spectrogram of (0 ~ 16 μM).Insert figure: fluorescence intensity I
541nmwith Hg
2+the linear relationship chart of (0 ~ 1.0 μM).Condition: [S3]=1.0 μM, λ
ex=525nm, 25 DEG C.
Fig. 8 display contains Hg through SM process
2+before and after the aqueous solution, add the fluorescence pattern after fluorescence chemical sensor S3.Condition: [S3]=1.0 μM, λ
ex=525nm, 25 DEG C.
Fig. 9 shows the impact of duration of oscillation on SM recovery rate.
Figure 10 shows the impact of pH on SM recovery rate.
Figure 11 shows the impact of concentration of metal ions on SM recovery rate.
Figure 12 shows the main component of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.Before SM process, detector: λ=254nm.
Figure 13 shows the main component of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.After SM process, detector: λ=254nm.
Figure 14 shows the main component partial enlarged drawing of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.Before SM process, detector: λ=254nm.
Figure 15 shows the main component partial enlarged drawing of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.After SM process, detector: λ=254nm.
Figure 16 shows the main component of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.Before SM process, detector: λ=203nm.
Figure 17 shows the main component of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.After SM process, detector: λ=203nm.
Figure 18 shows the main component partial enlarged drawing of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.Before SM process, detector: λ=203nm.
Figure 19 shows the main component partial enlarged drawing of the careless extract of ginseng spirit corresponding to HPLC chromatographic peak.After SM process, detector: λ=203nm.
Detailed description of the invention
" alkyl " used herein comprises straight chain and branched alkyl, includes but not limited to methyl, ethyl, propyl group, butyl and isobutyl group etc.
" aromatic ring " used herein refers to monocycle, dicyclo or three cyclic aromatic groups containing 6 to 14 carbon atoms.
Useful aromatic ring comprises C6-14 aromatic ring, more preferably C6-10 aromatic ring.Typical C6-14 aromatic ring comprises the loop section of phenyl, naphthyl, phenanthryl, anthryl and indenyl.
" carbocyclic ring " used herein comprises the carbon ring group of cycloalkyl and fractional saturation.Useful cycloalkyl is C3-8 cycloalkyl, more preferably C5-8 cycloalkyl.Typical cycloalkyl comprises ring third class, cyclobutyl, cyclopenta, cyclohexyl and suberyl.
The carbon ring group of useful fractional saturation is cycloalkenyl group, such as cyclopentenyl, cycloheptenyl and cyclo-octene base.
" heterocycle " used herein refers to 3-7 person's monocycle that is saturated or fractional saturation, or 7-10 person's bicyclic system, it by carbon atom and from O, N, S optional 1-4 hetero atom form.
Useful saturated or fractional saturation heterocycle comprises the loop section of tetrahydrofuran base, pyranose, piperidyl, piperazinyl, pyrrolidinyl, imidazolidinyl, imidazolinyl, indolinyl, iso-dihydro-indole-group, quininuclidinyl, morpholinyl, different Chromanyl, Chromanyl, pyrazolidinyl and pyrazolinyl.
" hetero-aromatic ring " used herein refers to containing 5-14 annular atoms, and has 6, and 10 or 14 pi-electrons share in member ring systems, and contained annular atoms is carbon atom and 1-3 optional from oxygen, nitrogen, a sulphur hetero atom.Hetero-aromatic ring preferably containing 5-10 annular atoms.
Useful hetero-aromatic ring comprises the loop section of thienyl, benzo [b] thienyl, benzo [2,3-b] thienyl, furyl, pyranose, different benzopyranyl, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, isoindolyl, indazolyl, purine radicals, 4H-quinolizine base, isoquinolyl, quinolyl, isothiazolyl, isoxazolyl, furazan base, benzimidazolyl etc.
Preferably, ring A is phenyl ring and C6-C8 cycloalkyl (such as cyclohexyl, suberyl, cycloheptenyl and cyclo-octene base etc.).
In one embodiment, R
1for C1-C2 alkyl-CHO.In another specific embodiment, R
1for-CHO.
In one embodiment, R
2and R
3for identical group.In another specific embodiment, R
2and R
3for different groups.
In one embodiment, R
4and R
5it can be identical group.In another specific embodiment, R
4and R
5for different groups.
In one embodiment, R
6for methyl.In one embodiment, R
7for ethyl.
In one embodiment, formula I is as follows:
Be applicable to carrier of the present invention and comprise various earth silicon material, polystyrene, polyacrylate, titanium oxide, polytetrafluoroethylene (PTFE) etc.Different carrier materials can carry out different surface-functionalized, draws active group as amino, halogen etc., and then Formula I compounds covalency keyed jointing.Preferably, mesoporous silica gel nano material.
In one embodiment, exemplary carrier structure is such as formula shown in II:
Can carry out different surface-functionalized to carrier material according to the method for bibliographical information.Such as, according to document (Chemistry of Materials.2002,14 (4): 1591-1597; Journal ofthe AmericanChemical Society.2002,124 (31): 9040-9041), the mesoporous silica gel particle of amino functional can be prepared.
Should be understood that the quantity of hydroxyl in formula II, amino quantity is all exemplary.The hydroxyl that those skilled in the art can adopt art technology method to prepare to have requirement according to actual needs and amino carrier.
An example of parting material of the present invention is as shown in formula III:
For example, formula I molecule of the present invention and parting material can adopt following synthetic route to synthesize:
As shown above, by raw material o-phenylenediamine, through halogenating reaction, obtain compound 4-1, then reacted by Vilsmeier-Haauc, introducing-CHO on aromatic ring, obtain intermediate product 4-2, finally carry out ester exchange reaction again, obtain multi-arm amide receptor 4-3, the acceptor 4-3 of gained and the mesopore silicon oxide of amido modified mistake are reacted, obtains parting material SM.
The chelation of parting material SM heavy metal ion mainly relies on the multi-arm imide structure of formula I, and has nothing to do with phenyl ring, can to its further structure of modification, and other rings such as naphthalene nucleus, phenanthrene ring, anthracene nucleus and indenes ring etc. can be used for replacing phenyl ring.
Parting material of the present invention can be used for the heavy metal ion in sample separation.
In one embodiment, parting material of the present invention is used for the separation of heavy metal ion in Chinese medicine extract, food or removes.
In one embodiment, lead ion, mercury ion and cadmium ion can be included but not limited to by the heavy metal ion that parting material of the present invention is separated or removes.
The method of directly soaking can be adopted parting material of the present invention to be added to pending sample as in Chinese medicine extract or food, thus the Chinese medicine extract containing heavy metal to be separated with food, Adsorption of Heavy Metal Ions.
Or can adopt and install in filled column by parting material of the present invention, the method utilizing post to be separated is separated with food the Chinese medicine extract containing heavy metal, Adsorption of Heavy Metal Ions.
Should be understood that herein, described " parting material " namely comprises by formula I and the covalently bound single parting material molecule formed of carrier, also comprises the mixture of multiple parting material molecule.
Adopt lead, mercury, cadmium harmful heavy metal in parting material separating traditional Chinese medicine extract of the present invention, the active ingredient of Chinese medicine extract is not affected.And, the harmful heavy metal ions such as lead, mercury, cadmium are had to high selectivity, adsorption rate are fast, the ability that removes is strong and reproducible feature.
Hereafter the present invention is described the mode with specific embodiment.Should be understood that these embodiments are only illustrative, and nonrestrictive.The reagent used in embodiment, unless otherwise stated, be all that routine is buied from the market, its usage and consumption all can use according to the usage of routine and consumption.
Instrument and reagent
Common solvents used all re-distillations through molecular sieve drying.Experiment test instrument has Avance 400MHz (Bruker) NMR (TMS is interior mark), HP 5989A mass spectrograph, Varian CaryEclipse XRF,
melting point apparatus, Vario EL III elemental analyser, all fluorescence emission spectrums are all 25 DEG C of tests.Hitachi S-520 SEM (SEM), JEM-2100 transmission electron microscope (TEM), Nicolet NEXUS 470 infrared spectrometer, Rigaku D/Max-RB diffractometer (CuK alpha ray (λ=0.15418nm) is radiation source), Quantachrome Nova 4000e specific surface and Porosimetry.Carried out the analysis (ICP-AES method) of tenor by ICP-AES (Varian 710ES), column chromatography silica gel is Haiyang Chemical Plant, Qingdao's product (200-300 order).
Embodiment 1: the synthesis of compound 4-1
Under argon shield; 10.0g (0.092mol) o-phenylenediamine, 13.0g (0.078mol) KI are dissolved in 250mL acetonitrile; add 75ml DIPEA, 100ml (0.92mol) bromoacetate; after adding hot reflux 24h; poured into by reactant liquor in 400ml distilled water, stir, dichloromethane extraction for several times; gained organic phase anhydrous sodium sulfate drying, decompression distillation obtains solid.Ethyl alcohol recrystallization, obtains white crystalline product, yield: 49.7% (20.80g).Fusing point: 35.4 ~ 37.0 DEG C.
1H NMR(400MHz，CDCl
3，25℃)：δ7.04(d，J＝5.6Hz，2H)，6.93-6.98(m，2H)，4.30(s，8H)，4.09-4.14(m，8H)，1.20(t，J＝7.2Hz，12H)。
Embodiment 2: the synthesis of compound 4-2
5.045g (0.011mol) compound 4-1 is dissolved in 120ml (1.63mol) N, in dinethylformamide, add 20ml (0.25mol) pyridine, be placed in ice bath, 50ml (0.22mol) POCl3 dropwise drips, 1h drips, continue in ice bath to stir 2h, then reaction 20h is continued under being warmed up to 50 DEG C of conditions, reactant liquor is poured in the ice water solution containing potash, stir 30min, dichloromethane extraction three times, gained organic phase anhydrous sodium sulfate drying, be spin-dried for solvent, rapid column chromatography (ethyl acetate: benzinum=2: 1v/v), decompression is spin-dried for solvent and obtains purplish red solid.Ethyl alcohol recrystallization, obtains white crystal.Yield: 40.45% (2.17g).Fusing point: 63.1 ~ 64.9 DEG C.
1H NMR(400MHz，CDCl
3，25℃)：δ9.85(s，-CHO，1H)，7.61(s，1H)，7.50(d，J＝8.0Hz，1H)，7.11(d，J＝8.4Hz，1H)，4.43(s，4H)，4.29(s，4H)，4.14(t，J＝7.2Hz，8H)，1.23(t，J＝7.2Hz，12H)。
Embodiment 3: the synthesis of compound 4-3
Under argon shield, the compound 4-2 of 2.0g (4.16mmol) is dissolved in 100ml acetonitrile solution, adds 100ml (2mol) monoethanolamine, after adding hot reflux 7h, decompression distillation obtains yellow oily liquid.Add 15ml (0.37mol) methyl alcohol, 6ml (0.079mol) trifluoroacetic acid, 1ml distilled water, stirs 30min at 50 DEG C.Rapid column chromatography (carrene: methyl alcohol: triethylamine=20: 4: 1; V/v/v), decompression distillation obtains dark brown oil product liquid.Yield: 90% (1.8g).
1H NMR(400MHz，D
2O，25℃)：δ9.61(s，-CHO，1H)，7.48(s，2H)，7.03(d，J＝4.4Hz，1H)，4.24(s，4H)，4.03(s，4H)，3.42～3.45(m，8H)，3.16～3.19(m，8H).
13C NMR(100MHz，D
2O，TMS)：δ194.68，181.42，172.55，172.45，172.39，172.29，172.15，170.10，147.57，139.96，130.12，127.17，122.49，120.34，59.85，54.82，54.50，54.42，48.88，41.27，41.17，23.30ppm.HR-MS(ES+)Calcd for([M+Na
+])，563.2441；Found，563.2433。
Embodiment 4: the synthesis of amino functional mesopore silicon oxide
According to method (Chemistry of Materials.2002,14 (4): 1591-1597 of bibliographical information; Journal of the American Chemical Society.2002,124 (31): 9040-9041), in the round-bottomed flask of 250mL, by 0.83g NaOH (20.75mmol) and 1.52g softex kw (CTAB, 4.2mmol) be mixed in 80mL water, 30min is stirred at 80 DEG C, completely soluble in water to CTAB.Subsequently, add 1.24g 3-(triethoxysilane) propyl group amine (5.6mmol), after stirring 2h in 80 DEG C, start to drip 7mL (3.46mmol) ethyl orthosilicate, 30min dropwises, and after continuing to stir 2h, stops reaction at 80 DEG C, hot suction filtration, obtains white filter cake.Filter cake is dispersed in (200mL) in the methyl alcohol containing 10mL hydrochloric acid, return stirring 24h, filters to obtain white solid after drying at 90 DEG C, dries, obtains the mesoporous silica gel particle of amino functional.
Embodiment 5: the synthesis of parting material SM
According to method (the AngewandteChemie-International Edition.2007 of the complex functionality mesoporous silica gel of bibliographical information, 46 (3): 338-352), in the round-bottomed flask of 100mL, the mesoporous silica gel uniform particle that 3g contains amino functional is scattered in 30mL methyl alcohol, add 100mg (0.185mmol) compound 4-3, under stable stirring, be warming up to backflow, after 8h, stop reaction, leave standstill and be cooled to room temperature.Suction filtration obtains thick product, washes for several times, dry, transfer in 30mL methyl alcohol with ethanol, and backflow 4h, suction filtration obtains the faint yellow final products of 3g, and this product is parting material SM.
Embodiment 6: the sign of parting material SM
Characterized by SEM (SEM) and transmission electron microscope (TEM).The shooting of SEM image is carried out under Hitachi S-520 SEM.Nano particle is dispersed in water, ultrasonic disperse, measures 10 μ L with micropipette rifle and drip on the glass surface, be placed in drier dried overnight, directly take.The shooting of TEM image is carried out under JEM-2100 transmission electron microscope (voltage k=200keV).Be dispersed in by nano particle in ethanol, ultrasonic disperse, be dispersed in (200mesh) on copper mesh, vacuum drying, directly takes.The analyzing and processing of SEM, TEM image is all carried out on DigitalMicrograph software.As shown in Figure 1, it is homogeneous distribution that above-described embodiment prepares gained SM to result, disperses separately.Calculated by DM (Digital Micrograph software) software, the diameter d=100 ± 8nm of SM also has poroid in more uniform hexagon (Fig. 1 b): TEM).
X-ray diffraction test is carried out under Rigaku D/Max-RB diffractometer, and with CuK alpha ray (λ=0.15418nm) for radiation source, sweep speed is 2 DEG C of min
-1, test specification is at 0.6 ~ 10 DEG C.As shown in Figure 2, contrast-NH
2the mesoporous silica gel nano particle of functionalization and the little angle X-ray powder diffraction pattern of parting material SM, X-ray diffraction peak, mesoporous silica gel nano particle typical little angle is in 2 θ=2 DEG C, and, do not change along with the introducing of multi-arm amide receptor, SM remains the characteristic of mesoporous silica gel carrier material.
Low temperature N
2adsorption isotherm is determined on Quantachrome Nova 4000e analyzer and carries out.Before sample test under 423K vacuum activating, be adsorbate with High Purity Nitrogen, under liquid nitrogen temperature, (77K) measures adsorption-desorption isothermal.Specific area obtains according to BET equation, and the pore volume of sample, pore-size distribution adopt BJH model treatment low temperature nitrogen desorption isotherm to calculate.The low temperature N of mesoporous silica gel material
2as shown in Figure 3, the mesoporous silica gel particle of amino functional and the adsorption-desorption isothermal of parting material SM are typical IV types to adsorption-desorption isothermal, at p/p
0obvious hysteretic loop is had between=0.3 ~ 0.5.The specific area of the mesoporous silica gel particle of amino functional is 1138m
2g
-1, average pore size, pore volume are 1.384nm, 0.875cm respectively
3g
-1(table 1).After the amino on surface and the reaction of multi-arm amide receptor, the aperture of gained SM, pore volume have no significant change (1.387nm, 0.817cm
3g
-1), specific area is changed to 955m
2g
-1, this is because mesoporous silica gel particle surface covalent bond has connected organic molecule, and specific area is declined to some extent.
Table 1: the mesoporous silica gel particle of functionalization and the BET specific surface area of SM, pore volume, aperture
| Material | BET specific surface area [m 2/g] | Average pore size [nm] | Pore volume [cm 3/g] |
| The mesoporous silica gel of functionalization | 1138 | 1.384 | 0.875 |
| SM | 955 | 1.387 | 0.817 |
FT-IR test is carried out under Nicolet NEXUS 470 infrared spectrometer.By nano particle vacuum drying, be with KBr mixing, carry out FT-IR test.Can be found out by contrast multi-arm amide receptor, the mesoporous silica gel particle of amino functional and the FT-IR spectrogram (Fig. 4,5,6) of parting material SM: as Fig. 5, wave number is at 1500 ~ 1750cm
-1vibration be attributed to the vibration of the mesoporous silica gel particle alkyl chain of functionalization; As Fig. 6, wave number is at 2450cm
-1vibration be the vibration of multi-arm amide receptor unsaturated double-bond, demonstrate acceptor covalent bond thus further and be connected on mesoporous silica gel particle.
Embodiment 7: the performance test of parting material SM
We adopt fluorescence chemical sensor S3 (Organic Letters.2006,8 (17): 3721-3724), for the mensuration of metal ion content.Concrete grammar is as follows: preparation, containing the aqueous solution ([S3]=1.0 μM) of fluorescence chemical sensor S3, drips Hg
2+, measure the fluorescence spectrum of system, and gained fluorescence pattern changed into the graph of a relation (the insertion figure in Fig. 7) of fluorescence intensity-concentration of metal ions, as the metal ion quantitation curves in follow-up test.
In following experiment, the recovery rate E (%) of SM to metal ion is calculated by following formula 1, wherein: C
0: the initial concentration of metal ion; C
e: concentration (the mol L of metal ion after SM process
-1).
E (%)=[(C
0-C
e)/C
0] × 100 (formula 1).
Preparation is containing Hg
2+(1 × 10
-5m) aqueous solution 20mL, gets 10mL containing Hg
2+the aqueous solution add SM (30mg), dispersed, stir 3min, centrifugation, gets supernatant liquor, adds fluorescence chemical sensor S3, measure fluorescence spectrum.As shown in Figure 8, the fluorescence intensity of system obviously reduces acquired results, quantitatively can be calculated according to calibration curve, SM to Hg
2+recovery rate can reach more than 95%.Meanwhile, we also compared for the mesoporous silica gel particle of amino functional to containing Hg
2+the impact of the aqueous solution, found that and there is no obvious adsorbing separation effect.Also confirm thus: the SM modified through multi-arm amide receptor can be used for Hg
2+adsorbing separation.
We have investigated different duration of oscillation t to the impact of SM recovery rate.Take 30mg SM respectively, add redistilled water, wetting, centrifugation, the SM (removing the physisorption of mesoporous silica gel material itself) of gained inactivation, even suspension is in containing Hg
2+(1 × 10
-5m) in the aqueous solution (10mL), suspension is at room temperature through the concussion of different time (1 ~ 10min), centrifugal, carefully measure supernatant liquor (3mL), add fluorescence chemical sensor S3, measure fluorescence spectrum, ask the concentration calculating metal ion according to calibration curve.As shown in Figure 9, in a short period of time (3min), SM is to Hg for result
2+recovery rate just reach capacity, this may be because multi-arm acid amides itself is to Hg
2+the porous of strong complexing power and mesoporous silica gel nanoparticulate carriers material, is easy to the diffusion of metal ion.
We have investigated again the impact of pH on SM recovery rate.Take 30mg SM respectively, add redistilled water, wetting, centrifugation, the SM (removing the physisorption of mesoporous silica gel material itself) of gained inactivation, even suspension is in the Hg of different pH value
2+(1 × 10
-5m) in the aqueous solution (10mL), suspension at room temperature shakes 180 seconds, centrifugal, carefully measures supernatant liquor (3mL), adds fluorescence chemical sensor S3, measures fluorescence spectrum, asks the concentration calculating metal ion according to calibration curve.As shown in Figure 10, in very wide pH 3 ~ 12 scope, SM is to Hg for acquired results
2+all there is good adsorption separation performance; this is the rare performance of solid-phase adsorbent of report at present; this also demonstrates mesoporous silica gel carrier material further while the performance of protection multi-arm amide receptor own; give again the performance that it is special, namely within the scope of very wide pH (pH3 ~ 12) can rapidly (t=3min) in conjunction with Hg
2+realize Hg
2+adsorbing separation.
We have also investigated different ions concentration to SM for Hg
2+the impact be separated.Take 30mgSM respectively, add redistilled water, wetting, centrifugation, gained SM (removing the physisorption of mesoporous silica gel material itself), even suspension is in the Hg of different content
2+(1 × 10
-7, 1 × 10
-6, 1 × 10
-5, 3 × 10
-5, 5 × 10
-5, 7 × 10
-5, 8.5 × 10
-5, 1 × 10
-4) in the aqueous solution (10mL, pH=6.56), suspension at room temperature shakes 180 seconds, centrifugal, carefully measure supernatant liquor (3mL), add fluorescence chemical sensor S3, measure fluorescence spectrum, ask the concentration calculating metal ion according to calibration curve.
Maximal absorptive capacity (Q, the mol g of SM
-1) be can be calculated by following formula 2, wherein: C
0: the initial concentration of metal ion; C: concentration (the mol L of metal ion after SM process
-1); V: metal ion solution volume (L); The quality (g) of m:FS
Q=[(C
0-C) × V]/m (formula 2).
By changing different Hg
2+the mensuration of concentration of aqueous solution, we can obtain the maximal absorptive capacity of parting material SM, can be calculated according to formula 2, the maximum adsorption capacity Q=21mg Hg of SM
2+/ g SM, the multi-arm acid amides quantity that the particle diameter of adsorption capacity and mesoporous silica gel particle carrier itself, structure, key connect is relevant.
Preparation is respectively containing Hg
2+, Pb
2+, Cd
2+the aqueous solution 20mL of (30ppm and 10ppm), gets 10mL and adds containing the aqueous solution of heavy metal ion the parting material (100mg) prepared by example 2, dispersed, stir 3min, centrifugation, gets supernatant liquor, and clear liquid is directly used in ICP-AES test.Parting material Hg
2+, Pb
2+, Cd
2+recovery rate the results are shown in Table 2 and table 3.
Table 2
Table 3
Embodiment 8:SM is used for the separation of heavy metal in Chinese medicine extract
In view of the separating property of SM uniqueness, we are applied to the separation of heavy metal in Chinese medicine extract.Concrete steps are as follows: get 25mL Chinese medicine stoste, add 500mg functional silica gel, after uniform stirring 3min, leave standstill 0.5h, a large amount of silica gel precipitates, gets supernatant liquor, centrifugation (r=4000 turns/min), removes a small amount of remaining silica gel, and clear liquid can be directly used in ICP-AES test.Shown in acquired results table 4, ion concentration is by ICP-AES quantitative analysis (ICP-AES test) gained.
Table 4 Chinese medicine extract is metal ion content change before and after SM process
| Metal ion | Content (ppm) before being separated | Content (ppm) after being separated |
| Hg 2+ | 0.008 | 0.002 |
| pb 2+ | 0.085 | 0.070 |
| Cd 2+ | 0.003 | 0.002 |
As shown in Table 4, the parting material that prepared by embodiment 5 still has adsorbing separation effect to the mercury of trace in Chinese medicine stoste, lead, cadmium heavy metal ion.
Embodiment 9:SM, active carbon, chitosan resin are used for the separation contrast of heavy metal in Chinese medicine extract
In order to embody the efficient separating property of SM, we compared for SM, active carbon, chitosan resin for the separating effect of heavy metal in Chinese medicine extract.Concrete steps are as follows: get 25mL Chinese medicine stoste three parts, add 500mg functional silica gel SM, active carbon, chitosan resin respectively, after uniform stirring 3min, leave standstill 0.5h, get supernatant liquor, centrifugation (r=4000 turns/min), removes adsorbent (functional silica gel SM, active carbon, chitosan resin), and clear liquid can be directly used in ICP-AES test.Shown in acquired results table 5, ion concentration is by ICP-AES quantitative analysis (ICP-AES test) gained.
Table 5
Can be obtained by table 5, SM still has adsorbing separation effect to the content of beary metal of trace in Chinese medicine extract, and active carbon, chitosan resin are not obvious to the adsorption effect of its heavy metal.Result can obtain thus, and SM prepared by the present invention, compared to other common heavy metal parting material, can be used for the separation of trace heavy metal in Chinese medicine extract.
In order to investigate the impact of SM on its Chinese medicine extract composition, we compared for by HPLC the change of component that the clever careless extract of ginseng is separated front and back.The main nutritional labeling of Chinese medicine extract comprises American Ginseng, glossy ganoderma, Cordyceps sinensis etc.Wherein, the main component of American Ginseng is ginsenoside and triterpenoid saponin, and this kind of material is generally adopt the wavelength UV detector of λ=203nm to detect; The main component of glossy ganoderma is GL-B and triterpene compound, comprise GL-B, glossy ganoderma polypeptide, triterpenes, 16 seed amino acids (wherein containing seven kinds of essential amino acids), protein, steroid class, sweet mellow wine, coumarin glycosides, alkaloid, organic acid, generally select λ=254nm UV-detector to detect; Cordyceps sinensis main component is cordycepic acid, cordycepin, amino acid, sterol, sweet mellow wine, alkaloid, vitamin B1, B2, polysaccharide and mineral matter etc.General is all for ucleosides analysis wherein, selects λ=254nm UV-detector to detect.Therefore, during the change of component that we utilize HPLC to analyze before and after the clever careless extract separation of ginseng, the UV-detector of two wavelength (λ=203,254nm) is selected to carry out trace analysis respectively.
We first adopt the UV-detector of λ=254nm wavelength to detect and analyze the impact of SM on the clever careless extract main component of ginseng.Contrast Figure 12,13, the main component (as t=1.95,2.08,2.50,3.90,14.25,15.74min etc.) of joining clever careless extract there is no significant change.
By Figure 14,15 enlarged drawing can obtain, some micro constitutents (as t=6.95,7.85,9.52,10.58,12.62,14.95,15.03min etc.) of joining clever careless extract do not have significant change after SM process yet.
We adopt again the detector of λ=203nm wave band to detect and analyze SM to the impact of its composition.Contrast Figure 16,17, the main component (as t=1.95,2.08,2.50,3.90,14.25,15.74min etc.) of joining clever careless extract there is no significant change.
By Figure 18,19 partial enlarged drawing can obtain, some micro constitutents (as t=6.95,7.85,9.52,10.58,12.62,14.95,15.03min etc.) of joining clever careless extract do not have significant change after SM process.
To sum up can obtain, SM can be used for joining trace metal (Hg in clever careless extract
2+, Pb
2+, Cd
2+) separation, what is more important, after SM process, extract steady quality, has no significant effect its main component.
The regeneration of embodiment 10:SM
Get the functional silica gel that metal ion is crossed in 1g complexing, add 15mL 1 × 10
-2the EDTA solution of M, dispersed, stir 3min, centrifugation, remove supernatant liquor, add clean deionized water, cyclic washing three times, centrifugation obtains functional silica gel, dries in 120 DEG C of baking ovens, obtains regenerating SM.
Claims (18)
1. a parting material, is characterized in that, it passes through R by compound shown in following formula I
1the carrier containing active group with surface is obtained by covalent bonding:
In formula,
Ring A is 5-14 unit aromatic ring, hetero-aromatic ring, heterocycle or carbocyclic ring;
R
1for-R
8-C (O) H;
R
2and R
3independently be selected from-NR separately
4r
5;
R
4and R
5independently be selected from-R separately
6-C (O)-NH-R
7-OH; With
R
6-R
7independently be selected from C1-C4 alkyl separately;
R
8for not existing or being selected from C1-C4 alkyl;
Wherein, R
2and R
3be connected with the adjacent carbon atom of ring A.
2. parting material as claimed in claim 1, it is characterized in that, ring A is selected from phenyl ring and C6-C8 cycloalkyl.
3. parting material as claimed in claim 1, is characterized in that, R
1for C1-C2 alkyl-CHO.
4. parting material as claimed in claim 2, is characterized in that, R
1for C1-C2 alkyl-CHO.
5. the parting material according to any one of claim 1-4, is characterized in that, R
2and R
3for identical or different group.
6. the parting material according to any one of claim 1-4, is characterized in that, R
6for methyl, R
7for ethyl.
7. parting material as claimed in claim 5, is characterized in that, R
6for methyl, R
7for ethyl.
8. parting material as claimed in claim 1, it is characterized in that, formula I is as follows:
9. the parting material according to any one of claim 1-4, it is characterized in that, described carriers selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), wherein, described carrier is through surface-functionalized and have the active group being selected from amino and halogen.
10. parting material as claimed in claim 5, it is characterized in that, described carriers selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), wherein, described carrier is through surface-functionalized and have the active group being selected from amino and halogen.
11. parting materials as claimed in claim 6, it is characterized in that, described carriers selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), wherein, described carrier is through surface-functionalized and have the active group being selected from amino and halogen.
12. parting materials as claimed in claim 7 or 8, it is characterized in that, described carriers selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), wherein, described carrier is through surface-functionalized and have the active group being selected from amino and halogen.
13. parting materials as claimed in claim 1, it is characterized in that, described parting material is as follows:
Parting material according to any one of 14. claim 1-13 or the purposes of formula I in separation of heavy metal ions.
15. purposes as claimed in claim 14, is characterized in that, described parting material removes for harmful heavy metal ions in Chinese medicine extract or food.
16. purposes as described in claims 14 or 15, it is characterized in that, described heavy metal ion is selected from lead ion, mercury ion and cadmium ion.
The method of the heavy metal ion in 17. 1 kinds of sample separation, is characterized in that, described method comprises the parting material processing sample used according to any one of claim 1-13, thus isolates described heavy metal ion.
18. methods as claimed in claim 17, it is characterized in that, described heavy metal ion is selected from lead ion, mercury ion and cadmium ion.
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| CN107986414A (en) * | 2017-12-08 | 2018-05-04 | 沈阳化工大学 | A kind of method of heavy metal ion in removal Chinese traditional medicine water extract |
| CN108434849B (en) * | 2018-04-25 | 2019-01-15 | 安徽百禾堂中药饮片有限公司 | A kind of Internet of Things and automation Chinese medicine remove removing heavy metals device |
| CN109046259B (en) * | 2018-09-13 | 2021-08-06 | 上海海关工业品与原材料检测技术中心 | Modified mesoporous silica material, preparation method and application thereof |
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