CN102806070A - 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 PDF

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CN102806070A
CN102806070A CN2011101487092A CN201110148709A CN102806070A CN 102806070 A CN102806070 A CN 102806070A CN 2011101487092 A CN2011101487092 A CN 2011101487092A CN 201110148709 A CN201110148709 A CN 201110148709A CN 102806070 A CN102806070 A CN 102806070A
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parting material
chinese medicine
heavy metal
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CN102806070B (en
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钱旭红
朱维平
何春生
徐玉芳
孙晓龙
任龙
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East China University of Science and Technology
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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

A kind of material and method that is used for separating traditional Chinese medicine extract, food heavy metal
Technical field
The invention belongs to the heavy metal separation field.Particularly, the present invention relates to a kind of material and method that is used for separating traditional Chinese medicine extract, food heavy metal.
Technical background
Heavy metal is one of important pollutant of Chinese medicine, food; It is the big key factor that restriction Chinese medicine, food product stride forward to the international market that content of beary metal exceeds standard; Because exceeding standard of Chinese medicine content of beary metal; Cause the Chinese medicine outlet to receive serious obstruction, this problem has more and more received people's attention and attention.Countries in the world have all proposed strict requirement to the content of the heavy metal in Chinese medicine and the Chinese patent drug at present; " Chinese pharmacopoeia has also increased plumbous (Pb), cadmium (Cd), arsenic (As), mercury (Hg), 5 kinds of determination of harmful elements methods of copper (Cu) and limit standard in the Chinese medicine to version in 2005; This is for improving the Chinese medicine quality; The medicine reputation in the world that upholds one's heritage goes to the world Chinese medicine, and promoting the well-being of mankind has great importance.
Trace heavy metals is polluted, and can produce enrichment through the biological chain effect.Because drink or the edible medicine that receives heavy metal pollution, during the heavy metal of body too high levels, just can cause various diseases as the people.To cause the pathology of liver, kidney and bone like cadmium poisoning, cause anaemia or neuralgia, popular Itai-itai diseases of Japan in one's early years, be exactly for a long time edible " cadmium rice " cause.It can suppress the liver cell mitochondria oxidative phosphorylation process, makes tissue metabolism that obstacle take place, and the people is had teratogenesis, carcinogenic, mutagenesis; 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 human harm.Particularly brain is in the nervous system children of sensitive periods, and lead is had special sensitiveness.The feeblemindedness incidence of disease that research shows children raises with the increasing of lead contamination degree.
Remove the method for heavy metal in the Chinese medicine, adopt that generally film separation, solvent extraction and macroporous absorbent resin separate etc.Film is separated in the Chinese medicine heavy metal and separates the decay that the film pollution can take place in the use and separate flux, and then has limited its further application; Solvent extraction has adopted a large amount of organic solvents when handling the Chinese medicine heavy metal, determined this method and be not suitable for being applied to the separation of heavy metal in the Chinese medicine; The influence of macroporous absorbent resin partition method centering pharmaceutically active ingredient is bigger, and to the inaccessible effective separation of the heavy metal of trace in the Chinese medicine.Therefore, still need be used for the material and the method for separating traditional Chinese medicine extract, food heavy metal, to overcome the deficiency of above-mentioned separation method.
Summary of the invention
The present invention provides a kind of parting material, and it contains amino carrier through R1 with the surface by compound shown in the formula I and obtains through covalent bonding:
Figure BDA0000066198780000021
formula I
In the 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 separately-NR 4R 5
R 4And R 5Independently be selected from separately-R 6-C (O)-NH-R 7-OH; With
R 6-R 7Independently be selected from the C1-C4 alkyl separately;
R 8For not existing or being selected from the C1-C4 alkyl;
Wherein, R 2And R 3Link to each other 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 1Be C1-C2 alkyl-CHO.
In one embodiment, R 2And R 3Be identical or different group.
In one embodiment, R 6Be methyl, R 7Be ethyl.
In one embodiment, formula I compound is as follows:
Figure BDA0000066198780000022
In one embodiment, said carrier is selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), and wherein, said carrier is through surface-functionalized and have an active group that is selected from amino and halogen.
The present invention relates to parting material of the present invention or the purposes of formula I compound in separation of heavy metal ions.
In one embodiment, said compound is used for removing of Chinese medicine extract or food harmful heavy metal ion.
The present invention provides the method for the heavy metal ion in a kind of sample separation, and said method comprises uses parting material of the present invention to handle sample, thereby isolates said heavy metal ion.
Description of drawings
Fig. 1 shows sem photograph (a:SEM) and the transmission electron microscope picture (b:TEM) of SM.
Fig. 2 shows little angle X-ray powder diffraction pattern (functionalization silica gel particle, parting material SM).
The mesoporous silica gel particle of Fig. 3 Presentation Functionization and the N of SM 2The absorption-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 that fluorescence chemical sensor S3 is at the aqueous solution (H 2O, pH=6.56) in to Hg 2+The titration fluorescence emission spectrogram of (0～16 μ M).Insert figure: fluorescence intensity I 541nmWith Hg 2+The linear relationship chart of (0～1.0 μ M).Condition: [S3]=1.0 μ M, λ Ex=525nm, 25 ℃.
Fig. 8 demonstration is handled through SM and is contained Hg 2+Before and after the aqueous solution, the fluorescence pattern behind the adding fluorescence chemical sensor S3.Condition: [S3]=1.0 μ M, λ Ex=525nm, 25 ℃.
Fig. 9 shows the influence of duration of oscillation to the SM recovery rate.
Figure 10 shows the influence of pH to the SM recovery rate.
Figure 11 shows the influence of concentration of metal ions to the SM recovery rate.
Figure 12 shows the main component of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.Before SM handles, detector: λ=254nm.
Figure 13 shows the main component of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.After SM handles, detector: λ=254nm.
Figure 14 shows the main component partial enlarged drawing of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.Before SM handles, detector: λ=254nm.
Figure 15 shows the main component partial enlarged drawing of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.After SM handles, detector: λ=254nm.
Figure 16 shows the main component of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.Before SM handles, detector: λ=203nm.
Figure 17 shows the main component of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.After SM handles, detector: λ=203nm.
Figure 18 shows the main component partial enlarged drawing of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.Before SM handles, detector: λ=203nm.
Figure 19 shows the main component partial enlarged drawing of the careless extract of ginseng spirit that the HPLC chromatographic peak is corresponding.After SM handles, detector: λ=203nm.
The specific embodiment
" 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 is meant monocycle, dicyclo or the three cyclophane family groups that contain 6 to 14 carbon atoms.
Useful aromatic ring comprises C6-14 aromatic ring, C6-10 aromatic ring more preferably.Typical C 6-14 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 the C3-8 cycloalkyl, more preferably the C5-8 cycloalkyl.Typical cycloalkyl comprises ring third class, cyclobutyl, cyclopenta, cyclohexyl and suberyl.
The carbon ring group of useful fractional saturation is a cycloalkenyl group, for example cyclopentenyl, cycloheptenyl and cyclo-octene base.
" heterocycle " used herein refers to 3-7 person's monocycle of saturated or fractional saturation, or 7-10 person's bicyclic system, and it is chosen 1-4 hetero atom wantonly by carbon atom with from O, N, S and forms.
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 contain 5-14 annular atoms, and has 6, and 10 or 14 pi-electrons are shared on member ring systems, and contained annular atoms be carbon atom and from oxygen, nitrogen, sulphur optional 1-3 hetero atom.The hetero-aromatic ring that preferably contains 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 (for example cyclohexyl, suberyl, cycloheptenyl and cyclo-octene base etc.).
In one embodiment, R 1Be C1-C2 alkyl-CHO.In another specific embodiment, R 1For-CHO.
In one embodiment, R 2And R 3Be identical group.In another specific embodiment, R 2And R 3Be different groups.
In one embodiment, R 4And R 5Can be identical group.In another specific embodiment, R 4And R 5Be different groups.
In one embodiment, R 6Be methyl.In one embodiment, R 7Be ethyl.
In one embodiment, formula I compound is as follows:
Figure BDA0000066198780000051
Be applicable to that carrier of the present invention comprises various earth silicon materials, polystyrene, polyacrylate, titanium oxide, polytetrafluoroethylene (PTFE) or the like.Different carrier materials can be carried out the different surface functionalization, draws active group like amino, halogen etc., and then cotype I compound covalency keyed jointing.Preferably, mesoporous silica gel nano material.
In one embodiment, exemplary carrier structure is suc as formula shown in the II:
Figure BDA0000066198780000061
Can carry out the different surface functionalization to carrier material according to the method for bibliographical information.For example, according to document (Chemistry of Materials.2002,14 (4): 1591-1597; Journal ofthe American Chemical Society.2002,124 (31): 9040-9041), can prepare the mesoporous silica gel particle of amino functional.
Should be understood that the quantity of hydroxyl among the formula II, amino quantity all are exemplary.Hydroxyl that those skilled in the art can adopt the 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 shown in formula III:
Figure BDA0000066198780000062
For example, formula I molecule of the present invention and parting material can adopt following synthetic route synthetic:
Figure BDA0000066198780000071
As shown above, begin, through halogenating reaction by the raw material o-phenylenediamine; Obtain compound 4-1, again through Vilsmeier-Haauc reaction, introducing-CHO on the aromatic ring; Obtain intermediate product 4-2, carry out ester exchange reaction at last again, obtain multi-arm acid amides acceptor 4-3; The acceptor 4-3 of gained and the mesopore silicon oxide of amido modified mistake are reacted, obtain parting material SM.
Parting material SM mainly is the multi-arm imide structure of dependence formula I compound to the chelation of heavy metal ion, and irrelevant with phenyl ring, can be to its further structure of modification, and other rings can be used for replacing phenyl ring like naphthalene nucleus, phenanthrene ring, anthracene nucleus and indenes ring etc.
Parting material of the present invention can be used for the heavy metal ion in the sample separation.
In one embodiment, parting material of the present invention is used for the separation of Chinese medicine extract, food heavy metal ion or removes.
In one embodiment, can be included but not limited to lead ion, mercury ion and cadmium ion by parting material separation of the present invention or the heavy metal ion that removes.
Can adopt the method for direct immersion that parting material of the present invention is added in pending sample such as Chinese medicine extract or the food, thereby the Chinese medicine extract that contains heavy metal is separated Adsorption of Heavy Metal Ions with food.
Perhaps, can adopt parting material of the present invention is installed in the filled column, the method for utilizing post to separate is separated Adsorption of Heavy Metal Ions to the Chinese medicine extract that contains heavy metal with food.
Should be understood that among this paper that said " parting material " promptly comprises by formula I compound and the covalently bound single parting material molecule that forms of carrier, also comprise the mixture of a plurality of parting material molecules.
Adopt lead, mercury, cadmium harmful heavy metal in the parting material separating traditional Chinese medicine extract of the present invention, to the not influence of active ingredient of Chinese medicine extract.And, to harmful heavy metal ions such as lead, mercury, cadmium have that high selectivity, adsorption rate are fast, the ability that removes is strong, and reproducible characteristics.
Hereinafter will be described the present invention with the mode of specific embodiment.Should be understood that these embodiment only are illustrative, and nonrestrictive.The reagent that is used among the embodiment except as otherwise noted, otherwise all is that routine is buied from the market, and its usage and consumption all can use according to the usage and the consumption of routine.
Instrument and reagent
Used common solvent all again the distillation and through molecular sieve drying.The experiment test instrument has Avance 400MHz (Bruker) NMR (TMS is interior mark); HP 5989A mass spectrograph; Varian Cary Eclipse XRF;
Figure BDA0000066198780000081
fusing point appearance; Vario EL III elemental analyser, all fluorescence emission spectrums are all 25 ℃ of tests.Hitachi S-520 SEM (SEM); JEM-2100 transmission electron microscope (TEM); Nicolet NEXUS 470 infrared spectrometers; Rigaku D/Max-RB diffractometer (CuK alpha ray (λ=0.15418nm) be radiation source), Quantachrome Nova 4000e specific surface and aperture analyzer.Carry out the analysis (ICP-AES method) of tenor through ICP-AES (Varian 710ES), column chromatography silica gel is Haiyang Chemical Plant, Qingdao's product (200-300 order).
Embodiment 1: compound 4-1's is synthetic
Figure BDA0000066198780000091
Under argon shield, 10.0g (0.092mol) o-phenylenediamine, 13.0g (0.078mol) KI are dissolved in the 250mL acetonitrile, add 75ml N; The N-diisopropylethylamine, 100ml (0.92mol) bromoacetate is behind the reflux 24h; Reactant liquor is poured in the 400ml distilled water, stirred, dichloromethane extraction for several times; Gained organic facies anhydrous sodium sulfate drying, decompression distillation gets solid.Ethyl alcohol recrystallization gets the white crystals product, yield: 49.7% (20.80g).Fusing point: 35.4～37.0 ℃.
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: compound 4-2's is synthetic
Figure BDA0000066198780000092
4-1 is dissolved in 120ml (1.63mol) N with 5.045g (0.011mol) compound, in the dinethylformamide, adds 20ml (0.25mol) pyridine; Place ice bath, 50ml (0.22mol) POCl3 dropwise drips, and 1h drips; Continue in the ice bath to stir 2h, be warmed up to then and continue reaction 20h under 50 ℃ of conditions, reactant liquor is poured in the frozen water solution of carbonated potassium; Stir 30min, dichloromethane extraction three times, gained organic facies anhydrous sodium sulfate drying; Revolve dried solvent, rapid column chromatography (ethyl acetate: benzinum=2: 1v/v), revolve dried solvent and obtain the purplish red solid by decompression.Ethyl alcohol recrystallization obtains white crystal.Yield: 40.45% (2.17g).Fusing point: 63.1～64.9 ℃.
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: compound 4-3's is synthetic
Figure BDA0000066198780000101
Under argon shield, be dissolved in the compound 4-2 of 2.0g (4.16mmol) in the 100ml acetonitrile solution, add 100ml (2mol) monoethanolamine, behind the reflux 7h, decompression distillation obtains yellow oily liquid.Add 15ml (0.37mol) methyl alcohol, 6ml (0.079mol) trifluoroacetic acid, 1ml distilled water, 50 ℃ are stirred 30min down.Rapid column chromatography (carrene: methyl alcohol: triethylamine=20: 4: 1; V/v/v), decompression distillation obtains dark brown oily liquids product.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: amino functional mesopore silicon oxide synthetic
Figure BDA0000066198780000102
Method (Chemistry of Materials.2002,14 (4): 1591-1597 according to bibliographical information; Journal of the American Chemical Society.2002; 124 (31): 9040-9041); In the round-bottomed flask of 250mL, (CTAB 4.2mmol) is mixed in the 80mL water with 0.83g NaOH (20.75mmol) and 1.52g softex kw; 80 ℃ are stirred 30min down, soluble in water fully to CTAB.Subsequently, add 1.24g 3-(triethoxysilane) propyl group amine (5.6mmol), behind 80 ℃ of stirring 2h, begin to drip 7mL (3.46mmol) ethyl orthosilicate, 30min dropwises, and after 80 ℃ 2h is stirred in continuation down, stops reaction, and hot suction filtration gets white filter cake.Filter cake is dispersed in (200mL) in the methyl alcohol that contains 10mL hydrochloric acid after 90 ℃ of oven dry, and refluxing and stirring 24h crosses and filters white solid, dries, and obtains the mesoporous silica gel particle of amino functional.
Embodiment 5: parting material SM's is synthetic
Figure BDA0000066198780000111
According to the method for the complex functionality mesoporous silica gel of bibliographical information (Angewandte Chemie-International Edition.2007,46 (3): 338-352), in the round-bottomed flask of 100mL; The mesoporous silica gel particle that 3g is contained amino functional is dispersed in the 30mL methyl alcohol; Add 100mg (0.185mmol) compound 4-3, be warming up to backflow under stable the stirring, behind the 8h; Stop reaction, leave standstill and be cooled to room temperature.Suction filtration obtains thick product, washes for several times with ethanol, and oven dry is transferred in the 30mL methyl alcohol, and backflow 4h, suction filtration get the faint yellow final products of 3g, and this product is parting material SM.
Embodiment 6: the sign of parting material SM
Characterize through 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 the water, and ultrasonic dispersion is measured 10 μ L with the micropipette rifle and is dropped on the glass surface, places the drier dried overnight, directly takes.The shooting of TEM image is carried out under JEM-2100 transmission electron microscope (voltage k=200keV).Nano particle is dispersed in the ethanol, and ultrasonic dispersion is dispersed in (200mesh) on the copper mesh with it, and vacuum drying is directly taken.Analyzing and processing to SEM, TEM image is all carried out on DigitalMicrograph software.The result is as shown in Figure 1, and the foregoing description prepares gained SM and is the homogeneous distribution, disperses separately.Through DM (Digital Micrograph software) computed in software, the diameter d of SM=100 ± 8nm also has poroid in the more uniform hexagon (Fig. 1 b): TEM).
X-ray diffraction test is carried out under Rigaku D/Max-RB diffractometer, and (λ=0.15418nm) is a radiation source, and sweep speed is 2 ℃ of min with the CuK alpha ray -1, test specification is at 0.6～10 ℃.As shown in Figure 2, contrast-NH 2The little angle X-ray powder diffraction pattern of the mesoporous silica gel nano particle of functionalization and parting material SM; X-ray diffraction peak, the typical little angle of mesoporous silica gel nano particle is in 2 θ=2 ℃; And; Do not change along with the introducing of multi-arm acid amides acceptor, SM has kept the characteristic of mesoporous silica gel carrier material.
Low temperature N 2Adsorption isotherm is determined on the Quantachrome Nova 4000e analyzer and carries out.Vacuum activation under 423K before the sample test is an adsorbate with high purity nitrogen, and (77K) measures the adsorption-desorption thermoisopleth under the liquid nitrogen temperature.Specific area obtains according to the BET equation, and the pore volume of sample, pore-size distribution adopt the BJH model to handle the low temperature nitrogen desorption isotherm and calculate.The low temperature N of mesoporous silica gel material 2The adsorption-desorption thermoisopleth is as shown in Figure 3, and the mesoporous silica gel particle of amino functional and the adsorption-desorption thermoisopleth of parting material SM are typical IV types, at p/p 0Tangible hysteretic loop is arranged 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 respectively 1.384nm, 0.875cm 3g -1(table 1).Behind amino and the multi-arm acid amides receptor response on surface, aperture, the pore volume of gained SM 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 descended to some extent.
Table 1: the mesoporous silica gel particle of functionalization and BET specific area, pore volume, the aperture of SM
Material BET specific 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
The FT-IR test is carried out under Nicolet NEXUS 470 infrared spectrometers.With the nano particle vacuum drying, be with the KBr mixing, carry out the FT-IR test.Can find out through contrast multi-arm acid amides acceptor, the mesoporous silica gel particle of amino functional and the FT-IR spectrogram (Fig. 4,5,6) of parting material SM: like Fig. 5, wave number is at 1500～1750cm -1Vibration ownership be the vibration of the mesoporous silica gel particle alkyl chain of functionalization; Like Fig. 6, wave number is at 2450cm -1Vibration be the vibration of multi-arm acid amides acceptor unsaturated double-bond, verified further that thus the acceptor covalent bond is connected on the mesoporous silica gel particle.
Embodiment 7: the performance test of parting material SM
Figure BDA0000066198780000131
We adopt fluorescence chemical sensor S3 (Organic Letters.2006,8 (17): 3721-3724), be used for the mensuration of metal ion content.Concrete grammar is following: preparation contains the aqueous solution ([S3]=1.0 μ M) of fluorescence chemical sensor S3, drips Hg 2+, measure the fluorescence spectrum of system, and change into the graph of a relation (the insertion figure among Fig. 7) of fluorescence intensity-concentration of metal ions to the gained fluorescence pattern, as the metal ion quantitative criterion curve in the follow-up test.
In the following experiment, SM calculates through following formula 1 the recovery rate E (%) of metal ion, wherein: C 0: the initial concentration of metal ion; C e: handle concentration (the mol L of metal ion afterwards through SM -1).
E (%)=[(C 0-C e)/C 0] * 100 (formula 1).
Preparation contains Hg 2+(1 * 10 -5M) aqueous solution 20mL gets 10mL and contains Hg 2+The aqueous solution add SM (30mg), evenly disperse, stir 3min, supernatant liquor is got in centrifugation, adds fluorescence chemical sensor S3, measures fluorescence spectrum.The gained result is as shown in Figure 8, and the fluorescence intensity of system obviously reduces, can get according to the calibration curve quantitative Analysis, SM to Hg 2+Recovery rate can reach more than 95%.Simultaneously, we also contrasted amino functional the mesoporous silica gel particle to containing Hg 2+The influence of the aqueous solution, the result finds not have tangible adsorbing separation effect.Also confirm thus: the SM that modifies through multi-arm acid amides acceptor can be used for Hg 2+Adsorbing separation.
We have investigated the influence of different duration of oscillation t to the SM recovery rate.Take by weighing 30mg SM respectively, add redistilled water, wetting, centrifugation, the SM of gained inactivation (removing the physisorption of mesoporous silica gel material itself) evenly is suspended in and contains Hg 2+(1 * 10 -5M) in the aqueous solution (10mL), suspension at room temperature pass through different time (1～10min) concussion, centrifugal, carefully measure supernatant liquor (3mL), add fluorescence chemical sensor S3, measure fluorescence spectrum, ask the concentration of calculating metal ion according to calibration curve.The result is as shown in Figure 9, and (3min) in a short period of time, SM is to Hg 2+Recovery rate just reach capacity, this possibly be since multi-arm acid amides itself 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 the influence of pH to the SM recovery rate again.Take by weighing 30mg SM respectively, add redistilled water, wetting, centrifugation, the SM of gained inactivation (removing the physisorption of mesoporous silica gel material itself) evenly is suspended in the Hg of different pH values 2+(1 * 10 -5M) in the aqueous solution (10mL), suspension at room temperature shakes 180 seconds, and is centrifugal, carefully measures supernatant liquor (3mL), adds fluorescence chemical sensor S3, measures fluorescence spectrum, asks the concentration of calculating metal ion according to calibration curve.The gained result is shown in figure 10, and in very wide pH 3～12 scopes, SM is to Hg 2+Good adsorption separation performance is all arranged; This is the rare performance of reporting at present of solid-phase adsorbent; This has verified further that also the mesoporous silica gel carrier material is in the performance of protection multi-arm acid amides acceptor own; Give its special performances again, i.e. the combination Hg of (pH3～12) ability rapid (t=3min) in very wide pH scope 2+Realize Hg 2+Adsorbing separation.
We have also investigated different ions concentration SM have been used for Hg 2+The influence that separates.Take by weighing 30mgSM respectively, add redistilled water, wetting, centrifugation, gained SM (removing the physisorption of mesoporous silica gel material itself) evenly is suspended 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) aqueous solution (and 10mL, pH=6.56) in, suspension at room temperature shakes 180 seconds, and is centrifugal, carefully measures supernatant liquor (3mL), adds fluorescence chemical sensor S3, measures fluorescence spectrum, asks the concentration of calculating metal ion according to calibration curve.
The maximal absorptive capacity of SM (Q, mol g -1) calculate and can get through following formula 2, wherein: C 0: the initial concentration of metal ion; C: handle concentration (the mol L of metal ion afterwards through SM -1); V: metal ion solution volume (L); The quality of m:FS (g)
Q=[(C 0-C) * V]/m (formula 2).
Through changing different Hg 2+The mensuration of concentration of aqueous solution, we can obtain the maximal absorptive capacity of parting material SM, calculate according to formula 2 and can get the maximum adsorption capacity Q=21mg Hg of SM 2+/ g SM, adsorption capacity is relevant with the multi-arm acid amides quantity that particle diameter, structure, the key of mesoporous silica gel particle carrier itself connect.
Preparation contains Hg respectively 2+, Pb 2+, Cd 2+The aqueous solution 20mL of (30ppm and 10ppm) gets 10mL and contains the parting material (100mg) of the aqueous solution adding of heavy metal ion by instance 2 preparations, evenly disperses, and stirs 3min, centrifugalizes, and gets supernatant liquor, and clear liquid directly is used for the ICP-AES test.Parting material is used Hg 2+, Pb 2+, Cd 2+The recovery rate result see table 2 and table 3.
Table 2
Figure BDA0000066198780000151
Table 3
Embodiment 8:SM is used for the separation of Chinese medicine extract heavy metal
In view of the unique separating property of SM, we are applied to the separation of heavy metal in the Chinese medicine extract.Concrete steps are following: get 25mL Chinese medicine stoste, add 500mg functionalization silica gel, evenly stir 3min after; Leave standstill 0.5h, a large amount of silica gel precipitate, get supernatant liquor; (r=4000 commentaries on classics/min), remove small portion of residual silica gel, clear liquid can directly be used for the ICP-AES test in centrifugation.Shown in the table 4, ion concentration is by ICP-AES quantitative analysis (ICP-AES test) gained as a result for gained.
Table 4 Chinese medicine extract metal ion content before and after SM handles changes
Metal ion Content (ppm) before separating Separate back content (ppm)
Hg 2+ 0.008 0.002
pb 2+ 0.085 0.070
Cd 2+ 0.003 0.002
Can know that by table 4 parting material of embodiment 5 preparations still has the adsorbing separation effect to mercury, lead, the cadmium heavy metal ion of trace in the Chinese medicine stoste.
Embodiment 9:SM, active carbon, chitosan resin are used for the separation contrast of Chinese medicine extract heavy metal
In order to embody SM separating property efficiently, we have contrasted the separating effect that SM, active carbon, chitosan resin are used for the Chinese medicine extract heavy metal.Concrete steps are following: get three parts of 25mL Chinese medicine stostes; Add 500mg functionalization silica gel SM, active carbon, chitosan resin respectively, evenly stir 3min after, leave standstill 0.5h; Get supernatant liquor; (r=4000 commentaries on classics/min), remove adsorbent (functionalization silica gel SM, active carbon, chitosan resin), clear liquid can directly be used for the ICP-AES test in centrifugation.Shown in the table 5, ion concentration is by ICP-AES quantitative analysis (ICP-AES test) gained as a result for gained.
Table 5
Can be got by table 5, SM still has the adsorbing separation effect to the content of beary metal of trace in the Chinese medicine extract, and active carbon, chitosan resin are to the adsorption effect of its heavy metal and not obvious.The result can get thus, and the SM of the present invention's preparation can be used for the separation of trace heavy metal in the Chinese medicine extract compared to other common heavy metal parting material.
In order to investigate the influence of SM to its Chinese medicine extract composition, we have contrasted through HPLC and have joined the change of component that clever careless extract separates 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 that ginsenoside is a triterpenoid saponin, and this type material detects for the general wavelength UV-detector of λ=203nm that adopts; 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; The Cordyceps sinensis main component is cordycepic acid, cordycepin, amino acid, sterol, sweet mellow wine, alkaloid, vitamin B1, B2, polysaccharide and mineral matter etc.General all is the ucleosides analysis that is directed against wherein, selects λ=254nm UV-detector to detect.Therefore, when we utilize HPLC to analyze the change of component of the clever careless extract separation of ginseng front and back, select for use the UV-detector of two wavelength (λ=203,254nm) to carry out trace analysis respectively.
We adopt the UV-detector check and analysis SM of λ=254nm wavelength to joining the influence of clever careless extract main component earlier.Contrast Figure 12,13, the main component (like t=1.95,2.08,2.50,3.90,14.25,15.74min etc.) of joining clever careless extract does not have significant change.
Can be got by Figure 14,15 enlarged drawing, some micro constitutents (like 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 yet after SM handles.
We adopt the influence of the detector check and analysis SM of λ=203nm wave band to its composition again.Contrast Figure 16,17, the main component (like t=1.95,2.08,2.50,3.90,14.25,15.74min etc.) of joining clever careless extract does not have significant change.
Can be got by Figure 18,19 partial enlarged drawing, some micro constitutents (like 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 handles.
To sum up can get, SM can be used for joining trace metal (Hg in the clever careless extract 2+, Pb 2+, Cd 2+) separation, what is more important, after handling through SM, the extract steady quality does not have obvious influence to its main component.
The regeneration of embodiment 10:SM
Get the functionalization silica gel that metal ion is crossed in the 1g complexing, add 15mL 1 * 10 -2The EDTA solution of M evenly disperses, and stirs 3min, and supernatant liquor is removed in centrifugation, adds clean deionized water, cyclic washing three times, and centrifugation obtains functionalization silica gel, in 120 ℃ of baking ovens, dries, and obtains the SM that regenerates.

Claims (10)

1. a parting material is characterized in that, it passes through R by compound shown in the following formula I 1The carrier that contains active group with the surface obtains through covalent bonding:
Figure FDA0000066198770000011
formula I
In the 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 separately-NR 4R 5
R 4And R 5Independently be selected from separately-R 6-C (O)-NH-R 7-OH; With
R 6-R 7Independently be selected from the C1-C4 alkyl separately;
R 8For not existing or being selected from the C1-C4 alkyl;
Wherein, R 2And R 3Link to each other with the adjacent carbon atom of ring A.
2. parting material as claimed in claim 1 is characterized in that, ring A is selected from phenyl ring and C6-C8 cycloalkyl.
3. according to claim 1 or claim 2 parting material is characterized in that R 1Be C1-C2 alkyl-CHO.
4. like the described parting material of aforementioned each claim, it is characterized in that R 2And R 3Be identical or different group.
5. like the described parting material of aforementioned each claim, it is characterized in that R 6Be methyl, R 7Be ethyl.
6. like the described parting material of aforementioned each claim, it is characterized in that formula I compound is as follows:
7. like the described parting material of aforementioned each claim; It is characterized in that; Said carrier is selected from silica, polystyrene, polyacrylate, titanium oxide and polytetrafluoroethylene (PTFE), and wherein, said carrier is through surface-functionalized and have an active group that is selected from amino and halogen.
8. each described parting material or the purposes of formula I compound in separation of heavy metal ions among the claim 1-7.
9. purposes as claimed in claim 8 is characterized in that, said parting material is used for removing of Chinese medicine extract or food harmful heavy metal ion.
10. the method for the heavy metal ion in the sample separation is characterized in that, said method comprises uses among the claim 1-7 each described parting material to handle sample, thereby isolates said heavy metal ion.
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