CN104045857B - A kind of silicon-dioxide Chitosan Composites, preparation method and application thereof - Google Patents
A kind of silicon-dioxide Chitosan Composites, preparation method and application thereof Download PDFInfo
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- CN104045857B CN104045857B CN201410267200.3A CN201410267200A CN104045857B CN 104045857 B CN104045857 B CN 104045857B CN 201410267200 A CN201410267200 A CN 201410267200A CN 104045857 B CN104045857 B CN 104045857B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 123
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229960001866 silicon dioxide Drugs 0.000 title claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002086 nanomaterial Substances 0.000 claims abstract description 37
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- -1 epoxy group modified silica Chemical class 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 9
- VNTPGSZQKARKHG-UHFFFAOYSA-N trimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](C)(C)CCCOCC1CO1 VNTPGSZQKARKHG-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 abstract description 27
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 6
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000007995 HEPES buffer Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- CBBHMYUUBDQHHS-UHFFFAOYSA-N butanoic acid;pyrene Chemical group CCCC(O)=O.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 CBBHMYUUBDQHHS-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a kind of silicon-dioxide Chitosan Composites, preparation method and application thereof, preparation method comprises: pyrene butyric acid beautify chitosan, prepare quaternised pyrene butyryl chitosan matrix material, epoxy group modified silica nano material and prepare silicon-dioxide Chitosan Composites.Utilize chitosan for carrier, finishing pyrene butyric acid fluorophor, and it is quaternized after, then react with the silica nano material of epoxy-modified, having prepared can to the absorption of mercury (II) ion collection and the multi-functional nanometer material that be detected on one.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of silicon-dioxide Chitosan Composites, preparation method and application thereof.
Background technology
Along with the development of modern science and technology level and the raising of people's living standard, environmental pollution is also increasing day by day, and problem of environmental pollution more and more becomes one of problem that world's every country pays close attention to jointly.Environmental pollution the most directly, the most easily to experience by people.The consequence of environmental pollution destroys the living environment of the mankind, affects the quality of life of the mankind, healthy and activity in production.Wherein heavy metal contamination causes huge injury to environment and human health, heavy metal contamination to the harm of health mainly " three cause ": carcinogenic, cause disease, mutagenesis.In numerous heavy metal contamination, the pollution of mercury (II) ion is particularly outstanding.
Mercury (II) ion has the bioconcentration of persistence, easily transport property and height, and this becomes one of environmental pollutant that the whole world is the most noticeable at present.The material of existing bibliographical information only can be used for absorption or the detection of mercury (II) ion at present, function singleness.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of silicon-dioxide Chitosan Composites, can detect and the Multifunction fluorescent silicon-dioxide Chitosan Composites of Adsorption of Mercury (II) ion.
Present invention also offers a kind of preparation method and application thereof of silicon-dioxide Chitosan Composites.
A kind of silicon-dioxide Chitosan Composites provided by the invention, its structural representation is as shown in Figure of description 10.
Present invention also offers a kind of preparation method of silicon-dioxide Chitosan Composites, comprise the following steps:
A, pyrene butyric acid beautify chitosan:
Chitosan is dissolved in 1% acetic acid, obtain chitosan solution, pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide are dissolved in methyl alcohol, pyrene butyric acid concentration in methyl alcohol is 0.4-0.5mol/L, join after mixing in the chitosan solution of acquisition, add methanol solution again, volume is 0.8-1 times of chitosan solution volume ratio, after stirring 20-30h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1-2, and product precipitates, washing, the product namely obtained;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01-0.02g/ml, after mixing, add the hydroxypropyl-trimethyl ammonium chloride aqueous solution that concentration is 0.1-0.3g/ml, be heated to 70-80 DEG C, stirring reaction 6-10h, cooling, suction filtration, wash to obtain luteotestaceous quaternised pyrene butyryl chitosan matrix material;
C, epoxy group modified silica nano material:
Silica nano material is joined in toluene, the concentration 0.01-0.02g/ml of silica nano material in toluene, stirring is warming up to 80-120 DEG C, dropwise add 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent, insulation at nitrogen protection back flow reaction 40-50h, product collected by centrifugation, washing final vacuum is dry;
D, prepare silicon-dioxide Chitosan Composites:
Quaternised pyrene butyryl chitosan matrix material is in water, concentration is 0.005-0.01g/ml, add sodium ethylate, epoxy group modified silica nano material prepared by step C is added after mixing, 20-30h is reacted at 20-30 DEG C, product collected by centrifugation, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
The mass ratio of pyrene butyric acid in steps A, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide and chitosan is (0.15-0.2): (0.3-0.4) (0.3-0.4): 1;
Obtaining chitosan solution concentration described in steps A is 0.01-0.02g/ml;
The volume ratio 1:50-60 of methyl alcohol/ammonia water mixture and chitosan solution described in steps A.
The quality of the product adding steps A in step B and the hydroxypropyl-trimethyl ammonium chloride added is than scope 1:1-5.
In step C, the mass ratio of 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent and silica nano material is 0.6-1:1;
In step C, described silica nano material, prepare by the following method:
Dehydrated alcohol, distilled water and ammoniacal liquor are mixed, obtained mixing solutions, adds tetraethoxy, and 10-40 DEG C of reaction 6-10h, leaves standstill 24-48h, freeze-day with constant temperature at collected by centrifugation, washing 50-60 DEG C, obtained silica nano material.
The mol ratio of dehydrated alcohol, distilled water and ammoniacal liquor is 50-60:1:1, and tetraethoxy concentration range in mixing solutions is 0.1-0.2mol/L.
In step D, the quality of epoxy group modified silica nano material prepared by quaternised pyrene butyryl chitosan matrix material used, sodium ethylate and step C is than scope 0.05-0.1:0.01-0.03:1.
A kind of silicon-dioxide Chitosan Composites provided by the invention, is detecting and the application of Adsorption of Mercury (II) ions.
The present invention utilizes chitosan for carrier, finishing pyrene butyric acid fluorophor, and it is quaternized after, then react with the silica nano material of epoxy-modified, having prepared can to the absorption of mercury (II) ion collection and the multi-functional nanometer material that be detected on one.
The present invention utilizes fluorescent substance, the feature of chitosan and nano material, makes functional group at chitosan molecule surface Relatively centralized, can complete simultaneously to the object that mercury (II) ion realizes absorption and detects.Containing pyrene fluorophor and quaternary ammonium salt in this material, existing absorption and fluoroscopic examination can be carried out to mercury (II) ion.Therefore, this product can realize absorption simultaneously and detect, and has multi-functional character.
Accompanying drawing explanation
Fig. 1 is the reaction process of steps A pyrene butyric acid beautify chitosan;
Fig. 2 is the reaction process that step B prepares quaternised pyrene butyryl chitosan matrix material;
Fig. 3 is the infrared spectrogram of silicon-dioxide Chitosan Composites prepared by embodiment 1,
A. chitosan, b. pyrene butyric acid beautify chitosan, c. quaternised pyrene butyric acid beautify chitosan,
D. silicon-dioxide Chitosan Composites;
Fig. 4 is the fluorescence spectrum figure of silicon-dioxide Chitosan Composites prepared by embodiment 1;
Fig. 5 is the graph of a relation of mercury (II) ionic concn and fluorescence intensity;
Fig. 6 be embodiment 1 prepare silicon-dioxide Chitosan Composites and Hg (II) act on quenching of fluorescence schematic diagram;
Fig. 7 is that the silicon-dioxide Chitosan Composites of embodiment 1 preparation is to the sorption isotherm of mercury (II) ion;
Fig. 8. be uv absorption spectra,
A. Mercury pernitrate reference solution (10 μm of ol/l), b. quaternary ammonium chitosan material (5mg/ml), c. quaternary ammonium chitosan material (1mg/ml) and Mercury pernitrate (10 μm of ol/l), d. quaternary ammonium chitosan material (5mg/ml) and Mercury pernitrate (10 μm of ol/l);
Fig. 9. be fluorescence spectrum figure,
A. pyrene butyric acid solution (2 μm of ol/l), b. pyrene butyric acid solution (2 μm of ol/l) and Mercury pernitrate (2 μm of ol/l), c. pyrene butyric acid solution (2 μm of ol/l), Mercury pernitrate (2 μm of ol/l) and quaternary ammonium chitosan material (0.1mg/ml);
Figure 10 is the structural representation of silicon-dioxide Chitosan Composites.
Embodiment
Embodiment 1
A, pyrene butyric acid beautify chitosan:
1g chitosan is dissolved in 100ml1% acetic acid, obtain chitosan solution, 0.27g pyrene butyric acid, 0.38g1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and 0.3gN-N-N-Hydroxysuccinimide are dissolved in 2ml methyl alcohol, join in chitosan solution after mixing, then add methanol solution, after stirring 24h, add methyl alcohol/ammonia water mixture 2ml, product precipitates, washing, the product namely obtained;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The 0.6g product of steps A is dissolved in 40ml Virahol, after mixing, add the 10ml hydroxypropyl-trimethyl ammonium chloride aqueous solution, concentration is 0.3g/ml, be heated to 80 DEG C, stirring reaction 8h, cooling, suction filtration, wash to obtain luteotestaceous quaternised pyrene butyryl chitosan matrix material;
C, epoxy group modified silica nano material:
0.5g silica nano material is joined in 50ml toluene, stir and be warming up to 100 DEG C DEG C, dropwise add 0.45 gram of 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent, be incubated 100 DEG C and at nitrogen protection back flow reaction 48h, product collected by centrifugation, washing final vacuum is dry;
Silica nano material preparation method is: measure 60mL dehydrated alcohol, and adds distilled water 4mL, and ammoniacal liquor 4mL, adds 2mLTEOS after magnetic agitation 30min, keeps room temperature to continue reaction 8h, leaves standstill 24h subsequently.Product collected by centrifugation, after high purity water washing at 60 DEG C freeze-day with constant temperature, obtained SiO
2nano material.
D, prepare silicon-dioxide Chitosan Composites:
0.1g quaternised pyrene butyryl chitosan matrix material is in 20ml water, add 0.03g sodium ethylate, epoxy group modified silica nano material prepared by 1g step C is added after mixing, 24h is reacted at 20 DEG C, product collected by centrifugation, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
The infared spectrum of the silicon-dioxide Chitosan Composites of chitosan, pyrene butyric acid beautify chitosan, quaternised pyrene butyric acid beautify chitosan and embodiment 1 preparation as shown in Figure 3.As we can see from the figure, chitosan, pyrene butyric acid beautify chitosan, quaternised pyrene butyric acid beautify chitosan is all at 1086cm
-1(C-O stretching vibration peak), 1160cm
-1the charateristic avsorption band of polysaccharide skeleton has been there is in (C-N key stretching vibration absorption peak) scope.The infared spectrum of pyrene butyric acid beautify chitosan and chitosan is closely similar, but at 1660cm
-1place occurs that chitosan and pyrene butyric acid react the phthalein amine bands of a spectrum formed.In the infrared spectra of quaternised pyrene butyric acid beautify chitosan, chitosan is at 1595cm
-1the N-H in-plane bending vibration absorption peak of place's primary amino disappears, and at 1485cm
-1, 1640cm
-1and 2952cm
-1having there is new absorption peak in place, is-CH in quaternization group
3formation vibration peak and the flexible peak that shakes, show chitosan molecule-NH
2in H by-CH
2cH (OH) CH
2n
+(CH
3)
3cl
-part replaces, and generates quaternised pyrene butyric acid beautify chitosan.In addition, by fluorescent silicon dioxide Chitosan Composites at 1083cm
-1there is the stretching vibration characteristic peak of Si-O-Si, 2930cm
-1and 2852cm
-1there is C-H vibration absorption peak in place, and 1654cm
-1for chitosan characteristic absorbance.Everything shows quaternised pyrene butyric acid beautify chitosan success and epoxy group modified earth silicon material compound.
Silicon-dioxide Chitosan Composites is to the detection of mercury (II) ion
Silicon-dioxide Chitosan Composites 0.1g prepared by Example 1 is in 250ml volumetric flask, ultrasonic dispersed.The Mercury pernitrate solution got this solution of 1ml subsequently respectively and increase concentration gradually, in 10ml color-comparison tube, respectively adds the HEPES buffered soln of 1mlpH7.0 simultaneously, is diluted to scale.Excitation wavelength is set in 330nm, measures the fluorescence spectrum under different mercury (II) ionic concn respectively.
As can be seen from Fig. 4,5, along with the increase adding Mercury pernitrate concentration, the fluorescence of system reduces gradually.The fluorescence intensity describing mercury (II) ion pair system has quenching effect, and the ion concentration of mercury added is larger, larger to the fluorescence intensity quencher effect of system.And the concentration of the fluorescence intensity of material and mercury (II) ion has linear relationship in certain scope, can draw the concentration of mercury (II) ion under known fluorescence intensity according to linear equation, therefore this patent product may be used for the detection of lower mercury (II) ion.
To the absorption property of mercury (II) ion
It is 20 DEG C in temperature, silicon-dioxide Chitosan Composites (as sorbent material) prepared by 0.1g embodiment 1 is taken respectively under pH7.0 condition, join in the 10mL Mercury pernitrate solution of different concns respectively, constant temperature oscillation, question response for some time, after making absorption reach balance, centrifugation, adopt the equilibrium concentration of mercury ion in atomic absorption spectroscopy determination supernatant liquor subsequently, and be calculated as follows the equilibrium adsorption capacity q of tropeolin-D
e
In formula, q
efor the equilibrium adsorption capacity (g/g) of mercury ion, V is liquor capacity (mL), C
ofor the initial mass concentration (g/L) of Mercury pernitrate solution, C
efor the mass concentration (g/L) of mercury ion in supernatant liquor after adsorption equilibrium, m is the quality (g) of fluorescent silicon dioxide Chitosan Composites functional particles.
As can be seen from Figure 7, along with the increase of equilibrium concentration, adsorptive capacity increases gradually, finally levels off to balance.Absorption meets Langmuir type monolayer adsorption.With Langmuir Tellurium determination, matching is carried out to it
Wherein K is Langmuir absorption constant, C
ethe equilibrium concentration (mg/L) of the mercury ion being, q
efor the equilibrium adsorption capacity of unit sorbent material, q
mit is the most high adsorption capacity to mercury ion.By matching, K and q
mmust be worth and be respectively 0.7L/mg, 98mg/g.
Shown in Fig. 8, a and b is respectively Mercury pernitrate reference solution 2 × 10
-5the ultra-violet absorption spectrum of mol/l and simple quaternary ammonium chitosan (5mg/ml), does not all have uv-absorbing at 227nm place.And after adding quaternary ammonium chitosan in Mercury pernitrate solution, obvious ultraviolet absorption peak appears in 227nm place, and the quaternary ammonium chitosan concentration added is higher, and the intensity of uv-absorbing is stronger.This phenomenon describes HgCl
2hgCl can be converted under quaternary ammonium cation induction
3 -negative ion, creates new absorption peak.
Fig. 9 is a. pyrene butyric acid solution (2 μm of ol/l), b. pyrene butyric acid solution (2 μm of ol/l) and Mercury pernitrate (2 μm of ol/l), c. pyrene butyric acid solution (2 μm of ol/l), the fluorescence spectrum of Mercury pernitrate (2 μm of ol/l) and quaternary ammonium chitosan material (0.1mg/ml).As can be seen from the figure, simple mercury (II) ion pair pyrene butyric acid is without quenching effect, and the fluorescence of mercury (II) ion obvious quencher pyrene butyric acid under quaternary ammonium chitosan exists.This phenomenon further illustrates quaternary ammonium cation and mercury (II) ion can be induced to form HgCl
3 -negative ion.
Therefore, experiment demonstrates the mechanism of supposition, and namely n-trimethyl chitosan chloride induction mercury (II) ion forms HgCl
3 -negative ion, HgCl
3 -negative ion and quaternary ammonium cation form ion pair and are adsorbed on material surface, and the fluorescence of quencher pyrene butyric acid group, realizes the object detecting simultaneously mercury (II) ion and adsorb.
Embodiment 2
A, pyrene butyric acid beautify chitosan:
Chitosan is dissolved in 1% acetic acid, obtain chitosan solution, concentration is 0.015g/ml, be dissolved in methyl alcohol by pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide, the mass ratio of pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide and chitosan is 0.16:0.35::0.35:1; Pyrene butyric acid concentration in methyl alcohol is 0.4mol/L, join after mixing in the chitosan solution of acquisition, add methanol solution again, volume is 0.8 times of chitosan solution volume ratio, after stirring 20h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is the volume ratio 1:50 of 1:1, methyl alcohol/ammonia water mixture and chitosan solution; After product precipitation, washing, the product namely obtained;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01g/ml, after mixing, add the hydroxypropyl-trimethyl ammonium chloride aqueous solution that concentration is 0.1g/ml, the product adding steps A is 1:1 with the mass ratio of the hydroxypropyl-trimethyl ammonium chloride added, be heated to 70 DEG C, stirring reaction 10h, cooling, suction filtration, wash to obtain luteotestaceous quaternised pyrene butyryl chitosan matrix material;
C, epoxy group modified silica nano material:
Silica nano material is joined in toluene, the concentration 0.02mol/L of silica nano material in toluene, stirring is warming up to 120 DEG C, dropwise add 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent, the mass ratio of 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent and silica nano material is 1:1; Insulation at nitrogen protection back flow reaction 40h, product collected by centrifugation, washing final vacuum is dry;
In step C, described silica nano material preparation method is with embodiment 1;
D, prepare silicon-dioxide Chitosan Composites:
Quaternised pyrene butyryl chitosan matrix material is in water, concentration is 0.005g/ml, add sodium ethylate, epoxy group modified silica nano material prepared by step C is added after mixing, react 30h at 20 DEG C, product collected by centrifugation, washing final vacuum is dry, obtain chitosan silicon dioxide composite material, the quality of epoxy group modified silica nano material prepared by quaternised pyrene butyryl chitosan matrix material used, sodium ethylate and step C is than scope 0.06:0.02:1.
Embodiment 3
A, pyrene butyric acid beautify chitosan:
Chitosan is dissolved in 1% acetic acid, obtain chitosan solution, concentration is 0.015g/ml, be dissolved in methyl alcohol by pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide, the mass ratio of pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide and chitosan is 0.2:0.4::0.4:1; Pyrene butyric acid concentration in methyl alcohol is 0.4mol/L, join after mixing in the chitosan solution of acquisition, add methanol solution again, volume is 1 times of chitosan solution volume ratio, after stirring 20h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is the volume ratio 1:55 of 1:1, methyl alcohol/ammonia water mixture and chitosan solution;
After product precipitation, washing, the product namely obtained;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01g/ml, after mixing, add the hydroxypropyl-trimethyl ammonium chloride aqueous solution that concentration is 0.1g/ml, the product adding steps A is 1:3 with the mass ratio of the hydroxypropyl-trimethyl ammonium chloride added, be heated to 80 DEG C, stirring reaction 10h, cooling, suction filtration, wash to obtain luteotestaceous quaternised pyrene butyryl chitosan matrix material;
C, epoxy group modified silica nano material:
Silica nano material is joined in toluene, the concentration 0.01mol/L of silica nano material in toluene, stirring is warming up to 100 DEG C, dropwise add 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent, the mass ratio of 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent and silica nano material is 0.9:1; Insulation at nitrogen protection back flow reaction 40h, product collected by centrifugation, washing final vacuum is dry;
In step C, described silica nano material preparation method is with embodiment 1;
D, prepare silicon-dioxide Chitosan Composites:
Quaternised pyrene butyryl chitosan matrix material is in water, concentration is 0.01g/ml, add sodium ethylate, epoxy group modified silica nano material prepared by step C is added after mixing, react 30h at 20 DEG C, product collected by centrifugation, washing final vacuum is dry, obtain chitosan silicon dioxide composite material, the quality of epoxy group modified silica nano material prepared by quaternised pyrene butyryl chitosan matrix material used, sodium ethylate and step C is than scope 0.1:0.03:1.
Claims (7)
1. a preparation method for silicon-dioxide Chitosan Composites, is characterized in that, comprises the following steps:
A, pyrene butyric acid beautify chitosan:
Chitosan is dissolved in 1% acetic acid, obtain chitosan solution, pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide are dissolved in methyl alcohol, pyrene butyric acid concentration in methyl alcohol is 0.4-0.5mol/L, join after mixing in the chitosan solution of acquisition, add methanol solution again, volume is 0.8-1 times of chitosan solution volume ratio, after stirring 20-30h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1-2, and product precipitates, washing, the product namely obtained;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01-0.02g/ml, after mixing, add the hydroxypropyl-trimethyl ammonium chloride aqueous solution that concentration is 0.1-0.3g/ml, be heated to 70-80 DEG C, stirring reaction 6-10h, cooling, suction filtration, wash to obtain luteotestaceous quaternised pyrene butyryl chitosan matrix material;
C, epoxy group modified silica nano material:
Silica nano material is joined in toluene, the concentration 0.01-0.02g/ml of silica nano material in toluene, stirring is warming up to 80-120 DEG C, dropwise add 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent, insulation at nitrogen protection back flow reaction 40-50h, product collected by centrifugation, washing final vacuum is dry;
D, prepare silicon-dioxide Chitosan Composites:
Quaternised pyrene butyryl chitosan matrix material is in water, concentration is 0.005-0.01g/ml, add sodium ethylate, epoxy group modified silica nano material prepared by step C is added after mixing, 20-30h is reacted at 20-30 DEG C, product collected by centrifugation, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
2. preparation method according to claim 1, is characterized in that, obtaining chitosan solution concentration described in steps A is 0.01-0.02g/ml.
3. preparation method according to claim 1, is characterized in that, the volume ratio 1:50-60 of methyl alcohol/ammonia water mixture and chitosan solution described in steps A.
4. preparation method according to claim 1, is characterized in that, the quality of the product adding steps A in step B and the hydroxypropyl-trimethyl ammonium chloride added is than scope 1:1-5.
5. preparation method according to claim 1, is characterized in that, in step C, the mass ratio of 3-(2,3-epoxypropyl) oxypropyl trimethyl silane coupling agent and silica nano material is 0.6-1:1.
6. preparation method according to claim 1, it is characterized in that, in step D, the quality of epoxy group modified silica nano material prepared by quaternised pyrene butyryl chitosan matrix material used, sodium ethylate and step C is than scope 0.05-0.1:0.01-0.03:1.
7. the application of silicon-dioxide Chitosan Composites prepared of method described in claim 1, is characterized in that, is detecting and the application of Adsorption of Mercury (II) ions.
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| CN106084311B (en) * | 2016-06-02 | 2018-05-08 | 中国科学院青海盐湖研究所 | A kind of method for preparing oxide-Chitosan Composites and oxide-Chitosan Composites |
| CN107121427B (en) * | 2017-04-26 | 2020-06-16 | 朱建华 | Reagent for detecting tyrosine phenol metabolites in human urine and preparation method thereof |
| CN109718726B (en) * | 2018-12-29 | 2021-08-03 | 江苏脒诺甫纳米材料有限公司 | Production process of amphiphilic silica-chitosan composite aerogel |
| CN111841508B (en) * | 2020-07-28 | 2021-08-17 | 南昌航空大学 | Sulfosalicylic acid modified chitosan/silicon dioxide microspheres and preparation method and application thereof |
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