CN104045857A - Silicon dioxide chitosan composite material, and preparation method and application thereof - Google Patents
Silicon dioxide chitosan composite material, and preparation method and application thereof Download PDFInfo
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- CN104045857A CN104045857A CN201410267200.3A CN201410267200A CN104045857A CN 104045857 A CN104045857 A CN 104045857A CN 201410267200 A CN201410267200 A CN 201410267200A CN 104045857 A CN104045857 A CN 104045857A
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Abstract
The invention provides a silicon dioxide chitosan composite material, and a preparation method and application thereof. The preparation method comprises the following steps: modifying chitosan with pyrenylbutyric acid, preparing a quaternized pyrenylbutyric acid chitosan composite material, modifying a silicon dioxide nano material with an epoxy group, and preparing the silicon dioxide chitosan composite material. By taking the chitosan as a carrier, performing surface modification with a pyrenylbutyric acid fluorophore, quaternizing and then reacting with the epoxy-modified silicon dioxide nano material, the multifunctional nano material having the functions of adsorbing and detecting mercury (II) ions is prepared.
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 common problem of paying close attention to of world's every country.Environmental pollution the most directly, the most easily by people experienced.The consequence of environmental pollution is to destroy the mankind's living environment, affects the mankind's quality of life, healthy and activity in production.Wherein heavy metal contamination has caused huge injury to environment and human health, and heavy metal contamination is mainly " three cause " to the harm of health: 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 the most noticeable environmental pollutant in the current whole world.The material of at present existing bibliographical information only can be used for absorption or the detection of mercury (II) ion, 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.
The present invention also provides 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.
The present invention also provides a kind of preparation method of silicon-dioxide Chitosan Composites, 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, after mixing, join in the chitosan solution of acquisition, add again methanol solution, volume is 0.8-1 times of chitosan solution volume ratio, stir after 20-30h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1-2, product precipitation, washing, the product obtaining;
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, adding concentration is the hydroxypropyl-trimethyl ammonium chloride aqueous solution of 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, the centrifugal collection of product, 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, the epoxy group modified silica nano material that adds step C to prepare after mixing, at 20-30 DEG C, react 20-30h, the centrifugal collection of product, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
In steps A, the mass ratio of pyrene butyric acid, 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;
Described in steps A, obtaining chitosan solution concentration is 0.01-0.02g/ml;
The volume ratio 1:50-60 of methyl alcohol/ammonia water mixture described in steps A and chitosan solution.
The product that adds steps A in step B with the quality of the hydroxypropyl-trimethyl ammonium chloride adding than scope 1:1-5.
The mass ratio of (2,3-epoxypropyl) the oxypropyl trimethyl silane coupling agent of 3-in step C and silica nano material is 0.6-1:1;
In step C, described silica nano material, by the following method preparation:
Dehydrated alcohol, distilled water and ammoniacal liquor are mixed, make mixing solutions, add tetraethoxy, 10-40 DEG C reaction 6-10h, leave standstill 24-48h, centrifugal collection, washing 50-60 DEG C at freeze-day with constant temperature, make 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.
The quality of the epoxy group modified silica nano material that in step D 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, in the application of detection and Adsorption of Mercury (II) ions.
The present invention utilizes chitosan for carrier, finishing pyrene butyric acid fluorophor, and after it is quaternized, then react with the silica nano material of epoxy-modified, having prepared can be to the absorption of mercury (II) ion collection and the multi-functional nanometer material that is detected on one.
The present invention utilizes fluorescent substance, and the feature of chitosan and nano material makes functional group relatively concentrated on chitosan molecule surface, can complete the object that mercury (II) ion is realized absorption and detected simultaneously.In this material, contain pyrene fluorophor and quaternary ammonium salt, can carry out existing absorption and fluoroscopic examination to mercury (II) ion.Therefore, this product can be realized absorption simultaneously and detect, and has multi-functional character.
Brief description of the drawings
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 the silicon-dioxide Chitosan Composites prepared of embodiment 1,
A. chitosan, b. pyrene butyric acid beautify chitosan, the quaternised pyrene butyric acid of c. beautify chitosan,
D. silicon-dioxide Chitosan Composites;
Fig. 4 is the fluorescence spectrum figure of the silicon-dioxide Chitosan Composites prepared of embodiment 1;
Fig. 5 is the graph of a relation of mercury (II) ionic concn and fluorescence intensity;
Fig. 6 is silicon-dioxide Chitosan Composites and Hg (II) effect quenching of fluorescence schematic diagram prepared by embodiment 1;
Fig. 7 is the sorption isotherm of the silicon-dioxide Chitosan Composites prepared of embodiment 1 to mercury (II) ion;
Fig. 8. be uv absorption spectra,
A. Mercury pernitrate reference solution (10 μ mol/l), b. quaternary ammonium chitosan material (5mg/ml), c. quaternary ammonium chitosan material (1mg/ml) and Mercury pernitrate (10 μ mol/l), d. quaternary ammonium chitosan material (5mg/ml) and Mercury pernitrate (10 μ mol/l);
Fig. 9. be fluorescence spectrum figure,
A. pyrene butyric acid solution (2 μ mol/l), b. pyrene butyric acid solution (2 μ mol/l) and Mercury pernitrate (2 μ mol/l), c. pyrene butyric acid solution (2 μ mol/l), Mercury pernitrate (2 μ mol/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 0.3g N-N-N-Hydroxysuccinimide are dissolved in 2ml methyl alcohol, after mixing, join in chitosan solution, then add methanol solution, stir after 24h, add methyl alcohol/ammonia water mixture 2ml, product precipitation, washing, the product obtaining;
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, the centrifugal collection of product, washing final vacuum is dry;
Silica nano material preparation method is: measure 60mL dehydrated alcohol, and add distilled water 4mL, ammoniacal liquor 4mL, adds 2mL TEOS after magnetic agitation 30min, keeps room temperature to continue reaction 8h, leaves standstill subsequently 24h.The centrifugal collection of product, after high purity water washing at 60 DEG C freeze-day with constant temperature, make SiO
2nano material.
D, prepare silicon-dioxide Chitosan Composites:
The quaternised pyrene butyryl chitosan of 0.1g matrix material is in 20ml water, add 0.03g sodium ethylate, the epoxy group modified silica nano material that adds 1g step C to prepare after mixing, at 20 DEG C, react 24h, the centrifugal collection of product, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
The infared spectrum of silicon-dioxide Chitosan Composites prepared by chitosan, pyrene butyric acid beautify chitosan, quaternised pyrene butyric acid beautify chitosan and embodiment 1 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
-1in (C-N key stretching vibration absorption peak) scope, there is the charateristic avsorption band of polysaccharide skeleton.The infared spectrum of pyrene butyric acid beautify chitosan and chitosan is closely similar, but at 1660cm
-1place occurs that chitosan reacts the phthalein amine bands of a spectrum that form with pyrene butyric acid.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
-1there is new absorption peak in place, in quaternary ammonium salinization group-CH
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 has generated 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, and success is compound with epoxy group modified earth silicon material.
The detection of silicon-dioxide Chitosan Composites to mercury (II) ion
Get silicon-dioxide Chitosan Composites 0.1g prepared by embodiment 1 in 250ml volumetric flask, ultrasonic dispersed.The Mercury pernitrate solution of getting respectively subsequently this solution of 1ml and increase gradually concentration, in 10ml color-comparison tube, respectively adds the HEPES buffered soln of 1ml pH7.0 simultaneously, is diluted to scale.Excitation wavelength is set in 330nm, measures respectively the fluorescence spectrum under different mercury (II) ionic concn.
From Fig. 4,5, can find out, along with adding the increase of Mercury pernitrate concentration, the fluorescence of system reduces gradually.The fluorescence intensity that mercury (II) ion pair system has been described has quenching effect, and the ion concentration of mercury adding 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 under known fluorescence intensity (II) ion according to linear equation, therefore this patent product can be for the detection of lower mercury (II) ion.
To the absorption property of mercury (II) ion
It is 20 DEG C in temperature, under pH7.0 condition, take respectively silicon-dioxide Chitosan Composites (as sorbent material) prepared by 0.1g embodiment 1, join respectively in the 10mL Mercury pernitrate solution of different concns, constant temperature oscillation, question response for some time, absorption is reached after balance, centrifugation, adopt subsequently the equilibrium concentration of mercury ion in atomic absorption spectroscopy determination supernatant liquor, 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.It is carried out to matching with Langmuir adsorption isotherm equation
Wherein K is Langmuir absorption constant, C
ethe equilibrium concentration (mg/L) of the mercury ion that is, q
efor the equilibrium adsorption capacity of unit sorbent material, q
mit is the 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 are 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 when adding in Mercury pernitrate solution after quaternary ammonium chitosan, obvious ultraviolet absorption peak appears in 227nm place, and the quaternary ammonium chitosan concentration adding is higher, and the intensity of uv-absorbing is stronger.This phenomenon has illustrated HgCl
2can under quaternary ammonium cation induction, be converted into HgCl
3 -negative ion, has produced new absorption peak.
Fig. 9 is a. pyrene butyric acid solution (2 μ mol/l), b. pyrene butyric acid solution (2 μ mol/l) and Mercury pernitrate (2 μ mol/l), c. pyrene butyric acid solution (2 μ mol/l), the fluorescence spectrum of Mercury pernitrate (2 μ mol/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 can induce mercury (II) ion to form HgCl
3 -negative ion.
Therefore, experimental results show that the mechanism of inferring, i.e. 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 is realized the object that mercury (II) ion is detected simultaneously and adsorbed.
Embodiment 2
A, pyrene butyric acid beautify chitosan:
Chitosan is dissolved in 1% acetic acid, obtain chitosan solution, concentration is 0.015g/ml, pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide are dissolved in methyl alcohol, and 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, after mixing, join in the chitosan solution of acquisition, add again methanol solution, volume is 0.8 times of chitosan solution volume ratio, stir after 20h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1, the volume ratio 1:50 of methyl alcohol/ammonia water mixture and chitosan solution; After product precipitation, washing, the product obtaining;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01g/ml, after mixing, adding concentration is the hydroxypropyl-trimethyl ammonium chloride aqueous solution of 0.1g/ml, adding the product of steps A is 1:1 with the mass ratio of the hydroxypropyl-trimethyl ammonium chloride adding, 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, the centrifugal collection of product, 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, the epoxy group modified silica nano material that adds step C to prepare after mixing, at 20 DEG C, react 30h, the centrifugal collection of product, 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, pyrene butyric acid, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide and N-N-N-Hydroxysuccinimide are dissolved in methyl alcohol, and 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, after mixing, join in the chitosan solution of acquisition, add again methanol solution, volume is 1 times of chitosan solution volume ratio, stir after 20h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1, the volume ratio 1:55 of methyl alcohol/ammonia water mixture and chitosan solution;
After product precipitation, washing, the product obtaining;
B, prepare quaternised pyrene butyryl chitosan matrix material:
The product of steps A is dissolved in Virahol, concentration is 0.01g/ml, after mixing, adding concentration is the hydroxypropyl-trimethyl ammonium chloride aqueous solution of 0.1g/ml, adding the product of steps A is 1:3 with the mass ratio of the hydroxypropyl-trimethyl ammonium chloride adding, 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, the centrifugal collection of product, 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, the epoxy group modified silica nano material that adds step C to prepare after mixing, at 20 DEG C, react 30h, the centrifugal collection of product, 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 (8)
1. a silicon-dioxide Chitosan Composites, is characterized in that, its structural representation as shown in figure 10.
2. a preparation method for silicon-dioxide Chitosan Composites claimed in claim 1, 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, after mixing, join in the chitosan solution of acquisition, add again methanol solution, volume is 0.8-1 times of chitosan solution volume ratio, stir after 20-30h, add methyl alcohol/ammonia water mixture, wherein the volume ratio of methyl alcohol, ammoniacal liquor is 1:1-2, product precipitation, washing, the product obtaining;
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, adding concentration is the hydroxypropyl-trimethyl ammonium chloride aqueous solution of 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, the centrifugal collection of product, 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, the epoxy group modified silica nano material that adds step C to prepare after mixing, at 20-30 DEG C, react 20-30h, the centrifugal collection of product, washing final vacuum is dry, obtains chitosan silicon dioxide composite material.
3. preparation method according to claim 2, is characterized in that, described in steps A, obtaining chitosan solution concentration is 0.01-0.02g/ml.
4. preparation method according to claim 2, is characterized in that, the volume ratio 1:50-60 of methyl alcohol/ammonia water mixture described in steps A and chitosan solution.
5. preparation method according to claim 2, is characterized in that, the product that adds steps A in step B with the quality of the hydroxypropyl-trimethyl ammonium chloride adding than scope 1:1-5.
6. preparation method according to claim 2, is characterized in that, the mass ratio of (2,3-epoxypropyl) the oxypropyl trimethyl silane coupling agent of 3-in step C and silica nano material is 0.6-1:1.
7. preparation method according to claim 2, it is characterized in that, the quality of the epoxy group modified silica nano material that in step D 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.
8. the application of silicon-dioxide Chitosan Composites claimed in claim 1, is characterized in that, in the application of detection and Adsorption of Mercury (II) ions.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001852A (en) * | 2015-06-08 | 2015-10-28 | 济南大学 | Preparation method and application of magnetic pyrenebutyric acid fluorescent probe detecting ferric ions |
| CN106084311A (en) * | 2016-06-02 | 2016-11-09 | 中国科学院青海盐湖研究所 | A kind of method preparing oxide shell polysaccharide composite material and oxide shell polysaccharide composite material |
| CN107121427A (en) * | 2017-04-26 | 2017-09-01 | 朱建华 | Detection reagent of tyrosine phenolic metabolism thing and preparation method thereof in human urine |
| CN109718726A (en) * | 2018-12-29 | 2019-05-07 | 江苏脒诺甫纳米材料有限公司 | A kind of production technology of parental type silica-chitosan composite aerogel |
| CN111841508A (en) * | 2020-07-28 | 2020-10-30 | 南昌航空大学 | Sulfosalicylic acid modified chitosan/silicon dioxide microspheres and preparation method and application thereof |
| CN113151403A (en) * | 2021-04-06 | 2021-07-23 | 中国科学技术大学 | DNA and methylation level detection kit thereof, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970463A (en) * | 2005-11-25 | 2007-05-30 | 浙江大学 | Polysilicate-chitosan composite flocculant and its acid type preparation method |
| CN102847522A (en) * | 2012-09-15 | 2013-01-02 | 安徽师范大学 | Preparation method and application of functional silica nano material |
| CN102990740A (en) * | 2012-09-15 | 2013-03-27 | 安徽师范大学 | Nano composite wood preservative and preparation method thereof |
| CN103041783A (en) * | 2012-12-18 | 2013-04-17 | 陕西宣和通科技发展有限责任公司 | Preparation method of chitosan-Ti02 adsorbent |
-
2014
- 2014-06-16 CN CN201410267200.3A patent/CN104045857B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970463A (en) * | 2005-11-25 | 2007-05-30 | 浙江大学 | Polysilicate-chitosan composite flocculant and its acid type preparation method |
| CN102847522A (en) * | 2012-09-15 | 2013-01-02 | 安徽师范大学 | Preparation method and application of functional silica nano material |
| CN102990740A (en) * | 2012-09-15 | 2013-03-27 | 安徽师范大学 | Nano composite wood preservative and preparation method thereof |
| CN103041783A (en) * | 2012-12-18 | 2013-04-17 | 陕西宣和通科技发展有限责任公司 | Preparation method of chitosan-Ti02 adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| 张军丽等: "DNS改性壳聚糖对重金属镍离子的吸附研究", 《非金属矿》, vol. 34, no. 4, 31 July 2011 (2011-07-31) * |
Cited By (8)
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| CN105001852A (en) * | 2015-06-08 | 2015-10-28 | 济南大学 | Preparation method and application of magnetic pyrenebutyric acid fluorescent probe detecting ferric ions |
| CN106084311A (en) * | 2016-06-02 | 2016-11-09 | 中国科学院青海盐湖研究所 | A kind of method preparing oxide shell polysaccharide composite material and oxide shell polysaccharide composite material |
| 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 |
| CN107121427A (en) * | 2017-04-26 | 2017-09-01 | 朱建华 | Detection reagent of tyrosine phenolic metabolism thing and preparation method thereof in human urine |
| CN109718726A (en) * | 2018-12-29 | 2019-05-07 | 江苏脒诺甫纳米材料有限公司 | A kind of production technology of parental type silica-chitosan composite aerogel |
| 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 |
| CN111841508A (en) * | 2020-07-28 | 2020-10-30 | 南昌航空大学 | Sulfosalicylic acid modified chitosan/silicon dioxide microspheres and preparation method and application thereof |
| CN113151403A (en) * | 2021-04-06 | 2021-07-23 | 中国科学技术大学 | DNA and methylation level detection kit thereof, and preparation method and application thereof |
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