CN107568245A - A kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent and preparation method thereof - Google Patents
A kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent and preparation method thereof Download PDFInfo
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- CN107568245A CN107568245A CN201710687741.5A CN201710687741A CN107568245A CN 107568245 A CN107568245 A CN 107568245A CN 201710687741 A CN201710687741 A CN 201710687741A CN 107568245 A CN107568245 A CN 107568245A
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Abstract
The invention discloses a kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.Using the chitosan magnetic micro-sphere that a step precipitation method are prepared as carrier, Zn (Ac) is placed on2·2H2In O solution, and certain density NaOH solution is added, temperature control stirring, react to obtain chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent by chemical deposition.The a large amount of Nanoparticulate zinc oxide of area load of the complex antimicrobials, to bacteria inactivation rate height in water and effect is lasting, and there is magnetic to be easy to reclaim.
Description
Technical field
The invention belongs to material preparation and environmental protection technical field, and in particular to a kind of chitosan magnetic micro-sphere/oxidation
Zinc compound bactericide and preparation method thereof.
Background technology
With the raising of health and environmental consciousness, people pursue nontoxic, harmless anti-biotic material and mode more and more.
Compared with traditional Water Disinfection agent, antibacterial agent have without chemical residue, without DBPs, do not produce resistance
The advantages that bacterium, the fields such as drinking water source purifies, water supply transmission and distribution network is degerming, circulation is degerming are can apply to, in recent years
To rapidly become the focus of concern.
Zinc oxide (ZnO) is a kind of inorganic antiseptic that good anti-microbial property is respectively provided with illumination and dark condition, it
Often it is prepared to powdered to increase its surface area, improves antibacterial effect.But because ZnO particle size is small, launched in water
After be difficult to reclaim, therefore in actual applications must be to its being fixed.Existing carrier exist load capacity it is small, recovery waste time and energy
The problems such as, and carrier is completely inert in itself, is helpless to improve removal of bacteria rate.
Chitosan is a kind of typical large biological molecule, contains multiple active hydroxyls and amino.These active groups
In the presence of determining that chitosan has good absorption and flocculating property.Studies have reported that preparing chitosan magnetic micro-sphere,
The advantages that greatly, easily being reclaimed because of its specific surface area, be renewable, given up as adsorbent in processing huge sum of money waste water, dyeing waste water, papermaking
It is widely used in water, phenol wastewater and food wastewater.Chitosan also has certain anti-microbial property, in its weakly acidic condition easily
In dissolving, amino (NH is produced2+), suppress bacterium by combining electronics.However, the data-searching carried out according to applicant, mesh
Before rarely have report using chitosan magnetic micro-sphere as water process antiseptic.
The content of the invention
For ZnO carrier load capacity is small, recovery is difficult, carrier poor activity itself technical problem, mesh of the invention
Be, there is provided a kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent and preparation method thereof, the obtained chitosan magnetic
Microballoon/zinc oxide composite antibiosis agent has magnetic, and possibility is provided for Future Development antiseptic automatic recovery device.
In order to realize above-mentioned task, the present invention takes following technical solution：
The preparation method of a kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent, it is characterised in that precipitated using a step
Method prepares chitosan magnetic micro-sphere, and then the chitosan magnetic micro-sphere is placed in zinc solution, and adds certain density
NaOH solution, temperature and stirring condition are controlled, carry out chemical deposition reaction, after the completion of reaction, treat solution natural cooling, pure water is clear
Wash, 95 DEG C of drying, that is, obtain chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
Specifically follow these steps to prepare：
(1) chitosan colloidal sol is prepared：
The Chitosan powder of appropriate deacetylation >=90% is weighed, is dissolved in the HCl solution that volume fraction is 1%, is made
Concentration is 13.8mg/mL chitosan colloidal sol；
(2) ferrous solution is prepared：
Weigh appropriate FeCl3·6H2O and FeCl2·4H2O is soluble in water so that Fe in solution3+Concentration is 1mol/L, Fe2+
Concentration is 0.5mol/L；
(3) chitosan colloidal sol mixes with ferrous solution：
By chitosan colloidal sol and ferrous solution with mass ratio 2:1 is mixed, and magnetic agitation makes its mixing；
(4) the one step precipitation method prepare chitosan magnetic micro-sphere：
Using the ammoniacal liquor that mass percentage concentration is 25% as precipitating reagent, the mixed liquor in step (3) is instilled into ammoniacal liquor, it is seen that have
Black microballoon generates；Alkali lye is abandoned after standing 7h, microballoon is cleaned to liquid shows neutral with pure water, then one time is cleaned with ethanol, then
Microballoon is moved into glass dish, 95 DEG C of drying 10h, that is, obtain the chitosan magnetic micro-sphere of black；
(5) zinc solution is prepared：
Weigh appropriate Zn (Ac)2·2H2O, water is dissolved in, Zn is made2+Concentration is 0.3mol/L zinc solution；
(6) chemical deposition prepares chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent：
Zinc solution made from step (5) is placed in beaker, 75 DEG C of water-baths and mechanical agitation, it is obtained to add step (4)
Chitosan magnetic micro-sphere, NaOH solution is then added, it is 0.2mol/L to make NaOH concentration, persistently stirs 90min.Take out beaker,
Cleaned after solution natural cooling with pure water, 95 DEG C of drying 1h, produce chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
Chitosan magnetic micro-sphere prepared by the present invention/zinc oxide composite antibiosis agent, it is using chemical deposition that ZnO particle is equal
Chitosan magnetic micro-sphere surface is deposited on evenly, and chitosan magnetic micro-sphere diameter about 1mm, there are a large amount of folds, specific surface area in surface
Greatly, zinc oxide load capacity can be significantly improved and there is magnetic, be easy to reclaim.
In addition, according to our experiments show that, the chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent can effectively go out
Bacterium in running water.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent of the present invention.
Fig. 2 is chitosan magnetic micro-sphere (CF) and the X ray of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent (CFZ)
Diffracting spectrum.Wherein, a is CF collection of illustrative plates, and b is CFZ collection of illustrative plates.
Fig. 3 is the SEM photograph of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.Wherein, a figures are 50 times of amplification；B schemes
For 1000 times of amplification；C figures are 20000 times of amplification.
Fig. 4 is the anti-microbial property of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent, zinc oxide and chitosan magnetic micro-sphere
Comparison diagram.
Fig. 5 is to change over time situation using total number of bacteria in water after chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment
The technical thought of applicant is, by ZnO superior anti-microbial property and chitosan magnetic micro-sphere high adsorption, load capacity
Characteristic that is high, being easy to recovery combines, so as to obtain the antibacterial agent with excellent properties.Prepared by a step precipitation method
Go out chitosan magnetic micro-sphere, the chitosan magnetic micro-sphere is placed in zinc solution, and add certain density NaOH solution, control
Temperature and stirring condition, chemical deposition reaction being carried out, after the completion of reaction, treat solution natural cooling, pure water cleaning, 95 DEG C dry,
Obtain millimetre-sized chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
Specific implementation process is as follows：
1st, equipment and reagent
(1) SEM
(2) X-ray diffractometer
(3) flame atomic absorption spectrophotometer
(4) electric heating constant-temperature blowing drying box
(5) vertical high-pressure sterilizing pot
(6) table-type high-speed refrigerated centrifuge
(7) water-bath constant temperature oscillator
(8) mechanical agitator
(9) constant incubator
(10) water purification machine
(11) magnetic stirring apparatus
(12) hydrochloric acid
(13) chitosan (deacetylation >=90%)
(14) ferric chloride hexahydrate
(15) Iron dichloride tetrahydrate
(16) sodium hydroxide
(17) concentrated ammonia liquor
(18) absolute ethyl alcohol
(19) Zinc diacetate dihydrate
(20) LB meat soups
(21) nutrient agar
(22) potassium dihydrogen phosphate
(23) disodium hydrogen phosphate
(24) Escherichia coli (ATCC 25922)
2nd, preparation of reagents
The preparation of LB meat soups：
The LB broth bouillon dry powder for weighing 1g is dissolved in 40mL water, is sterilized at 121 DEG C of high steam, 20min；
The preparation of ordinary nutrient agar culture medium：
3.3g nutrient agar dry powder is weighed, is dissolved in 100mL water, boils, 121 DEG C of high pressure steam sterilization,
20min；
The preparation of phosphate buffer (PBS, 0.03mol/L, pH are 7.2~7.4)：
Weigh 2.83g disodium hydrogen phosphate (Na2HPO4, it is anhydrous), 1.36g potassium dihydrogen phosphate (KH2PO4) be dissolved in
In 1000mL distilled water, (121 DEG C) sterilizings of high steam, 20min.
3rd, preparation method
According to the preparation technology flow shown in Fig. 1, further provide and prepare chitosan magnetic micro-sphere/zinc oxide composite antibiosis
The specific steps of agent：
(1) chitosan colloidal sol is prepared：
The Chitosan powder of 5.52g deacetylation >=90% is weighed, is dissolved in the HCl solution that 400mL volume fractions are 1%
In, the chitosan colloidal sol (hereinafter referred to as C colloidal sols) that concentration is 13.8mg/mL is made；
(2) mixing ferrous solution is prepared:
32.436g FeCl are weighed respectively3·6H2O and 11.928g FeCl2·4H2O is dissolved in 120mL water so that c (Fe3 +)=1mol/L, c (Fe2+)=0.5mol/L (hereinafter referred to as F solution)；
(3) chitosan colloidal sol mixes with ferrous solution：
By chitosan colloidal sol and mixing ferrous solution with mass ratio 2:1 is mixed, and magnetic agitation mixes；
(4) the one step precipitation method prepare chitosan magnetic micro-sphere：
Using 25% concentrated ammonia liquor as precipitating reagent, the 480mL mixed liquors in step (3) are respectively dropped into two glasss with 1mL needle tubings
(in order to ensure that solution remains stronger alkaline state during this so that ferrous solution is met alkali and generated completely in 300mL ammoniacal liquor
Fe3O4, it is separately added into 40mL 4mol/L NaOH solution), 7h is stood, alkali lye is then outwelled, is cleaned with pure water to neutrality, then use
Ethanol cleans one time, is subsequently poured into glass dish, 95 DEG C of drying 10h, obtains the chitosan magnetic micro-sphere of black (hereinafter referred to as
CF)；
(5) zinc solution is prepared：
Weigh 19.76g Zn (Ac)2·2H2O crystal, is dissolved in water so that c (Zn in solution2+)=0.3mol/L；
(6) chemical deposition prepares chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent：
Zinc solution made from step (5) is placed in beaker, 75 DEG C of heating water baths and mechanical agitation, adds step (4) system
The CF obtained, then adds NaOH solution so that c (NaOH)=0.2mol/L in mixed liquor, persistently stir 90min.Take out beaker,
Solution natural cooling is treated, is cleaned repeatedly with pure water, 95 DEG C of drying 1h, produces chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent
(hereinafter referred to as CFZ).
4th, material characterization
Using Cu target K α lines as radiation source, accelerating potential and applied current are respectively 40kV and 40mA, and scanning range is 5 °-
80 °, X-ray diffraction is carried out to CF and CFZ using the D8Advance types x-ray powder diffraction instrument of German Bruker companies respectively
Collection of illustrative plates measure analysis.Fig. 2 be CF and CFZ XRD spectrum, analysis collection of illustrative plates understand CF in main diffraction peak correspond to chitosan with
Fe3O4Characteristic peak, wherein 2 θ=12.8 ° and 20.6 ° of relatively broad peak correspond to the characteristic peak of chitosan, Fe3O4The θ of characteristic peak 2
=30.1 °, 35.5 °, 43.1 °, 53.4 °, 57.0 °, 62.6 ° correspond to crystal face (220) respectively, (311), (400), (422),
(511), (440)；And the diffraction pattern for contrasting CFZ and CF can be seen that characteristic peak corresponding to chitosan in CFZ and not become substantially
Change, and Fe3O4The intensity of characteristic peak is decreased obviously, and in 2 θ=31.9 °, 34.6 °, 36.4 °, 47.3 ° new peak occur, point
ZnO (100), (002), (101), (102) crystal face are not corresponded to.As can be seen here, CFZ main component is chitosan, Fe3O4With
ZnO。
Surface shape using the JSM-6700F cold field emissions SEM that Japanese JOEL companies produce to CF, CFZ
Looks are observed, and accelerating potential is 5kV during analysis.Fig. 3 is CFZ SEM photograph, it can be seen that CFZ bulb diameter is about 1mm,
There are many folds on surface, and this provides very big specific surface area for the load of zinc oxide, and amplifies 20000 times of photograph from CFZ
It can be clearly seen that there are a large amount of small ZnO particles on its surface in piece, the size of these ZnO particles is nanoscale.
The Zn content in CFZ is measured using the WFX-210 flame atomic absorption spectrophotometers of Beijing Rayleigh company.Claim
0.1g CFZ is taken, 100 times are diluted after resolution, the absorbance for measuring Zn-ef ficiency is 0.1595 (deducting blank sample absorbance), root
The Zn-ef ficiency concentration checked according to standard curve after diluting in digestion solution is 0.3538mg/L, then the ZnO content in CFZ is：
5th, anti-microbial property test
With Escherichia coli (ATCC25922) for tested strain, with reference to " nano inorganic material anti-microbial property detection method (GB/
T 21510-2008) " carry out anti-microbial property test.
5mL Escherichia coli (ATCC25922) bacteria suspension is added into 95mL PBS to mix, is separately added into 0.3g ZnO powder
End, 3g CF and 3g CFZ (ZnO containing 0.13g) are used as test sample, and blank sample is not added with any antiseptic.Test sample and blank sample
Bacterium solution initial concentration is each about 105CFU/mL.By test sample and blank sample at 37 DEG C, water-bath vibration under conditions of 80r/min, one
Bacteria Culture counting is carried out after fixing time, and calculates inactivation ratio (R) and logarithm inactivation respectively according to following formula (1) and (2)
Rate (R ').
In formula, N0The viable count at-blank sample moment, CFU/mL；
NiThe viable count at-test sample moment, CFU/mL.
As shown in figure 4, CFZ shows very high bacteria inactivation effect, oscillating contact 2h inactivation ratios are 99.18% (right
Number inactivation ratio 2.09-log), 4h inactivation ratios are 99.96% (logarithm inactivation ratio 3.42-log), and 12h inactivation ratios are up to 99.998%
(logarithm inactivation ratio 4.67-log)；And ZnO powder and CF reach maximum inactivation ratio in oscillating contact 4h, it is only respectively
95.41% (logarithm inactivation ratio 1.34-log) and 53.56% (logarithm inactivation ratio 0.33-log).As can be seen here, CFZ antibacterial effect
Fruit is much better than ZnO and CF, and its high bacteria inactivation rate is probably that the huge specific surface area of chitosan magnetic micro-sphere discharges with ZnO
Fungicidal active substance synergy result.
Take surface water to add 1g CFZ as test specimen, at 37 DEG C, under the conditions of 80r/min water-bath vibrate, certain time
Sampling carries out Bacteria Culture counting afterwards, continues to 272h.From fig. 5, it can be seen that in surface water initial bacterial count be 2 ×
105CFU/100mL；8h is tested, total number of bacteria is down to 3.64 × 102CFU/100mL；24h is down to 2.27 × 102CFU/
100mL；272h, total number of bacteria are only 50CFU/100mL.This illustrates that CFZ antibacterial action has long-term effect.
In summary, the chitosan magnetic micro-sphere that the present embodiment provides/zinc oxide composite antibiosis agent (CFZ) is being prepared and pushed away
There is following significant advantage during wide：
(1) chitosan magnetic micro-sphere is prepared by a step precipitation method, it is then micro- in chitosan magnetic using chemical deposition
ZnO nano particle is generated on ball, chitosan magnetic micro-sphere is combined closely with ZnO particle, forms complex antimicrobials CFZ；
(2) CFZ obtained has efficient anti-microbial property, and the logarithm inactivation ratio for testing 12h is up to 4.67-log；
(3) CFZ has long-term antimicrobial efficiency, after being added in surface water water sample in 10d total number of bacteria all maintain it is very low
It is horizontal；
(4) CFZ has magnetic matrix, can combine magnetic material recovery technology in actual applications, solves little particle and resists
Microbial inoculum is difficult to the technical barrier reclaimed.
Claims (5)
1. the preparation method of a kind of chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent, it is characterised in that this method uses a step
The precipitation method prepare chitosan magnetic micro-sphere, and the chitosan magnetic micro-sphere is placed in zinc solution, and add certain density
NaOH solution, temperature and stirring condition are controlled, carry out chemical deposition reaction, after the completion of reaction, treat solution natural cooling, pure water is clear
Wash, 95 DEG C of drying, that is, obtain chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
2. the method as described in claim 1, it is characterised in that specifically follow these steps to prepare：
(1) chitosan colloidal sol is prepared：
The Chitosan powder of appropriate deacetylation >=90% is weighed, is dissolved in the HCl solution that volume fraction is 1%, concentration is made
For 13.8mg/mL chitosan colloidal sol；
(2) ferrous solution is prepared：
Weigh appropriate FeCl3·6H2O and FeCl2·4H2O is soluble in water so that Fe in solution3+Concentration is 1mol/L, Fe2+Concentration
For 0.5mol/L；
(3) chitosan colloidal sol mixes with ferrous solution：
By chitosan colloidal sol and ferrous solution with mass ratio 2:1 is mixed, and magnetic agitation makes it mix completely；
(4) the one step precipitation method prepare chitosan magnetic micro-sphere：
Using 25% concentrated ammonia liquor as precipitating reagent, the mixed liquor in step (3) is instilled in ammoniacal liquor with 1mL needle tubings, it is seen that have black
Microballoon generates.Alkali lye is abandoned after standing 7h, microballoon is cleaned to liquid shows neutral with pure water, then is cleaned one time with ethanol, then will be micro-
Ball is moved into glass dish, 95 DEG C of drying 10h, that is, obtains the chitosan magnetic micro-sphere of black；
(5) zinc solution is prepared：
Weigh appropriate Zn (Ac)2·2H2O, water is dissolved in, Zn is made2+Concentration is 0.3mol/L solution；
(6) chemical deposition prepares chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent：
Zinc solution made from step (5) is placed in beaker, 75 DEG C of water-baths and mechanical agitation, adds magnetic made from step (4)
Chitosan microball, NaOH solution is then added, make the final concentration of 0.2mol/L of NaOH, persistently stir 90min.Beaker is taken out, is treated
Cleaned after solution natural cooling with pure water, 95 DEG C of drying 1h, produce chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent.
3. chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent prepared by the methods described of claim 1 or 2.
4. chitosan magnetic micro-sphere as claimed in claim 3/zinc oxide composite antibiosis agent, it is characterised in that the magnetic crust
Glycan microballoon/zinc oxide composite antibiosis agent is grade magnetic microsphere, and there are a large amount of folds on surface, and specific surface area is big, and zinc oxide is born
Carrying capacity is high, and has magnetic, is easy to reclaim.
5. chitosan magnetic micro-sphere/zinc oxide composite antibiosis agent described in claim 3 is used for the application for inactivating bacterium in water.
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| CN111610227A (en) * | 2019-02-25 | 2020-09-01 | 天津理工大学 | 2D ZnO @3D CF nano composite material and preparation method and application thereof |
| CN111729664A (en) * | 2020-06-05 | 2020-10-02 | 吉林大学 | Supported nano zinc oxide and preparation and application thereof |
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| CN111610227A (en) * | 2019-02-25 | 2020-09-01 | 天津理工大学 | 2D ZnO @3D CF nano composite material and preparation method and application thereof |
| CN111610227B (en) * | 2019-02-25 | 2023-01-31 | 天津理工大学 | 2D ZnO @3D CF nano composite material and preparation method and application thereof |
| CN111729664A (en) * | 2020-06-05 | 2020-10-02 | 吉林大学 | Supported nano zinc oxide and preparation and application thereof |
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