CN103535377B - The preparation method of the inorganic nano combined molluscacide of a kind of HAP/ZnO - Google Patents
The preparation method of the inorganic nano combined molluscacide of a kind of HAP/ZnO Download PDFInfo
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Abstract
The invention discloses the preparation method of the inorganic nano combined molluscacide of a kind of HAP/ZnO, the present invention uses nano-HAP, nano-ZnO, starch (or sucrose), gum arabic powder and coupling agent as raw material, obtained according to the mixing of certain ratio.The molluscacide that the present invention obtains has the features such as fine targeting killing effect, efficient low-consume, environmental protection, and manufacture craft is simple, cost is low, be convenient to storage, transport, to people and animals' nonhazardous, to raising fish and shrimp environmental nonpollution, its application value is high, social benefit, economic benefit and and ecological benefits remarkable.
Description
technical field:
The present invention relates to the preparation method of the inorganic nano combined molluscacide of a kind of HAP/ZnO.This molluscacide is mainly used in blood fluke epidemic-stricken area, propagating, being widely used for killing oncomelania, belonging to materials chemistry and field of public health for blocking blood fluke.
background technology:
Schistosomiasis is one of five large parasitosis of harm our people health, not only badly influence the healthy of people, also greatly constrain place to invite outside investment and expanding economy, concerning people's livelihood safety and stability, now become very important Social Events.Oncomelania is bilharzial unique intermediate host, therefore is only limitted to the area of oncomelania, just may have schistosomiasis endemic.In China, schistosomiasis is also popular in 12 provinces (city) such as Jiangsu, Zhejiang, Shanghai, Anhui, Jiangxi, Hunan, Hubei, Sichuan, Yunnan, Guangxi, Guangdong, Fujian on the south two sides, the Changjiang river and the Changjiang river so far, especially comparatively serious with In Middle And Lower Reaches of Changjiang River, wherein Chizhou Prefecture of Anhui Province is exactly storied severely afflicated area.What for many years China followed in prevention and cure of schistosomiasis is its intermediate host-oncomelania of elimination is main general prevention and treatment strategy and the strategies for disease prevention and control based on Population And Cattle Chemotherapy.Killing oncomelania fundamentally can block the propagation of schistosomiasis, and the chemicals spiral shell that goes out is acknowledged as and controls oncomelania the most effective major measure.Niclosamidum is unique a kind of chemical snail killing agent with good sn ail control effect that the World Health Organization (WHO) is recommended, and Ye Shi China present stage uniquely allows and the chemical molluscacide used.But the 50% Niclosamide ethanolamine salt wettable powder agent generally used at present, because its drug cost price is high in practical application, and also exist poorly soluble, suspensibility is low, very easily block the defect such as drug-spraying instrument, overt toxicity is had to aquatic animal, chemicals can not use in the culture zone such as fish, crab, is thus difficult to the welcome being subject to common people.But be at present conduct a research around the formulation of niclosamidum and compatibility or organic chemistry molluscacide of the same type mostly, do not obtain substantial progress.Although though concerns about bio molluscacide has caused the positive regard of Chinese scholars, but find in reality use biological reagent goes out spiral shell process, sn ail control effect is still undesirable, mainly because the reasons such as diffusion cause active ingredient concentration unstable, a lot of sprinkling region does not reach effectively kills concentration, and the extraction of microbe snail-killing effective ingredient, cost is too high, is difficult to by large scale application.Therefore, about the research and development of novel high-efficiency environment friendly molluscacide, remain pendulum and have challenging problem in face of vast researcher.
ZnO is a kind of traditional inorganic antibacterial material, because it is when contacting with bacterium, zinc ion slow releasing, can with organic carboxyl and hydroxyl reaction, destroy its structure, reach sterilization object.Nano-ZnO crystal grain granular, its Electronic Structure and crystal structure change, and create skin effect, bulk effect, quantum size effect and macroscopical tunnel-effect and the feature such as the high grade of transparency, polymolecularity that macro object do not have.In recent years, about the preparation and application of nano-ZnO, extremely Chinese scholars paid close attention to.People study and find that nano ZnO material is in many-sides such as catalysis, optics, magnetics, mechanics and sterilizations, show the special excellent function that many common ZnO are incomparable, make it have important using value in many fields such as pottery, chemical industry, electronics, optics, biology, medicine.Wherein, nano-ZnO, as a kind of desirable bactericide, has very strong bactericidal property and is recognized already, if itself and its related functionality nano material is carried out effective compound, build the drug delivery system with Special Targets tropism, just can produce nanometer cooperative synergy.The current research of this seminar finds, nano zine oxide has the toxic action of highly significant to oncomelania, can effective Killing Oncomelania Hupensis, simultaneously also free from environmental pollution.The research report that nano-ZnO has water-snail eradication performance is there is not yet, not seen in there being this type of patent outside Now Domestic.
Hydroxyapatite (hydroxyapatite, Ca
10(PO
4)
6(OH)
2) be called for short HA or HAP, being extensively present in human body and animal skeleton, tooth, is desirable hard tissue substituting material.In biomimetic material field, HAP, except transplanting for making in filling material of bone, skin, can also prepare HAP Biocomposite material with other Material cladding; At field of medicaments, HAP can be used for drug loading, forms drug sustained release system; At sterilization, catalytic field, utilize the biocompatibility that it is good, can composite antibacterial material and catalyzer etc. be prepared; In fields such as bioactivator Separation & Purification, daily use chemicals, its application is also quite extensive.If when the particle size of HAP is reduced to nanoscale, the nano material obtained has the physicochemical property more excellent than common material: as large in surface area, solvability is high, has better biologically active, biocompatibility and stability etc.Nano composite material is one of the focus in investigation of materials field in recent years, often owing to there is nanometer cooperative effect in this kind of material, performance is made more to be better than common nano material, as larger specific surface area, higher activity and more excellent effect, thus be used in the fields such as medicine carries, fills, catalysis, storage, environmental improvement more widely.
The inorganic nano combined molluscacide of a kind of HAP/ZnO that the present invention relates to, mainly utilize biocompatibility, absorption property and the easy performance suspended in water that nano-HAP nano material tool is good, can be combined with each other with nano zine oxide well, the nano-ZnO being compounded in nano-HAP nano-material surface then can kill the oncomelania touched.By the synergy of nano-HAP nano material and nano-ZnO, not only can realize molluscacide and to go out the significantly lifting of spiral shell usefulness, and the object reducing ZnO consumption can be reached.In addition, the HAP adopted due to the present invention has special chondritic, and the active ingredient nano zine oxide of molluscacide can be suspended in the formulation preferably, and have good mobility, this effect also uses merely nano-ZnO to realize.The inorganic nano combined molluscacide of the HAP/ZnO that the present invention relates to; compare the niclosamidum chemistry molluscacide that the World Health Organization (WHO) is recommended; not only cost is low, raw material sources are wide; be suitable for local large-scale production; the more important thing is while guaranteeing sn ail control effect; to aquatic biological avirulence, environmentally safes such as fishes and shrimps, it is a kind of inorganic molluscacide of efficient, green safety.Applying of this invention, will provide a kind of effective spiral shell new drug that goes out for blood fluke control, simultaneously to the demand of HAP raw material, also for local this type of abundant nonmetal mineral resource deep processing application brings new growth engines.Believe enforcement of the present invention, will produce good Social benefit and economic benefit, have very strong promotional value, application prospect is very good.
Summary of the invention
The object of this invention is to provide the preparation method of the inorganic nano combined molluscacide of a kind of HAP/ZnO.The present invention adopts nano-ZnO and spherical nano-HAP to be raw material, the biocompatibility utilizing HAP nano material good and absorption property, add coupling agent, after contributing to both compounds securely, add appropriate oncomelania food starch again or sucrose is attractant, be mixed into graininess by a certain percentage, then can obtain the inorganic nano combined molluscacide of HAP/ZnO.This molluscacide has Heat stability is good, go out that spiral shell ability is strong, production cost is low, physics and chemistry active strong, to advantages such as human body fanout free region and environmentally safes, meet Green Chemistry requirement.
The present invention is achieved through the following technical solutions:
A preparation method for the inorganic nano combined molluscacide of HAP/ZnO, comprises the following steps:
(1) measure according to the ratio of 65-85wt% shared by HAP nano material in compound molluscacide, take the HAP nano material of certain mass, be added in beaker, fully stir after adding water;
(2) coupling agent of the 0.01-0.1wt% accounting for ZnO and HAP nano material gross mass is added, sonic oscillation or be stirred to evenly;
(3) in the ratio of 15-35wt% shared by ZnO nano material, take ZnO powder, be mixed in above-mentioned system, sonic oscillation or the system that is stirred to are uniformly dispersed;
(4) sucrose or the starch of the 4.0-6.0wt% accounting for ZnO and HAP nano material gross mass is added, add the gum arabic powder of the 3.0-5.0wt% accounting for ZnO and HAP nano material gross mass again, dry after sonic oscillation or the system that is stirred to are uniformly dispersed, graininess molluscacide can be obtained.
Described coupling agent is non-ionic surface active agent or anion surfactant; Non-ionic surface active agent preferred fat alcohols, polyethylene glycols, polyvinyl alcohol, alkylolamides class, alkyl amine, alkylbenzene phenols or its mixture; Anion surfactant optimization acid salt, phosphate, sulphate, sulfonate or its mixture.
Described ZnO nano material is spherical, sheet, bar-shaped, wire, unformed shape particle or its mixture, and particle diameter is 1-40nm.
Described HAP nano material is the nanometer assembling ball of particle diameter between 1-100nm.
The using method of the inorganic nano combined molluscacide of HAP/ZnO of the present invention, comprises the steps:
In 500mL beaker, load onto the natural clear water of 200mL, put into 20, the oncomelania of the unsoundness vigor taked from locality at random; Add molluscacide particle 3-5 gram, cover with gauze, soaked by 24,72,144 hours respectively, after soak time, repeatedly rinse with clear water immediately, after removing the liquid sticked, be transferred in the culture dish under about 20 DEG C room temperatures and add a small amount of dechlorination Shui Hui and raise 24 hours again, adopt needle point method and hammering method to judge that whether oncomelania is dead.
beneficial effect of the present invention
The present invention compared with prior art, has following outstanding feature and remarkable advantage:
1, the present invention uses advanced nanometer technology, the spiral shell effective ingredient ZnO and HAP that goes out is utilized to stablize the nanometer cooperative synergy of compound generation, improve spiral shell usefulness of going out, the pesticide resistance of target biology is prevented to increase, particularly avoid the organic chemistry molluscacide niclosamidum of existing use while the spiral shell that goes out, the aquatic biologicals such as fishes and shrimps are produced to toxicity, water environment brought to the deficiency of pollution, meets the national conditions needs of Green Chemistry and sustainable development;
2, the spiral shell effective ingredient ZnO and HAP that goes out that the present invention utilizes is all inorganic matters that are nontoxic, tasteless, that can use hand and direct skin contact, after making pill, is convenient to storage, transport, is convenient to the safe handling of field common people;
3, the present invention optionally with the addition of coupling agent in molluscacide, ensure that the high stability of ZnO and HAP composite; In molluscacide, add sugarcane sugar and starch, oncomelania can be induced to eat, make molluscacide of the present invention have more targeting killing effect, improve the service efficiency of molluscacide, effectively reduce use cost;
4, the present invention with the addition of the HAP of tool bigger serface in molluscacide, because it has excellent absorption property and environment friendly, the property of medicine of molluscacide can be made effectively to be controlled slowly-releasing and put.The source of this raw material has abundant natural Advantage of Mineral Resources in this area, output is high, product are of fine quality, and the present invention, to the demand of HAP raw material, is also that the development of local nonmetallic ore deep processing applicable industry brings new growth engines;
5, manufacture craft of the present invention is simple, abundant raw material source, and processing cost is low, and drug effect is high, and than simple use chemistry molluscacide or plant molluscacide, spiral shell performance of going out more significantly and low price.
Embodiment
Below by specific embodiment, the present invention is further illustrated:
Embodiment 1
Take HAP nano material 65g to be dispersed in 200 ml waters, add anionic surfactant sodium dodecylbenzene sulfonate 0.02g wherein, after sonic oscillation 10min, add 35gZnO nano material wherein, then sonic oscillation 10min, namely obtain liquefied mixture; Take the gum arabic powder of 4.00g starch, 3.00g more respectively, dry after sonic oscillation or the system that is stirred to are uniformly dispersed, graininess molluscacide can be obtained.
Take 3 grams of molluscacides and put into oncomelania sample, oncomelania killing rate is 24h:80%; 72h:90%; 144h:100%.
Embodiment 2
Taking HAP nano material 70g is dispersed in 200 ml waters, adds non-ionic surface active agent polyethylene glycol 0.05g wherein, after fully stirring 10min, adds 30gZnO nano material wherein, then sonic oscillation 10min, namely obtains liquefied mixture; Take the gum arabic powder of 5.00g sucrose, 4.00g more respectively, dry after sonic oscillation or the system that is stirred to are uniformly dispersed, graininess molluscacide can be obtained.
Take 3.5 grams of molluscacides and put into oncomelania sample, oncomelania killing rate is 24h:40.3%; 72h:80%; 144h:100%.
Embodiment 3
Taking HAP nano material 80g is dispersed in 200 ml waters, adds non-ionic surface active agent soil temperature-600.08g wherein, after fully stirring, adds 20gZnO nano material wherein, then sonic oscillation 10min, namely obtains liquefied mixture; Take the gum arabic powder of 6.00g starch, 5.00g more respectively, dry after sonic oscillation or the system that is stirred to are uniformly dispersed, graininess molluscacide can be obtained.
Take 5 grams of molluscacides and put into oncomelania sample, oncomelania killing rate is 24h:60%; 72h:90%; 144h:100%.
Claims (3)
1. a preparation method for the inorganic nano combined molluscacide of HAP/ZnO, is characterized in that comprising the following steps:
(1) measure according to the ratio of 65-85wt% shared by HAP nano material in compound molluscacide, take the HAP nano material of certain mass, be added in beaker, fully stir after adding water;
(2) coupling agent of the 0.01-0.1wt% accounting for ZnO and HAP nano material gross mass is added, sonic oscillation or be stirred to evenly;
(3) in the ratio of 15-35wt% shared by ZnO nano material, take ZnO powder, be mixed in above-mentioned system, sonic oscillation or the system that is stirred to are uniformly dispersed;
(4) sucrose or the starch of the 4.0-6.0wt% accounting for ZnO and HAP nano material gross mass is added, add the gum arabic powder of the 3.0-5.0wt% accounting for ZnO and HAP nano material gross mass again, dry after sonic oscillation or the system that is stirred to are uniformly dispersed, graininess molluscacide can be obtained;
Described ZnO nano material is spherical, sheet, bar-shaped, wire, unformed shape particle or its mixture, and particle diameter is 1-40nm; Described HAP nano material is the nanometer assembling ball of particle diameter between 1-100nm.
2. the preparation method of the inorganic nano combined molluscacide of HAP/ZnO according to claim 1, is characterized in that, described coupling agent is non-ionic surface active agent or anion surfactant; Non-ionic surface active agent is aliphatic alcohols, polyethylene glycols, polyvinyl alcohol, alkylolamides class, alkyl amine, alkylbenzene phenols or its mixture; Anion surfactant is carboxylate, phosphate, sulphate, sulfonate or its mixture.
3. the using method of the inorganic nano combined molluscacide of the HAP/ZnO utilizing method described in claim 1 to prepare
It is characterized in that, the using method of described compound molluscacide comprises the steps: in 500mL beaker, load the natural clear water of 200mL, put into 20, the oncomelania of the unsoundness vigor taked from locality at random, add molluscacide particle 3-5 gram, cover with gauze, soaked by 24,72,144 hours respectively, after soak time, repeatedly rinse with clear water immediately, after removing the liquid sticked, be transferred in the culture dish under 20 DEG C of room temperatures and add a small amount of dechlorination water and raise 24 hours, adopt needle point method and hammering method to judge that whether oncomelania is dead.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077589A (en) * | 1992-04-15 | 1993-10-27 | 南京市寄生虫病防治所 | A kind of composition of killing oncomelania |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN102499256A (en) * | 2011-10-18 | 2012-06-20 | 池州学院 | Nano-silver composite biological molluscicide and preparation method thereof |
-
2013
- 2013-09-17 CN CN201310423738.4A patent/CN103535377B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077589A (en) * | 1992-04-15 | 1993-10-27 | 南京市寄生虫病防治所 | A kind of composition of killing oncomelania |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN102499256A (en) * | 2011-10-18 | 2012-06-20 | 池州学院 | Nano-silver composite biological molluscicide and preparation method thereof |
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